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Various multi-panel, quick opening or window envelope or carton packages are known. Examples of such include those described in:
(a) U.S. Pat. No. 2,828,065 which describe a quick-opening construction for window envelopes,
(b) U.S. Pat. No. 3,835,988 which describes a window carton, for display of bacon or the like, and
(c) U.S. Pat. No. 3,955,750 which describes a multi-panel envelope form made of single ply, multi panel forms, having at least one intermediate, removable panel made from a continuous web, for fast construction of advertising or circular-type matter envelopes.
However, to our knowledge, no prior art web format has solved the problem of how to provide a simplified format for use by (a) research office personnel for identification and labeling of randomized samples of test substances (including test drug and placebo formulations) (b) clinical investigator personnel teams who must administer the coded test substances to the human or animal patients, in blinded situations (so that neither the clinical investigator team personnel nor the patient knows what the test substance is), and then observe what they consider to be the medical effects of the test substance, but who, must if necessary, learn the identity of the active test substance, to treat the patient to counteract any severe adverse effects of any particular coded test substance, without jeopardizing the results of the tests in other members of the patient test group; and (c) statisticians who must be confident that the coded, blinded nature of the clinical trials, in doing their statistical analyses of the effects of the various test substances in the test group of patients, has not been compromised by the clinical team's need to know the identity of a particular numbered test sample in that group; and who desire to quickly determine which test sample numbers are to be discarded in their statistical evaluation of the observed effects of the remaining blinded, clinical test observations. | {
"pile_set_name": "USPTO Backgrounds"
} |
1. Field of the Invention
This invention relates to Entomological apparatuses, more particularly to an apparatus for permitting the observation and study of insects, especially insects of the hymenopterous order, i.e. wasps, bees, ants, etc. Insects of these species usually exhibit some degree of social organization and consequently live in communities or colonies making them susceptible for group observation and study of their behavior patterns.
The entomological apparatus of this invention is suitable for research and scientific experiments, as well as educational purposes for children and adults.
2. Prior Art
Entomological apparatuses are known in the art, see for example the following U.S. Pat. Nos.:
2,080,160 to Austin; PA1 3,088,134 to Abel; and PA1 3,653,357 to Sheidlower et al. PA1 (a) a first substantially transparent enclosure having inner and outer surfaces; PA1 (b) a second enclosure within the first enclosure, the second enclosure having inner and outer surfaces, wherein a portion of the outer surface of the second enclosure and a portion of the inner surface of the first enclosure form an environmental chamber for observing insects; and PA1 (c) an access means through the first enclosure for enabling placement of insects and environmental elements therein.
Generally, these known apparatuses are rectangular enclosures having a shallow chamber between two transparent surfaces with various surfaces for the insects contained therein to crawl upon for observation. In this chamber are placed environmental elements necessary for the insects growth and maintenance.
These known apparatuses suffer in that they are not decorative and they are complicated in structure and difficult to assemble and manufacture. | {
"pile_set_name": "USPTO Backgrounds"
} |
This application is a 371 of PCT/EP00/04300, published May 12, 2000.
The present invention relates to novel processes for preparing methoxyimino-acetamides.
A process for preparing N-methyl-[2-(2-hydroxy)phenyl]-2-methoxyimino-acetamide has already been described (cf. EP 0 398 692 A2). However, the compounds prepared by this process are only obtainable in moderate yields.
It has now been found that according to process part 1) compounds of the formula (I)
in which
R1, R2, R3 and R4 are identical or different and independently of one another each represents hydrogen, halogen, cyano, nitro, in each case optionally halogen-substituted alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl,
R5 represents substituted or unsubstituted alkyl,
R6 represents hydrogen, substituted or unsubstituted alkyl,
are obtained when
A) according to process step 2), compounds of the formula (IV),
xe2x80x83in which
R1, R2, R3 and R4 are as defined above,
are reacted, in the presence of an acid or an acidic ion exchanger, with an alcohol of the formula (V),
R7xe2x80x94OHxe2x80x83xe2x80x83(V)
xe2x80x83in which
R7 represents substituted or unsubstituted alkyl,
and with a carbonyl compound, which binds the hydroxylammonium chloride eliminated in the reaction forming an oxime, to give compounds of the formula (VI),
xe2x80x83in which
R1, R2, R3, R4 and R7 are as defined above,
and the resulting compounds of the formula (VI) are either
a) according to process step 3), reacted with a hydroxylammonium salt, if appropriate in the presence of a diluent and if appropriate in the presence of an acid or an acid acceptor, to give compounds of the formula (VII),
xe2x80x83in which
R1, R2, R3, R4 and R7 are as defined above,
and the resulting compounds of the formula (VII) are, according to process step 4), reacted with an alkylating agent of the formula (VIII),
R5xe2x80x94Xxe2x80x83xe2x80x83(VIII)
xe2x80x83in which
R5 is as defined above and
X represents halogen, xe2x80x94Oxe2x80x94COxe2x80x94OR5xe2x80x94 or xe2x80x94Oxe2x80x94SO2xe2x80x94Oxe2x80x94R5, where R5 is as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of a base,
or
b) are, according to process step 5), reacted with an alkoxyamine of the formula (IX),
R5xe2x80x94Oxe2x80x94NH2xe2x80x83xe2x80x83(IX)
xe2x80x83in which
R5 is as defined above,
xe2x80x94 or an acid addition complex thereofxe2x80x94, if appropriate in the presence of a diluent and if appropriate in the presence of an acid or an acid acceptor,
or when
B) according to process step 6), compounds of the formula (IV),
xe2x80x83in which
R1, R2, R3 and R4 are as defined above,
are reacted with an alkoxyamine of the formula (IX),
R5xe2x80x94Oxe2x80x94NH2xe2x80x83xe2x80x83(IX)
xe2x80x83in which
R5 is as defined above,
xe2x80x94 or an acid addition complex thereofxe2x80x94if appropriate in the presence of a diluent and if appropriate in the presence of an acid,
or when
C) according to process step 7), compounds of formula (IV),
xe2x80x83in which
R1, R2, R3 and R4 are as defined above,
are reacted, in the presence of an acid or an acidic ion exchanger, with an alcohol of the formula (V),
R7xe2x80x94OHxe2x80x83xe2x80x83(V)
in which R7 is as defined above,
if appropriate with addition of a hydroxylammonium salt, and the resulting compounds of the formula (VII),
xe2x80x83in which
R1, R2, R3, R4 and R7 are as defined above,
are reacted according to process step 4),
or when
D) according to process step 8), compounds of the formula (X),
xe2x80x83in which
R1, R2, R3, R4 and R5 are as defined above,
are reacted, in the presence of an acid or an acidic ion exchanger, with an alcohol of the formula (V),
R7xe2x80x94OHxe2x80x83xe2x80x83(V)
xe2x80x83in which R7 is as defined above, if appropriate in the presence of a carbonyl compound which binds the hydroxylammonium chloride eliminated in the reaction forming an oxime,
and the compounds of the formula (II) obtained according to proceses A)-D),
xe2x80x83in which
R1, R2, R3, R4 and R5 are as defined above and
R7 represents unsubstituted or substituted alkyl,
are, if appropriate without intermediate isolation of the compounds of the formula (II) (one-pot process),
reacted according to process step 1) with an alkylamine of the formula (III),
R6xe2x80x94NH2xe2x80x83xe2x80x83(III)
in which R6 is as defined above, if appropriate in the presence of a diluent.
Moreover, it has been found that, according to process part 2), compounds of the formula (XI),
in which
Z represents unsubstituted or substituted cycloalkyl, aryl or heterocyclyl,
Q represents oxygen or sulphur,
Y represents halogen and
R1, R2, R3, R4, R5 and R7 are as defined above,
are obtained when compounds of the formula (I) are reacted according to the novel process part 1), and these compounds (I) are either
E) according to process step 9) reacted with pyrimidine derivatives of the formula (XII),
xe2x80x83in which
T1 and T2 are identical or different and represent halogen or xe2x80x94SO2xe2x80x94R8, where R8 is alkyl, aryl or benzyl, and
Y is as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of a base, and the resulting compounds of the formula (XIII),
xe2x80x83in which
T2, Y, R1, R2, R3, R4, R5 and R7 are as defined above,
are reacted, according to process step 10), with a cyclic compound of the general formula (XIV),
Zxe2x80x94Qxe2x80x94Hxe2x80x83xe2x80x83(XIV)
xe2x80x83in which
Z and Q are as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid acceptor and if appropriate in the presence of a catalyst,
or
F) are reacted according to process step 11) with compounds of the formula (XV),
in which
Z, Q, T1 and Y are as defined above,
if appropriate in the presence of a diluent and if appropriate in the presence of a base.
Furthermore, it has been found that the Z-isomeric compounds of the formula (XI) are isomerized to E-isomeric compounds of the formula (XI) when Z isomers or E/Z isomer mixtures of the compounds of the formula (XI) are treated with acids, if appropriate in a diluent. The isomerization affords the E isomers in good yields.
Furthermore, it has been found that the Z-isomeric compounds of the formula (XIII) are isomerized to E-isomeric compounds of the formula (XIII) when Z isomers or E/Z isomer mixtures of the compounds of the formula (XIII) are treated with acids, if appropriate in a diluent. The isomerization affords the E isomers in good yields.
In the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkanediyl, alkenyl or alkinyl, are, including in combination with heteroatoms, such as, for example, in alkoxy, alkylthio or alkylamino, in each case straight-chain or branched having in particular 4 carbon atoms.
Aryl denotes aromatic, mono- or polycyclic hydrocarbons rings, such as, for example, phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, in particular phenyl.
Halogen generally denotes fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine. Heterocyclyl denotes saturated or unsaturated, and also aromatic, cyclic compounds in which at least one ring member is a heteroatom, i.e. an atom different from carbon. If the ring contains a plurality of heteroatoms, these can be identical or different. Preferred heteroatoms are oxygen, nitrogen or sulphur. If appropriate, the cyclic compounds form a polycyclic ring system together with further carbocyclic or heterocyclic fused-on or bridged rings. Preference is given to mono- or bicyclic ring systems, in particular to mono- or bicyclic aromatic ring systems.
Cycloalkyl denotes saturated carbocyclic compounds which may, if appropriate, form a polycyclic ring system with further carbocyclic, fused-on or bridged rings.
Halogenoalkyl denotes partially or fully halogenated alkyl. In the case of polyhalogenated halogenoalkyl, the halogen atoms can be identical or different. Preferred halogen atoms are fluorine and chlorine and in particular fluorine. If the halogenoalkyl also carries other substituents, the maximum number of halogen atoms possible is reduced to the remaining free valencies.
The compounds according to the invention can, if appropriate, be present as mixtures of different possible isomeric forms, in particular of stereoisomers, such as, for example E and Z. What is claimed are both the E and the Z isomers, and any mixtures of these isomers.
In general, Z represents in particular:
cycloalkyl having 3 to 7 carbon atoms which is in each case optionally mono- to disubstituted by halogen, alkyl or hydroxyl;
heterocyclyl having 3 to 7 ring members which is optionally substituted by alkyl having 1 to 4 carbon atoms;
or phenyl or naphthyl, each of which is optionally mono- to tetrasubstituted by identical or different substituents, where the possible substituents are preferably selected from the list below:
halogen, cyano, nitro, amino, hydroxyl, formyl, carboxyl, carbamoyl, thiocarbamoyl;
in each case straight-chain or branched alkyl, hydroxyalkyl, oxoalkyl, alkoxy, alkoxyalkyl, alkylthioalkyl, dialkoxyalkyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 8 carbon atoms;
in each case straight-chain or branched alkenyl or alkenyloxy having in each case 2 to 6 carbon atoms;
in each case straight-chain or branched halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl having in each case 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
in each case straight-chain or branched halogenoalkenyl or halogenoalkenyloxy having in each case 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms;
in each case straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, arylalkylaminocarbonyl, dialkylaminocarbonyloxy, alkenylcarbonyl or alkinylcarbonyl having 1 to 6 carbon atoms in the respective hydrocarbon chains;
cycloalkyl or cycloalkyloxy having in each case 3 to 6 carbon atoms;
in each case doubly attached alkylene having 3 or 4 carbon atoms, oxyalkylene having 2 or 3 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms, each of which is optionally mono- to tetrasubstituted by identical or different substituents from the group consisting of fluorine, chlorine, oxo, methyl, trifluoromethyl and ethyl;
or a grouping
xe2x80x83in which
A1 represents hydrogen, hydroxyl or alkyl having 1 to 4 carbon atoms or cycloalkyl having 1 to 6 carbon atoms and
A2 represents hydroxyl, amino, methylamino, phenyl, benzyl or represents in each case optionally cyano-, hydroxyl-, alkoxy-, alkylthio-, alkylamino-, dialkylamino- or phenyl-substituted alkyl or alkoxy having 1 to 4 carbon atoms, or represents alkenyloxy or alkinyloxy having in each case 2 to 4 carbon atoms,
and phenyl, phenoxy, phenylthio, benzoyl, benzoylethenyl, cinnamoyl, heterocyclyl or phenylalkyl, phenylalkyloxy, phenylalkylthio, or heterocyclylalkyl having in each case 1 to 3 carbon atoms in the respective alkyl moieties, each of which is optionally mono- to trisubstituted in the ring moiety by halogen and/or straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms.
Generally, R5 represents in particular methyl or ethyl.
Generally, R6 represents in particular hydrogen or methyl.
Generally, R7 represents in particular methyl.
Generally, Q represents in particular oxygen or sulphur.
Generally, Y represents in particular fluorine, chlorine, bromine or iodine.
Generally, T1 represents in particular fluorine or chlorine.
Generally, T2 represents in particular fluorine or chlorine.
In general, R1, R2, R3 and R4 are identical or different and independently of one another each represents in particular hydrogen, halogen, cyano, nitro, or alkyl, alkoxy, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms and being in each case optionally substituted by 1 to 5 halogen atoms.
Preference is given to inventions in which Z represents cyclopentyl or cyclohexyl, each of which is optionally mono- to disubstituted by fluorine, chlorine, methyl, ethyl or hydroxyl;
represents optionally methyl- or ethyl-substituted thienyl, pyridyl or furyl;
or represents phenyl or naphthyl, each of which is optionally mono- to tetrasubstituted by identical or different substituents, where the possible substituents are preferably selected from the list below:
fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxyl, formyl, carboxyl, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-, 2-, 3-, neo-pentyl, 1-, 2-, 3-, 4-(2-methylbutyl), 1-, 2-, 3-hexyl, 1-, 2-, 3-, 4-, 5-(2-methylpentyl), 1-, 2-, 3-(3-methylpentyl), 2-ethylbutyl, 1-, 3-, 4-(2,2-dimethylbutyl), 1-, 2-(2,3-dimethylbutyl), hydroxymethyl, hydroxyethyl, 3-oxobutyl, methoxymethyl, dimethoxymethyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, vinyl, allyl, 2-methylallyl, propene-1-yl, crotonyl, propargyl, vinyloxy, allyloxy, 2-methylallyloxy, propene-1-yloxy, crotonyloxy, propargyloxy;
trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulphinyl or trifluoromethylsulphonyl, methylamino, ethylamino, n- or i-propylamino, dimethylamino, diethylamino, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, ethylaminocarbonyl, dimethylaminocarbonyl, diethylaminocarbonyl, dimethylaminocarbonyloxy, diethylaminocarbonyloxy, benzylaminocarbonyl, acryloyl, propioloyl, cyclopentyl, cyclohexyl,
in each case doubly attached propanediyl, ethyleneoxy, methylenedioxy, ethylenedioxy, each of which is optionally mono- to tetrasubstituted by identical or different substituents from the group consisting of fluorine, chlorine, oxo, methyl and trifluoromethyl,
or a grouping
xe2x80x83where
A1 represents hydrogen, methyl or hydroxyl and
A2 represents hydroxyl, methoxy, ethoxy, amino, methylamino, phenyl, benzyl or hydroxyethyl, and
phenyl, phenoxy, phenylthio, benzoyl, benzoylethenyl, cinnamoyl, benzyl, phenylethyl, phenylpropyl, benzyloxy, benzylthio, 5,6-dihydro-1,4,2-dioxazin-3-ylmethyl, triazolylmethyl, benzoxazol-2-ylmethyl, 1,3-dioxan-2-yl, benzimidazol-2-yl, dioxol-2-yl, oxadiazolyl, each of which is optionally mono- to trisubstituted in the ring moiety by halogen and/or straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms.
Preference is given to compounds in which R5 represents methyl.
Preference is given to compounds in which R6 represents hydrogen or in particular methyl.
Preference is given to compounds in which R7 represents methyl.
Preference is given to compounds in which Q represents sulphur or in particular oxygen.
Preference is given to compounds in which Y represents fluorine or chlorine.
Preference is given to compounds in which R1, R2, R3 and R4 are identical or different and independently of one another each represents hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or ethylsulphonyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulphinyl or trifluoromethylsulphonyl.
In a very particularly preferred group of compounds, Z represents optionally substituted phenyl.
In a further very particularly preferred group of compounds
R1 and R3 independently of one another represent methyl and in particular hydrogen and
R2 and R4 represent hydrogen.
Particular preference is given to compounds in which Y represents fluorine.
Particular preference is given to compounds in which Q represents oxygen.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and/or the formula (XI) and also correspondingly to the starting materials or intermediates required in each case for the preparation.
The radical definitions given in the respective combinations or preferred combinations of radicals for these individual radicals are, independently of the combination of radicals given in each case, also replaced by any radical definitions of other preferred ranges.
These radical definitions can be combined with each other at will, i.e. including combinations between the given ranges of preferred compounds.
The compound of the formula (XI-1, E-isomer) is novel and inventive and forms also part of the subject-matter of the invention. It can be used by way of example as pesticide.
The compound of the formula (XI-1, Z-isomer) is novel and inventive and forms also part of the subject-matter of the invention. It can be used by way of example as pesticide.
The isomerization of the compounds of the formula (XI) is preferably carried out after process steps 10 and 11.
Suitable diluents for carrying out the process according to the invention are, by way of example and by way of preference, alcohols, in particular methanol; ethers, in particular tetrahydrofuran; or alkylnitriles, in particular acetonitrile.
Preferred diluents for carrying out the process step 1 are ethers, in particular tetrahydrofuran; or alcohols, in particular ethanol, preferably methanol.
Preferred diluents for carrying out the process step 2 are alcohols, in particular methanol, pyridine, water or mixtures thereof.
Preferred diluents for carrying out process step 3 are alcohols, in particular methanol; dialkyl ketones, in particular acetone; dialkylformamides, in particular dimethylformamide, pyrrolidone, or dialkylacetamides; in particular dimethylacetamide.
Preferred diluents for carrying out the process step 4 are alkylnitriles, in particular acetonitrile.
Preferred diluents for carrying out the process step 5 are alcohols, in particular methanol, pyridine, water or mixtures thereof.
Preferred diluents for carrying out the process step 6 are alcohols, in particular methanol.
Preferred diluents for carrying out the process step 7 are alcohols, in particular methanol.
Preferred diluents for carrying out the process step 8 are alcohols, in particular methanol.
Preferred diluents for carrying out the process step 9 are alkylnitriles, in particular acetonitrile, dialkyl ketones, in particular acetone, dialkylformamides, in particular dimethylformamide, pyrrolidone, or dialkylacetamides, in particular dimethylacetamide.
Preferred diluents for carrying out the process step 10 are alkylnitriles, in particular acetonitrile, dialkyl ketones, in particular acetone, dialkylformamides, in particular dimethylformamide, pyrrolidone, or dialkylacetamides, in particular dimethylacetamide.
Preferred diluents for carrying out the process step 11 are alkylnitriles, in particular acetonitrile, dialkyl ketones, in particular acetone, dialkylformamides, in particular dimethylformamide, pyrrolidone, or dialkylacetamides, in particular dimethylacetamide.
Suitable diluents for carrying out the isomerization are all inert organic solvents. These preferably include aromatic hydrocarbons, such as for example toluene or xylene, esters, such as, for example, ethyl acetate or n-butylacetate, ethers, such as, for example tert-butyl methyl ether, dioxane, tetrahydrofuran or dimethoxyethane, ketones, such as, for example, acetone, butanone, cyclohexanone or methyl isobutylketone, or alcohols, such as, for example methanol, ethanol, n- or i-propanol, n-, i-, or t- butanol, or mixtures thereof with water.
For the purpose of the invention, acids are relatively highly concentrated acids, in particular mineral acids or hydrogen chloride gas.
The preferred mineral acid is hydrochloric acid, in particular hydrogen chloride gas.
For the isomerization, relatively highly concentrated acids, in particular mineral acids or sulfonic acids, for example and in particular sulfuric acid, methanesulfonic acid, hydrochloric acid and hydrogen chloride gas are employed.
The acidic ion exchangers used in the processes according to the invention are preferably perfluorinated ion exchangers.
The processes according to the invention are, if appropriate, carried out in the presence of a suitable acid acceptor/base. Suitable acid acceptors/bases are all customary inorganic or organic bases. These preferably include alkaline earth metal or alkali metal carbonates, such as, for example, potassium carbonate; alkaline earth metal or alkali metal bicarbonates, such as, for example , potassium bicarbonate; primary amines, such as methylanine, tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU), particularly preferably alkali metal acetates, in particular sodium acetate.
In process step 1, preference is given to using methylamine.
In process step 3, preference is given to using sodium acetate.
In process step 4, preference is given to using potassium bicarbonate.
In process step 5, preference is given to using sodium acetate.
In process step 9, preference is given to using potassium carbonate.
In process step 10, preference is given to using potassium carbonate.
In process step 11, preference is given to using potassium carbonate.
The alkoxyamines used in process step 5 are in particular methoxyamine and/or its hydrochloride salt.
The alkoxyamines used in process step 6 are in particular methoxyamine and/or its hydrochloride salt.
When carrying out the processes according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the processes are carried out in a temperature range of from 0xc2x0 C. to the reflux temperature of the mixture in question, in particular at reflux temperature.
The reactions according to process step 1 are preferably carried out in a temperature range from 0xc2x0 C. to room temperature, in particular at 5-15xc2x0 C.
The reactions according to process step 2 are preferably carried out in a temperature range from room temperature to the reflux temperature of the mixture in question, in particular at reflux temperature.
The reactions according to process step 3 are preferably carried out in a temperature range from room temperature to the reflux temperature of the mixture in question, in particular at room temperature.
The reactions according to process step 4 are preferably carried out in a temperature range from room temperature to the reflux temperature of the mixture in question, in particular at reflux temperature.
The reactions according to process step 5 are preferably carried out in a temperature range from room temperature to the reflux temperature of the mixture in question, in particular at reflux temperature.
The reactions according to process step 6 are preferably carried out in a temperature range from room temperature to the reflux temperature of the mixture in question, in particular at reflux temperature.
The reactions according to process step 7 are preferably carried out in a temperature range from room temperature to the reflux temperature of the mixture in question.
The reactions according to process step 8 are preferably carried out in a temperature range from room temperature to the reflux temperature of the mixture in question.
The reactions according to process step 9 are preferably carried out in a temperature range from room temperature to the reflux temperature of the mixture in question.
The reactions according to process step 10 are preferably carried out in a temperature range from room temperature to the reflux temperature of the mixture in question.
The reactions according to process step 11 are preferably carried out in a temperature range from room temperature to the reflux temperature of the mixture in question.
The reactions of the processes according to the invention are carried out under atmospheric pressure, under elevated or under reduced pressure, preferably under atmospheric pressure.
Preferred carbonyl compounds are dialkyl ketones, in particular acetone, aldehydes or glyoxylic acid.
Preferred alkylating agents are carbonates, in particular dialkyl carbonates, particularly preferably dimethyl carbonate, dialkyl sulphates, in particular dimethyl sulphate, or particularly preferably alkyl halides, in particular methyl chloride.
Preferred pyrimidine derivatives of the formula (XII) in process step 9) are trifluoropyrimidine or fluorodichloropyrimidines, in particular 5-fluoro-4,6-dichloropyrimidine.
Particular preference is given to carrying out process part 1A)a) without intermediate isolation of the compounds of the formulae (VI), (VII) and (II) (one-pot process).
Particular preference is given to carrying out process part 1A)b) without intermediate isolation of the compounds of the formulae (VI) and (II) (one-pot process).
Particular preference is given to carrying out process part 1B) without intermediate isolation of the compounds of the formula (II) (one-pot process)
Particular preference is given to carrying out process part 1C) without intermediate isolation of the compounds of the formula (VII) and (II) (one-pot process).
Particular preference is given to carrying out process part 1D) without intermediate isolation of the compounds of formula (II) (one-pot process).
Particular preference is given to carrying out process part 1 and part 2 without isolation of the intermediate compounds (one-pot process).
The starting materials of the formula (IV) used for carrying out the process steps 2), 6) and 7) are known and can be prepared by known processes (cf. Beilstein, E (II) 17, 462; Mameli, G. 56, 768; Chem. Ber. 35 (1902), 1640-1646; Proc. Indian Acad. Sci. Sect. A (1976) 83A(6), 238-242).
Some of the compounds of the formula (VII) required as starting materials for carrying out the process step 4) according to the invention are known (cf. Giannella; Pigini, FRPSAX, Farmaco Ed.Sci., 28, 1973, 157,159), and they are obtained by a novel route according to process step 7) from compounds of the formula (IV), or according to process step 3) from compounds of the formula (VI).
On the one hand, the compounds of the formula (VI) required as starting materials for carrying out the known process step 5) are known and can be prepared by processes known per se, on the other hand, they are obtained by a novel route according to process step 2).
The compounds of the formula (IV) required as starting materials for carrying out the process step 3) according to the invention have already been described in the description of the process step 5).
The starting materials of the formula (X) used in process step 8) in which R1, R2, R3 and R4 represent hydrogen and R5 represents methyl are mentioned by name in EP-398692, the starting materials of the formula (X), used in process step 8) in which R1, R2, R3 and R4 represent hydrogen and R5 represents alkyl are described under formula (VIII) on page 8 and page 14 and page 36 in WO9746542. They are also described under formula (IV) on page 7 and 8 and on pages 17, 19 and 20 in EP-846691.
The starting materials of the formula (II) used for carrying out the process step 1) can be prepared by process part 1Aa), process part 1Ab), process part 1B, process part 1C or by process part 1D by carrying out the process steps successively or by a one-pot process.
The starting materials used for carrying out the process steps 9), 10) and 11) are described in WO 98/21189.
The compounds of the formula (XI) used for carrying out the isomerization are obtained according to process part 1 and part 2.
All other starting materials are customary commercial products or can be prepared from these by simple processes.
Process step 2 is novel and also forms part of the subject-matter of the invention.
The process step 3) according to the invention yields the compounds of the formula (VII). The compounds of the formula (VII) are novel and inventive and form part of the subject-matter of the invention, except for the compounds of the formula (VII-a)
The process step 7) according to the invention yields the compounds of the formula (VII). The compounds of the formula (VII) are novel and inventive and form part of the subject-matter of the invention.
With the aid of the entire process (process part 1 and process part 2), the preparation of the known pesticides of the formula (XI) (cf. WO 98/21189) is considerably improved and simplified.
The process part 1 according to the invention serves to prepare important intermediates of the formula (I) and gives these intermediates a high and improved yield.
In process part 2 according to the invention, too, an increased yield in comparison to known processes can be observed.
By carrying out the isomerization after process part 2, in particular after process steps 10 and 11, the proportion of the E isomer in the isomer mixture is increased. | {
"pile_set_name": "USPTO Backgrounds"
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The persistent rise in the proportion of overweight individuals in Western society over the past 30 years has been associated with substantial excess morbidity and is widely recognized as a major public health concern. To address this problem, intensive efforts exist to clarify neuroendocrine contributions to weight gain. Starting with the isolation of leptin (1), a series of hormones acting centrally and peripherally to influence body mass have been discovered. Among these, the gastric peptide hormone acyl-ghrelin has generated considerable interest as an important stimulus for weight gain (2-5) and modulator of glucose homeostasis (6-8). Various strategies in therapeutic development have been described for the antagonism of acyl-ghrelin (9), although none has yet emerged as clinically beneficial.
The biosynthesis of acyl-ghrelin involves an unusual post-translational octanoylation of the serine at the 3 position of the ghrelin peptide. This octanoylation is necessary for its bioactivity, which occurs via interaction with the growth hormone secretagogue receptor (GHSR). The enzyme responsible for this esterification, ghrelin O-acyltransferase (GOAT), has recently been cloned (10, 11).
There remains a need in the art for improved therapeutic agents for use in the treatment of obesity and diabetes, especially ones that target neuroendrocrine pathways. In countering the global pandemic of obesity, which causes an estimated 10,000 premature deaths per week, an effective appetite-reduction medication can be potentially life-saving on a grand scale. | {
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The present invention relates to a series of new thiazole derivatives, in which the thiazole ring is attached via an unsaturated carbon chain to a rhodanine or thiazolidine-2,4-dione ring system. The invention also provides a process for preparing the compounds as well as methods and compositions for using them.
The enzyme aldose reductase is implicated in many of the complications of diabetes, and inhibitors of its activity can, therefore, be used in the treatment and prevention of such complications. A number of thiazolidine and/or rhodanine derivatives have been found to have the ability to inhibit the activity of aldose reductase. Thus, certain compounds of this type are disclosed in European Patent Publication Nos. 47,109 and 208,040, and in the published Japanese Patent Application Kokai Nos. 56,175/86, 238,286/87 and 179,873/88 (the latter being published after the priority date hereof).
We have now discovered a new series of thiazole derivatives having a very marked ability to inhibit the activity of aldose reductase, which ability is believed to be significantly better than that of the above-mentioned prior art compounds, from which they differ structurally primarily by virtue of the thiazole group. Moreover, these new derivatives include compounds which, upon oral administration, have been found to combine excellent absorption from the gastro-intestinal tract with very low toxicity. | {
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1. Technical Field
The present invention relates to a group judgment device that judges whether a device connected to its network belongs to a predetermined group.
2. Background Art
Recent years have seen the realization of home networking, i.e., networking home devices for sharing various pieces of content among them. As one form of home networking, devices including a television set and a videocassette recorder are star-connected, via one router installed in a home, to a server storing pieces of content. Within such a home network, the router is assumed to be the only device connected to an external network. The server obtains various pieces of content from the external network via this router, and stores therein the obtained pieces of content. The server can then distribute various pieces of content to the devices according to their requests. In this way, the devices can share various pieces of content among them.
In view of copyright protection, however, unlimited sharing of content is not permitted. For pieces of content whose use is limited only to devices within the home network, their distribution to devices external to the home network should be strictly prohibited. In this specification, a group that is composed of exclusive devices permitted to share content is referred to as the “AD (Authorized Domain)”. Upon every receipt of a content distribution request from a device, therefore, the server first judges whether the device belongs to the AD.
One method for the judgment uses IDs of devices belonging to the AD. This method requires the user to manually register, with the server, IDs of all the devices belonging to the AD.
As one example, the TCP Wrapper can be used to realize this judgment method. In the case of the TCP Wrapper, the user manually registers, into a file named “hosts. allow”, computers having access to service provided by the server.
Reference: Sakae Kumehara “Linux Network Firewall Management Guide”, Softbank, Chapter 4.2.2 | {
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This invention relates to poly(arylene sulfide)s. It relates to methods for preparing poly(arylene sulfides). In a specific aspect, the invention relates to the production of poly(arylene sulfide)s and products produced therefrom having improved thermal stability.
Polyarylene sulfides are an important class of engineering thermoplastics. The favored commercial process for the production of polyarylene sulfides involves the reaction of an aromatic compound such as dichlorobenzene with a sulfur source such as sodium sulfide in a polar reaction medium such as N-methylpyrrolidone. The polymer produced is resistant to many chemicals and exhibits good thermal stability. However, for the increasing industrial applications of polyarylene sulfide, improved thermal stability is desirable. One application is the use of nonwoven fabrics prepared from polyarylene sulfide fibers as filter bags for industrial smokestacks. For this and similar applications, improved heat stability of the polyarylene sulfide fibers is desirable. For certain applications such as thick films, a polyarylene sulfide having relatively low Tmc is desirable.
It is therefore an object of this invention to provide a method for the preparation of polyarylene sulfides. It is a further object to provide a method for preparing polyarylene sulfides having improved heat stability. In one embodiment, it is an object to produce a polyarylene sulfide fiber or monofilament having improved heat stability. In a further embodiment, it is an object to produce low Tmc polyarylene sulfide. | {
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Subcutaneous injection is a standard method for the delivery of medication. To facilitate frequent or continuous subcutaneous injection of medication, subcutaneous injection ports are often used. Such injection ports extend through the skin and may remain in place for several days. Currently a major application of such injection ports is to provide chronic delivery of medication such as insulin from portable pumps. When used with a pump, a fluid line is required to connect the injection port to the portable pump. Another application of a subcutaneous injection port is to permit multiple injections without the need to repuncture the skin. In this application, medication is injected from a standard hypodermic syringe and needle through a soft elastomer septum into the injection port which delivers the medication subcutaneously.
If a hollow metal needle is left in place through the skin to provide medication delivery, after one or two days the needle becomes uncomfortable to the patient. To solve this problem, a disposable injection port was described in U.S. Pat. No. 3,547,119 by Hall et al which has a soft, thin-walled cannula which is subcutaneously inserted over a metal needle. After insertion, the metal needle is removed leaving only the soft cannula through the skin. However the Hall invention has several limitations, namely:
(1) it is designed for infusion into the bladder and not for subcutaneous injection;
(2) the soft, thin-walled cannula which is subcutaneously inserted over the metal needle is placed in compression during insertion which can result in buckling of the cannula;
(3) the device has an extremely high profile making it impractical for ambulatory use where it is highly desirable to be hidden under clothing; and
(4) it does not provide a bacterial filter.
More recently, a soft cannula subcutaneous injection set described in U.S. Pat. No. 4,755,173 by Kanopka et al has become available. While being lower in profile than the Hall device and specifically designed for subcutaneous delivery of medication, the Kanopka invention also has several shortcomings, namely:
(1) there is no method for disconnecting the tubing near the point of subcutaneous insertion, thus requiring a long length of tubing to remain connected while showering, exercising or performing other activities for which having a long length of tubing is disadvantageous;
(2) many separate parts are required to construct the injection set which increases costs and the probability of leakage;
(3) like the Hall device, the soft, thin-walled cannula which is subcutaneously inserted over a hollow needle is placed in compression during insertion which can result in buckling of the cannula;
(4) the multiple parts design results in a comparatively high outward protrusion from the skin;
(5) there is a fluid chamber within the device which is a dead space for medication; and
(6) the cylindrical segment of the catheter hub which extends below the holding pad presses on the skin and often becomes uncomfortable for the patient.
Another soft cannula subcutaneous injection port is described in U.S. Pat. No. 4,531,937 by Yates. The Yates device, however, has several disadvantages, namely:
(1) it requires a fluid trapping capability in the needle hub for the expulsion of air from the inside of the device;
(2) like the inventions by Hall and Kanopka, the soft, thin-walled cannula which is subcutaneously inserted over a hollow needle is placed in compression during insertion which can result in buckling of the cannula;
(3) it has a "stepped bore" diameter which forms a fluid chamber within the device which is a dead space for medication;
(4) it does not provide a bacterial filter; and
(5) it lacks a flat surface for attachment to the skin to prevent bending of the soft cannula during prolonged insertion.
Still another soft cannula injection port is described in U.S. Pat. No. 4,311,137 by Gerard. The Gerard device, however, has several disadvantages, namely:
(1) it requires a complex movable needle/septum assembly with one position for flushing and a second position for insertion;
(2) it has a lumen (referred to as a passage) which forms a fluid chamber within the device which is a dead space for medication;
(3) it does not provide a bacterial filter;
(4) the Gerard design results in a comparatively high outward protrusion from the skin; and
(5) like the inventions by Hall, Kanopka, and Yates, the soft, thin-walled cannula which is subcutaneously inserted over a hollow needle is placed in compression during insertion which can result in buckling of the cannula. | {
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A thrust bearing having a bearing face with tapered lands is conventionally used for supporting thrust loads applied to the bearing face by means of a rotating shaft engaging the bearing face. The conventional thrust bearing of this type is made of a copper-type metal material containing lead or tin or an aluminum-type metal material containing tin, and is conventionally produced from a strip of the above-mentioned metal material by the employment of the press working method. As illustrated in FIGS. 1A and 1B, the conventional thrust bearing of this type has at its center a hole 1 through which will penetrate a rotating shaft with a shoulder, a bearing face 2 which is formed around the hole 1 to carry a thrust load, and a back face 3 which is formed on the opposite side of the bearing face 2. The conventional thrust bearing also has a plurality of tapered lands 4 formed in series in the bearing face 2 along the circumferential direction. The tapered lands 4 are shaped so that a wedge-shaped oil film is formed between the bearing face 2 and the surface of the shoulder of the rotating shaft. The tapered lands 4 are formed by the stamping method employing a stamping mold during the punching step by a press machine, and subsequently subjected to the well known tufftriding treatment for hardening the entire surfaces of the tapered lands 4. The tapered lands 4 are then subjected to buffing so that coarse surface of the tapered lands 4 are polished to a fine mirror surface. The tops of the tapered lands 4 are slightly rounded by the above-mentioned buffing step, although the general configuration of sharp edges of the tapered lands 4 still remain. According to such a conventional thrust bearing with tapered lands, the height of each tapered land 4 is usually from 5 to 10 microns. It is therefore difficult to form all of the tapered lands 4 maintaining the same height. Accordingly, the thrust load carried by the bearing face 2 of the thrust bearing is inevitably concentrated onto the tapered land 4 having the greatest height. Consequently, the oil film is broken on the highest tapered land 4 on which is concentrated the thrust load. Thus, so-called metal contact occurs between the highest tapered land 4 and the rotating shaft while resulting in the occurrence of abnormal wear and seizure due to high friction heat. Moreover, such an unstable factor is presented that the frictional torque changes depending upon a change in the thrust load.
In order to eliminate the above-mentioned defects, it has been proposed to flatten the tops of the tapered lands 4 by the method of polishing so that each tapered land 4 has an equal height. That is to say, one improvement over the conventional thrust bearing with tapered lands 4 has been proposed in which flat lands 5 are formed in the portions of the tapered lands 4 as shown in FIG. 2. According to the structure of tapered lands 4 having flat lands 5 as shown in FIG. 2, however, the circumferential length of the angled surface 6 for forming the wedge-shaped oil film is shortened. As a result, the surface area for carrying the thrust load is reduced. Consequently, the oil film pressure is increased for a given thrust load which will act on the oil film by means of the rotating shaft, so that the thickness of the oil film is inevitably reduced regardless of an increase in the allowable load. Accordingly, there easily takes place metal contact between the tapered lands 4 and the surface of the rotating shaft. Particularly, the thickness of the oil film is reduced at a boundary 7 between the angled surface 6 and the surface of the flat land 5, presenting the probability that the friction heat is generated at the boundary 7, which gives rise in the occurrence of seizure. | {
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The invention relates to mass spectrometry imaging of histologic thin tissue sections. The term “mass spectrometric image” of a thin tissue section which is obtained by mass spectrometry imaging (MSI) is defined here as an image which contains a mass spectrum with molecular information for every image point. The “mass spectrometric image” thus corresponds precisely to term “color image” which contains a color spectrum for every image point. The color spectrum contains the complete color information of the visible light spectrum, even if our eye summarizes the color spectrum into a single color impression. And just as it is possible to generate images of selected colors from a color image, for example red, yellow and blue images for a color print, it is possible to use a mass spectrometric image to generate “mass-selective images”, each of which displays the concentration of a molecular ion in its spatial distribution across the thin tissue section. Images which are derived from several selective images, and which can be used to spatially characterize the tissue states, are also of interest.
Histology is the science of human, animal and plant tissues, in particular of their structure and function. A histologic classification is generally carried out on a stained thin tissue section a few micrometers thick, and concerns the cell types present, the organ-specific differentiation of the tissue, bacterial and parasitic pathogens in the tissue, the disease states of the tissue and distributions of pharmaceutical products or their metabolites. The classification can be limited to one or more sub-areas of a tissue section or even apply to only one or more individual cells or organelles. The disease states of human tissue may relate to inflammatory diseases, metabolic diseases and the detection of tumors, especially the differentiation between benign and malignant forms of tumor or the prognosis of therapeutic success and survival expectation of a patient.
The generation of histologic tissue sections for an optical analysis involves the following steps: (a) the tissue is stabilized by deep freezing or chemical fixation, e.g. with formalin. (b) a thin section around 10 micrometers thick is cut with a microtome and (c) the tissue section is fixed, e.g. on a microscope slide, and stained.
Tissue stabilization means that the tissue structures, the cells of the tissue themselves and even intracellular structures (organelles such as the cell nucleus, endoplasmic reticulum, and mitochondria) are preserved in the tissue section. Usually, tissue stabilization is performed by deep-freezing. A well-known chemical tissue stabilization is termed “formalin-fixed paraffin-embedded” (FFPE); whereby the proteins within the tissue are cross-linked by reaction with formalin. Clinical archives hold millions of tissue samples, collected for more than a hundred years, stabilized by FFPE or similar methods. In routine histologic analyses, the structures of the tissue section are imaged with the aid of optical microscopes or with a “slide scanner”. A visual image of the tissue section recorded in this way can have a spatial resolution of about 250 nanometers.
The state of a tissue in relation to disease or infection with pathogens as compared to a healthy tissue sample can become apparent by a characteristic composition of substances. Usually, the substances are measured mass spectrometrically without imaging from homogenized pieces of tissue. The tissue state can be characterized by molecular information, in detail by the concentrations of different substances in relation to each other. If the substances are soluble and their concentrations sufficiently high, their concentrations can be detected by mass spectrometric analysis. The substances can be all types of biological substances, e.g. proteins, nucleic acids, lipids, polysaccharides or conjugates like glycoproteins or glycolipids. An unusual pattern can result when certain biological substances are modified, underexpressed or overexpressed. Proteins, in particular, can be modified in characteristic ways, e.g. by posttranslational modifications (PTM) or controlled degradation of the protein chain.
Mass spectrometry with ionization of the samples by matrix-assisted laser desorption and ionization (MALDI) has been used successfully for many years for the determination of molecular masses, and for the identification of biological substances, particularly proteins and peptides. This type of analytical technique can also be used for complex mixtures with some success. For example, methods of mathematical statistics can be used to mass spectrometrically determine the state of a tissue sample. Before these methods are used, a large number of tissue samples of different classifications (so-called “cohorts”) have to be provided, e.g. for the adjustment or learning of parameters. The sample formats can be homogenates of pieces of tissue or extracts.
In imaging mass spectrometric analysis, i.e. the acquisition of a mass spectrometric image, tissue sections are mass spectrometrically analyzed, usually with ionization by matrix-assisted laser desorption (MALDI). To this end, a thin-tissue section is placed onto an electrically conductive microscope slide as sample support. A thin layer of a matrix substance is then applied onto the tissue section by a suitable method not generating much lateral mixing of the tissue components, in such a way that finally the dried matrix substance layer contains the soluble peptides (and also other soluble substances) in an extracted form. The sample support is introduced into a mass spectrometer, and mass spectra of the individual image points are acquired.
The raster scan method according to Caprioli (U.S. Pat. No. 5,808,300 A) is predominantly used for the imaging mass spectrometric analysis; however, it is also possible to acquire a stigmatic image of a region of the tissue sample (Luxembourg et al., Analytical Chemistry, 76(18), 2004, 5339-5344: “High-Spatial Resolution Mass Spectrometric Imaging of Peptide and Protein Distributions on a Surface”).
In both cases, a “mass spectrometric image” of the tissue section is obtained, where for every image point the molecular information is present in the form of a mass spectrum. As is usual for MALDI, every mass spectrum is summed from a large number of individual spectra and covers an appropriate mass range, which can extend from around 100 to 60,000 atomic mass units. The region below 800 atomic mass units is measured to determine lipid distribution and the distribution of pharmaceutical products and their metabolites. The range between 800 and 60,000 atomic mass units is measured to determine the distribution of endogenous peptides and soluble proteins.
Various suitable methods for the preparation of tissue sections for mass spectrometry imaging analysis are known from the documents DE 10 2006 019 530 B4 and DE 10 2006 059 695 B3 (M. Schurenberg et al.; 2006). The matrix solution can be applied to the tissue section by pneumatic spraying, nebulizing by vibration, or by nanospotting of droplets, for example. It is no trivial task to apply the matrix solution because, firstly, a strong lateral diffusion of the biological substances must be avoided, secondly, the soluble biological substances must be extracted from the tissue section as completely as possible and incorporated into the crystals of the matrix layer, and thirdly, a favorable ratio of biologically relevant substances to impurities must be achieved. Some impurities greatly reduce the ionization yield. The kind of application of the matrix substance to the thin tissue section, the limitations for the spot diameter of the laser beam on the specimen, and also the quantities of substance required for the laser desorption mean that mass spectrometric images of tissue sections are currently limited to a spatial resolution of around 20 micrometers.
If the mass spectrometric images are acquired with a relatively coarse grid of 50 micrometers, this already produces 240,000 mass spectra for an area of 20 by 30 millimeters. Each time-of-flight mass spectrum can, in turn, comprise around 30,000 ion current measurement values or more. As is usual for MALDI, a hundred or more individual time-of-flight spectra are acquired and summed for each mass spectrum. Even in modern mass spectrometers with a high laser pulse rate, the acquisition of a mass spectrometric image takes many hours or even days depending on the size of the thin section and the width of the scanning raster selected.
One of the advantages of ionization by matrix-assisted laser desorption is that practically only singly charged ions of unfragmented analyte substance molecules are produced. It is therefore relatively easy to interpret the mass spectra. The mass spectra of the individual image points each show usually the mass signals of 20 to 400 soluble endogenous peptides in the mass range between 800 and 5,000 atomic mass units. The signals of the peptides emerge from a broad chemical background. Lighter proteins with less than around 5,000 atomic mass units are usually called peptides.
When MALDI time-of-flight mass spectrometers are used for imaging, a mass accuracy of around 50 millionths of the mass (50 ppm) can be achieved in the mass spectra of the image. If MALDI is used with other mass spectrometers, for example ion cyclotron resonance mass spectrometers or time-of-flight mass spectrometers with orthogonal ion injection, even better mass accuracies can be achieved.
“Monoisotopic ions” are defined as those ions from an isotopic group which are composed only of 1H, 12C, 14N, 16O, 31P, and 32S and contain no other isotopes of these elements. The monoisotopic ions are always the lightest ions of the isotopic group, which also contains ions with admixtures of other isotopes such as 2H, 13C, 15N, 17O, 18O, and 34S.
If peptides with molecular weights in the range between 1,000 and 5,000 atomic mass units are used for the imaging at correspondingly high mass resolution, a well-resolved isotopic group comprising several individual mass signals appears in the mass spectra of the thin-section image for every peptide. As is usual in mass spectrometry, individual mass signals of an isotopic group can immediately be summarized in the monoisotopic mass by known methods and entered in a table which corresponds to a reduced mass spectrum. It is possible to use either the monoisotopic molecular mass or the monoisotopic ion mass, which differ by the mass of one proton in the case of ionizations by MALDI. The document DE 198 03 309 C1 (C. Koster, GB 2 333 893 B; U.S. Pat. No. 6,188,064 B1, 1998) describes in detail a preferred method for the determination of the ion masses, and particularly the mass of the monoisotopic ions, which has become well known under the term “SNAP”. This method is also capable of recognizing the overlapping of isotopic groups of several peptides which differ by one or more mass units.
When the term “monoisotopic mass” is used below, it can mean either the molecular mass, i.e. the mass of the neutral molecule, or the ion mass, i.e. the mass of the protonated molecule.
The term “mass-selective image” designates an image of the tissue section which shows only the intensity distribution of the ions of this mass of a peptide, usually a monoisotopic ion mass. These images of selected masses are usually very noisy. Special types of smoothing process (see patent application DE 10 2010 009 853, for example) can be used to produce low-noise images which are very impressive and informative.
Mass spectrometry imaging is already eminently suited for classifying tissue sections according to tissue states, such as tumorous developments, and the visual representation of the tissue states. See for this the document DE 10 2004 037512 A1 (D. Suckau et al.; GB 2 418 773 B; US 2006/0063145 A1; 2004). These images are also good for measuring the distribution of pharmaceutical products of sufficient molecular dimension and their metabolites in the tissue, because the molecular weight of the pharmaceutical products and their metabolites are known and they can therefore be easily identified.
So far, however, it has only been possible in exceptional cases, and with laborious methods, to identify some of the peptides and proteins involved from such mass spectra of individual image points from thin sections, and to show, in particular, the distribution of these peptides in the thin section (see for example L. H. Cazares: “Imaging Mass Spectrometry of a Specific Fragment of Mitogen-Activated Protein Kinase/Extracellular Signal-Regulated Kinase Kinase Kinase 2 Discriminates”, Clin Cancer Res (17), 15; 2009). The identification is of particular interest in the search for biomarkers for certain tissue states, such as cancerous tumors.
In mass spectrometry imaging, a direct identification of endogenous peptides and proteins from the thin section is so far only possible in rare cases; an identification therefore requires additional measures. In non-imaging mass spectrometry, these measures usually entail a fragmentation of the proteins or their ions to increase the information content, whether fragmentations of the protein molecules by enzymatic digest, or fragmentations of selected parent ions for the generation of daughter ions, or even combinations of both. Proteolytic peptides, measurable between 800 and 4,000 atomic mass units, are peptides which result from the enzymatic degradation of the protein chain, e.g. by digestion with the protease trypsin. Large portions of the amino acid sequence can be read from daughter ion mass spectra; this makes an identification of these proteins possible. The methods for acquiring daughter ion mass spectra consume, however, considerable quantities of substance; for mass spectrometric imaging, the amount of substance of an image point is hardly sufficient for a daughter ion spectrum acquisition. Up to now, attempts at generating daughter ion spectra showed that daughter ion spectra of moderate quality only can be obtained from one or sometimes two high-intensity peptides of an image point (see for example D. Debois et al, “MALDI-In Source Decay Applied to Mass Spectrometry Imaging: A New Tool for Protein Identification”, Analytical Chemistry, Vol. 82, 4036-45; 2009), but this is by no means sufficient for a substance identification on a larger scale.
For non-imaging MALDI mass spectrometry on individual samples it is known that the identification of proteins is particularly successful via an enzymatic, for example tryptic, digestion of the proteins in conjunction with precise mass determination of the digest peptides or acquisition of their daughter ion spectra. An excellent measurement method, known by the term “LC-MALDI” (an abbreviation for “liquid chromatography matrix-assisted laser desorption and ionization), combines a separation of the digest peptides by liquid chromatography (HPLC), preparation of MALDI samples for separated fractions and acquisition of MALDI mass spectra and daughter ion spectra by a MALDI time-of-flight mass spectrometer (see U.S. Pat. No. 7,070,949 B2; D. Suckau et al.; 2001; equivalent to GB 2 387 653 B and DE 101 58 860 B4). On the basis of the precise masses of the digest peptides and their daughter ion spectra, computer programs can be used to select proteins from large protein databases which would lead to these digest peptides and their daughter ion spectra, given known digestion and fragmentation schemes. The protein databases usually contain the sequences of the amino acids; but it is also possible to use DNA information to identify the proteins (“open reading frames”).
Some research groups have therefore already attempted to enzymatically digest the proteins of a thin tissue section in situ for a better identification of individual proteins with the aid of the digest peptides. However, this digestion leads to a strong lateral diffusion of the digest peptides, and thus to an image with far less spatial resolution. In addition, the diffusion causes a strong dilution if the digested protein was localized in a small spot only, which puts many digest peptides below the detection limit.
But even if a digestion were successful with conservation of the protein positions, one would still not have achieved the goal. Since the thin tissue sections contain complex mixtures of proteins, an extremely high mass accuracy would be required for identification. A short example might explain this: for a species whose thin section is investigated, there can easily be 50,000 known proteins in the database, and digestion of these proteins would produce millions of digest peptides. If only around half of these digest peptides, let us say half a million, fell into the favorable mass range from 800 to 4,000 atomic mass units, the digest peptide of a certain monoisotopic mass number could be one of, on average, around 150 digest peptides which could occur per atomic mass unit in the mass range between 800 and 4,000 atomic mass units. The masses of these 150 digest peptides are also relatively close together; they each have a roughly Gaussian distribution with a full width at half-maximum of around 0.25 atomic mass units. The digest peptides of the thin section could only rarely be distinguished from each other, even with maximum mass resolution and maximum mass accuracy.
Therefore, the prior art direct mass spectrometric imaging methods essentially only detect and analyze the endogenous peptides and some soluble light proteins. There is no access to the most interesting non-soluble, large or immobilized biomolecules, whether the biomolecules are immobilized by chemical preparation or by the natural structure within cells. In FFPE samples with completely cross-linked peptides and proteins, not even the endogenous peptides can be analyzed. However, if, the biomolecules of the tissue section are in situ enzymatically digested, the vast and complex mixture of digest products in each image point and the limited mass accuracy does not allow the identification of the biomolecules by the usual identification procedures. | {
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1. Field of the Invention
The present invention relates to an improved data processing system and, in particular, to a symmetric data processing system with unified process environment and distributed system functions.
2. Discussion of the Prior Art
A recurring problem in symmetric multiprocessing systems of the prior art, that is, in systems having a plurality of processes wherein any of a plurality of multi-threaded processes may be executed concurrently or in any sequence on any of a plurality of processors, is in providing an environment which is unified from the viewpoint of the processes executing therein but wherein the system functions, such as memory space management, bus access, and data management, are not concentrated in a single processor. Such concentration of system functions, usually resulting from an attempt to present a unified processing environment, presents fundamental limitations in the capabilities of the centralized facility for performing such functions have an upper limit. The use of centralized system functions frequently results in a non-unified environment in that a centralized system cannot handle or even be aware of the requirements of each functional unit in the system. | {
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Hundreds of thousands of computing devices are lost or stolen each year. For example, more than 600,000 laptops are reportedly lost or stolen each year in U.S. airports alone. Although many computing devices utilize encryption techniques (such as full disk encryption) in an attempt to prevent data stored on lost or stolen computing devices from being compromised, these encryption techniques may be unable to fully secure onboard data if a computing device is lost or stolen while in a power-saving or power-management mode.
For example, during some power-management modes (e.g., sleep states S1, S2, and S3), a computing device may preserve an encryption key within memory (such as random-access memory) located on the computing device. The encryption key may enable the computing device to encrypt and decrypt data stored in a storage device (such as a disk storage device) located on the computing device. Since the encryption key may remain within memory during some power-management modes, an attacker may be able to access the encryption key stored in memory and use the same to decrypt the encrypted data stored in the storage device.
Such a vulnerability may significantly weaken system security by potentially compromising sensitive information stored on lost or stolen computing devices. As such, the instant disclosure identifies a need for effectively protecting against the unauthorized access of encrypted data stored on a computing device while the device is in a power-saving or power-management mode. | {
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The present invention relates generally to voltage regulators, and more particularly to control systems for switching voltage regulators.
Voltage regulators, such as DC to DC converters, are used to provide stable voltage sources for electronic systems, particularly electronic systems that include integrated circuits. Efficient DC to DC converters are particularly needed for battery management in low power devices, such as laptop notebooks and cellular phones, but are also needed for higher power demand products, e.g., desktop computers or servers. Switching voltage regulators (or more simply “switching regulators”) are known to be an efficient type of DC to DC converter. A switching regulator generates an output voltage by converting an input DC voltage into a high frequency voltage, and filtering the high frequency voltage to generate the output DC voltage. Typically, the switching regulator includes a switch for alternately coupling and de-coupling an unregulated input DC voltage source, such as a battery, to a load, such as an integrated circuit. An output filter, typically including an inductor and a capacitor, is coupled between the input voltage source and the load to filter the output of the switch and thus provide the output DC voltage. A controller measures an electrical characteristic of the circuit, e.g., the voltage or current passing through the load, and sets the duty cycle of the switch in order to maintain the output DC voltage at a substantially uniform level.
Voltage regulators for microprocessors are subject to ever more stringent performance requirements. One trend is to operate at ever lower voltages, e.g., less than 1 volt, and at higher currents, e.g., 50-150 amps. Another trend is to turn on or off different parts of the microprocessor in each cycle in order to conserve power. This requires that the voltage regulator react very quickly to changes in the load, e.g., several nanoseconds to shift from the minimum to the maximum load, and to have a fast transient response, e.g., to quickly stabilize without significant voltage or current ripple.
Still another trend is to place the voltage regulator close to the microprocessor in order to reduce parasitic capacitance, resistance and/or inductance in the connecting lines and thereby avoid current losses. However, in order to place the voltage regulator close to the microprocessor, the voltage regulator needs to be small and have a convenient form factor.
In addition to these specific trends, high efficiency is generally desirable in order to avoid thermal overload at high loads and to increase battery life in portable systems. Another desirable feature is for the voltage regulator to have a “standby mode” which consumes little power at low loads. | {
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The present invention generally relates to semiconductor manufacturing and more particularly to fabricating reworkable interconnect structures having integrated testing capabilities.
Typical semiconductor integrated circuit (IC) chips may have layers stacked such that layer features overlay one another to form individual devices and connect devices together. ICs are mass produced by forming an array of chips on a thin semiconductor wafer. Each array location is known as a die and each die may harbor a multilayered structure, such as an IC chip or a structure for test or alignment.
As transistor technologies advance, chip features and devices are increasingly smaller having minimum dimensions that may be well below one micrometer (1 μm) or 1 micron. Smaller chip features and devices allow IC manufacturers to integrate more function in the same chip real estate. However, scaling of wafer test probes to finer pitch may pose numerous challenges, as the cost and complexity of wafer probe technology increases. By way of example, in existing approaches, challenges in test probe manufacturing may include scalability, material selection flexibility, and cost of fabrication. Probe card and test probe technologies have been adapted to cover area array interconnection pitches down to the range of 150-200 microns. These technologies may not offer a workable solution for fine-pitch probing in three-dimensional (3D) silicon devices with area array pitches 50 microns and smaller. | {
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1. Technical Field
The present invention relates to a method and apparatus for repairing bodily tissue in vivo and has particular utilization in repairing a meniscal tear during arthroscopic surgery of the knee.
2. Discussion of the Prior Art
Although the following description is directed specifically to repairing meniscus tissue in vivo in a human knee, it should be understood that the principles of the present invention are applicable to the repair of any bodily tissue, such as cartilage, bone, skin and ligaments, in an in vivo surgical procedure.
The knee is a hinge joint which permits a limited amount of rotation. The opposing curvature of the articulating surfaces of the femur and tibia are equalized, to a certain degree, by the menisci, the wedge-shaped fibrocartilaginous structures located on the periphery of the articular surface. The menisci are mobile buffers functioning to inhibit displacement of the joint and to distribute the force exerted by the femur over a larger area of the tibia. Possible causes of damage or injury to the menisci are multiple. Damage or tear of a meniscus usually occurs when the weight-bearing joint is subjected to a combined flexion-rotation or extension-rotation motion. The elastic and fibrous structure of the menisci, the rigid fixation of the anterior and posterior attachments, and their connections with the joint capsule, cause the menisci to return to their normal positions at the periphery of the joint if there is displacement. Disturbance of the normal mechanism of the joint and interference with mobility of the menisci can exceed their elasticity and cause tears of the cartilaginous substance. This appears to occur most frequently when a meniscus that has been displaced into the joint is caught between the femoral and tibial condyles as the result of a sudden change of movement.
Treatment for torn menisci has changed considerably over the years. At one time it was advocated that a peripherally detached meniscus be removed, even though the tissue was not damaged. The rationale was that excision of the meniscus prevents meniscal re-injury in a joint in which the mechanics may have been disturbed. In many cases a complete meniscectomy (i.e., total removal of the meniscus) was performed. Results from a complete meniscectomy ultimately showed degenerative arthritis, instability and changes in the transmission of loads in the knee. Because of these complications a partial meniscectomy became an alternative to a complete meniscectomy. Recently, there has been a strong movement to save as much of the meniscus as possible, leading to the development of techniques for meniscal suturing. Animal studies have been performed to demonstrate the safety and efficiency for this procedure.
An arthrotomy, or open technique, requires large incisions to gain access to the joint. Utilizing the open technique for meniscal suturing repair provided the opportunity of returning the knee to its prior pre-injury level of performance; however, the resulting large incisions require longer periods of immobilization and consequently longer periods of rehabilitation and recovery. Recent advances in instrumentation have made it possible to repair some meniscal lesions under arthroscopic visualization. Generally, this instrumentation is for inserting and receiving the suture as it passes through the meniscus. Typically, suture is passed through the meniscal rim and body of the meniscus, guided by special cannulas through the knee. The suture is then tied posterior to the knee and placed subcutaneously. Most of these procedures are performed using a larger (i.e., four to eight centimeters) incision than the standard portals used in arthroscopy. Depending upon the meniscus to be repaired, the incision is placed on the medial or lateral side of the knee; however, because of the long needles generally employed in meniscal repair, extreme caution must be observed during this procedure in order to avoid the possibility of the needle penetrating the popliteal artery or posterior tibial nerve and catching the fat pad during passage of the needle into and out of the knee joint. A spoon-shaped instrument is generally employed to act as a needle shield or guard for the popliteal structures. Nevertheless, there have been reported instances of injury to these vital areas with consequential damage to arteries and nerve palsy in the limb. Surgical techniques are being perfected, as are improvements to instrumentation, by various groups in order to minimize these risks and to decrease the procedural time.
It is known to use certain types of metal staples in conjunction with surgery for repairing bone tissue. The legs or shafts of the staple have a series of barbs which hold the staple and surrounding base tissue in place during the healing process. Another known device serving a similar function is the Smillie nail which is a single shaft device employed for securing bone tissue parts in place during the healing process. These staple and nail devices are effective for holding the bone tissue together during healing; however, they require a second surgical procedure in order to remove the device after the tissue has healed. | {
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The present invention is directed toward a garment worn by a person using a corded electrical appliance and more particularly, toward a garment that allows a person to safely work unhindered by an electrical cord while using the electrical appliance.
Often when using an electrical appliance or electrically powered tool, a power cord is associated with the appliance or tool. Although various battery operated power tools are available, corded tools are still frequently more desirable as they are normally more powerful and can operate for longer periods of time.
One concern when using such appliances or tools is, however, that the cord must be kept out of the person's way while he or she works. It is not only inconvenient to constantly have to move the cord out of one's way while working, it is also a matter of safety. That is, it is important that the cord not get in the way of the appliance being used. Also, a person must be able to see clearly and without any obstructions while using an electrical appliance. For example, a sander, a buffer, a hedge trimmer, and the like all typically involve an electrical cord that must be kept out of the way of the user. Various attempts have been made to provide an electrical cord holder that keeps the cord away from a person as he or she uses an electrical appliance.
For instance, U.S. Pat. No. 5,758,809 to Bonner discloses a cord holding harness that includes a suspender-like strap that fits over the upper torso of a person and a sleeve attached to one of the straps. The strap includes a hook for engaging the cord of the electrical appliance. This cord holder, however, does not appear to be very versatile as the device is in the form of suspenders that must be secured to a person's clothing using clips that attach to the belt or pants being worn by the person.
U.S. Pat. No. 3,862,709 to Roshaven discloses a cable holder that includes a shoulder plate having a hook to hold the cable and a plurality of straps disposed about the waist and upper portion of the wearer's body. This cable holder also must be attached to the wearer's clothing.
Also, U.S. Pat. No. 6,523,227 to Goodall discloses a shoulder mounted cord retaining clip that includes a shoulder pad portion that is positioned on a person's shoulder. Clips attached to the pad are used to hold the cord of an electrical appliance while a person is using the appliance. This device, however, does not appear to be very comfortable for the person to wear and use as the cord can still be in front of the person and potentially block his or her view of the work area or otherwise hinder the person while using the appliance.
Therefore, a need exists for an electrical cord holder that is convenient to use and will safely and securely hold a cord away from a person while he or she is using an electrical appliance. | {
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The present invention relates to a method of gaming, a gaming system and a game controller.
Gaming systems are known that have a re-spin feature where a player can select an option to hold one or more spinning reels. The one or more held reels may be used in the generation of a subsequent game outcome.
While such gaming systems provide players with enjoyment, a need exists for alternative gaming systems in order to maintain or increase player enjoyment. | {
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The invention relates to a device for exhaust gas recirculation in diesel engines which are equipped downstream of the internal-combustion engine with a soot burn-off filter in the exhaust pipe of the exhaust gas stream, with an exhaust gas recirculation pipe which branches in the further course of the exhaust pipe and in which an exhaust filter for the recirculated exhaust gas is arranged.
Nowadays, with motor vehicles it is endeavored in principle to process the emission gases of the internal-combustion engines in such a way that the exhaust gases are discharged into the free atmosphere without any great environmental pollution. This can happen on the one hand by filter elements which clean the exhaust stream of particles to be separated out being arranged directly in the exhaust pipe of the exhaust gas stream. It is also already known in the case of internal-combustion engines to perform an exhaust gas recirculation to improve the quality of the exhaust gases. For this purpose, a part of the exhaust gases is returned via a so-called recirculation pipe from the exhaust pipe of the internal-combustion engine to its intake side.
The cleaning of the exhaust gas stream is particularly problematical in the case of diesel internal-combustion engines. The exhaust gases of the diesel engines namely contain a greater degree of solid particles, predominantly carbon particles.
These carbon particles are produced due to an incomplete combustion of the hydrocarbon fuel under certain operating conditions. In order to free the exhaust gas stream of these carbon particles in the case of diesel engines, it is also already usual to install a filter element in the exhaust pipe downstream of the internal-combustion engine. In addition, it is also already known to arrange a further filter in the exhaust gas recirculation pipe for the purpose of a still further-reaching cleaning of returned exhaust gases (European Patent Specification No. 0,010,384).
However, such a filter installed directly in the exhaust gas recirculation pipe can very easily clog at its surface with a layer of soot particles and other contaminants still entrained into the exhaust gas stream and become blocked. This can then have the result that, due to the blocked filter, considerable counter-pressures can build up in the exhaust gas stream, which can have adverse effects on the operating conditions of the engine. The danger that such a filter arranged directly in the exhaust gas recirculation pipe becomes blocked by contaminants entrained in the returned exhaust gas flow is particularly great in the case of engines which are equipped downstream of the internal-combustion engine with a soot burn-off filter in the exhaust pipe of the exhaust gas stream. These soot burn-off filters normally consist of ceramic elements which can lose their strength during prolonged use on account of the high thermal and mechanical stress. This has the consequence that very fine particles are removed from the ceramic element and carried away with the exhaust gas. These particles are then deposited on the surface of the filter in the exhaust gas recirculation pipe and can impair its serviceability even after a short time.
If there is no filter arranged in the exhaust gas recirculation pipe, the cylinder space is exposed to the action of wear particles of ceramic, which can result in failure of the engine.
An object of the invention is therefore to create a device for exhaust gas recirculation in diesel engines, in which the disadvantages specified above do not occur and the contaminants are removed reliably and to the greatest extent from the exhaust gases returned from the exhaust pipe to the internal-combustion engine.
This object is achieved according to the invention by providing an arrangement wherein the exhaust filter is arranged in the branch of the exhaust gas recirculation pipe in such a way that its surface on the contamination side lies at least approximately parallel to the direction of flow of the main exhaust gas stream and in the region and course of a normal flow line, preferably close to the wall, and the branch for the exhaust gas recirculation is fitted in the region of a pipe extension of the exhaust pipe which is restricted locally to an axial region and in the inside of which a tubular filter insert is inserted in a sealed manner, the clearance profile of which coincides in position, shape and size approximately with the clearance profile of the exhaust pipe of the main exhaust gas stream, the pipe extension enclosing the filter insert on the outside at a distance.
Especially preferred embodiments of the invention include one or more of the following advantageous features:
i. the filter insert consists of a dimensionally stable porous pipe of sintered ceramic or of sintered metal; PA1 ii. the pore size of the filter in the branch of the exhaust gas recirculation pipe is 0.1 to 20 mm; PA1 iii. the filter-effective length of the tubular filter insert is greater than the clear diameter of the filter insert; and PA1 iv. the branch is arranged in relation to the direction of gravity in such a way that the direction of removal is directed at least approximately counter to the direction of gravity.
During the operation of the motor vehicle, the exhaust gases coming from the internal-combustion engine, possibly also already directed via a soot burn-off filter, flow past the surface on the contamination side of the second exhaust filter arranged in the branch of the exhaust gas recirculation pipe, a proportion of the exhaust gases being returned through the filter to the intake side of the internal-combustion engine. In the case of prolonged use of the device according to the invention, a certain coating of the surface on the contamination side with soot particles and other contaminants may occur. However, these remain of the orders of magnitude such as are known from the usual exhaust systems and which do not substantially impair the serviceability of the device. The flow of the main exhaust gas stream has the effect to a certain extent of continuously removing contaminants from the surface on the contamination side of the filter and carrying them away with the main exhaust gas stream out of the exhaust pipe.
Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings. | {
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This invention relates to a brassiere (bra) shield usable with a bra that both absorbs moisture and is disposable. Moisture managing brassieres or bras are known. In one earlier invention a moisture management bra is made from a stretch fabric material having a moisture transport fabric layer constructed of hydrophilic yarn.
Another moisture managing bra was made from a material which wicks moisture away from the skin of the wearer. Perspiration absorbent pads secured to bra cups can be used to absorb perspiration from the skin of a wearer in other inventions.
One invention discloses a pad made of moisture absorbent material that is secured by adhesive to the bra such that a shield fits under the breasts and extends between the breasts.
Still another moisture absorbing bra has a perspiration absorbent pad which can be secured into the cups of the bra to absorb perspiration from the skin of a wearer. | {
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The subject matter of this invention is related to a static, current-limiting, bilateral force commutated switch with a reverse parallel pair of thyristor stacks as the main conduction element.
It has been long known that current limiting in an electrical circuit subject to high values of overload current is desirable. In the fuse art, for example, current limiting fuses are known which not only melt upon the presence of an overload but operate to reduce the amount of overload current during the short interval between the time that circuit interruption begins and the time that circuit interruption is completed. It has been long recognized that in the latter time interval though of relatively short duration, perhaps only a few hundred microseconds, there is sufficient time for the current in the circuit to rise to such a high value as to permanently damage those elements for which the circuit protective device was designed to protect. Analogously, certain current limiting apparatus is known in electrical circuits protected by circuit breakers, non-current limiting fuses or the like. Take the case of mechanical circuit breaker apparatus, for example. Generally these devices are highly reliable and well thought of in the art of circuit interruption. However, since they are mechanical devices, interruption time may become relatively long. As was mentioned previously, the value to which a fault current may rise in these relatively long circuit opening times can become prohibitive in terms of protection for the circuit. To remedy this the concept of utilizing a force commutated circuit in series with the mechanical circuit breaker was introduced into the art. The circuit essentially consists of oppositely disposed, parallel connected, unidirectional, solid state devices such as thyristors. Connected across the oppositely disposed thyristors is a relatively high resistive element for current limiting and a commutating circuit. In operation, the control circuit for the gates of the thyristors maintains the thyristors in a conductive state for alternating current during a normal operating situation. Consequently, the normal operating alternating current sees the relatively small resistance or forward voltage drop of a thyristor during each half cycle. Even when peak inverse voltage constraints in the circuit require that numerous thyristors be connected in series stacks, the net resistive effect and voltage drop effect though somewhat undesirable is usually deemed acceptable in view of the very desirous current limiting operation provided by the commutating circuit and resistive means which parallels the normally conducting thyristors. In the event of the onset of a fault current or the like, appropriate sensing apparatus associated with the commutating circuit quickly determines that a fault current of unacceptable magnitude is in the process of developing. The sensing circuit then quickly reacts to this phenomenon by deenergizing the gates of the thyristors, thus attempting to render the thyristor non-conductive. Furthermore, the sensing circuit switches the commutating circuit into operation. The commutating circuit usually consists of a precharged capacitor which sinks current away from the conducting thyristor and through the capacitor. It does this very quickly, often within a time span of a few microseconds. The reason for this is well known in the art. A thyristor will not stop conducting merely because its gate signal has been removed. Two additional characteristics must be satisfied before the thyristor will cease to conduct. First, the current flow in the thyristor must be reduced to zero and, second, the anode-to-cathode voltage of the thyristor must be reverse biased for a relatively short period of time (recovery time) to sweep out the carriers that might otherwise lead to reconduction. It can be seen therefore that the capacitor generally provides a dual function; it quickly sinks away the current from the main thyristor path thus reducing the current in that path to zero to meet the first characteristic, and it reverse biases the thyristor thus meeting the second requirement. In performing its second function, i.e. reverse biasing, the voltage of the capacitor is usually so high that its reverse biasing characteristic is known as "hard" reverse biasing. This is usually associated with high voltage but, more importantly, it is associated with utilizing the capacitor as a voltage source rather than a current source. Generally, the means for connecting the charged capacitor to the circuit for accomplishing its stated purposes is an auxiliary switching thyristor. Unfortunately the gating of the auxiliary switching thyristor may cause current to be commutated away from the main thyristor and into the capacitor circuit at such a high rate as to destroy the auxiliary thyristor. It is well known that thyristors have a maximum rate of rise of current with respect to time which they can tolerate without being destroyed. In order to solve this problem in the prior art, an inductor is used in series with the capacitor to limit the rate of current rise. When the main thyristor ceases to conduct in the prior art, the hard capacitor voltage appears across that thyristor, as reverse bias, and in series with the system voltage. This results in the first drawback of a hard commutation circuit; namely, since the system voltage is boosted by the capacitor voltage, the fault current rises even faster than before. The second drawback of a hard commutation circuit is that the current limiting resistor which is connected directly across the thyristor starts to deplete the capacitor charge from the moment the compensating branch is actuated. Consequently, a larger capacitor is needed to provide the necessary reverse bias time (recovery time) than would be needed if the resistance were not present. In prior art, U.S. Pat. No. 3,921,038 issued Nov. 18, 1975 to Kernick et al entitled "Static Surge-Current Limiter" and U.S. Pat. No. 3,737,759 issued June 5, 1973 to Pollard entitled "Static Switch Including Surge Suppressing Means", the latter-mentioned problem was circumvented by connecting a current limiting resistive element in series with a diode but in parallel with the capacitor. As a result, the circuit branch containing the resistor does not start to conduct until after the reverse bias interval is over. This saves commutating capacitance at the cost of utilizing a relatively high voltage diode which must have a short duration current rating equal to the limited transient fault current. The third drawback of a hard commutating circuit lies in the fact that the previously discussed inductance is utilized merely to limit the rate of rise of current through the discharge circuit. The presence of the inductance, though needed, actually degrades the circuit to a certain extent because reverse biasing of the thyristor will not start until after the entire line current has been commutated into the capacitor, by which time a non-negligible portion of the charge of the capacitor may have been depleted. In the previously mentioned prior art patents, a number of things were done to eliminate certain problems associated with the previous generation of current limiters. One of the things done was to introduce the concept of the "soft" commutation circuit. With soft commutators, the capacitive element acts not as a voltage source but as a current source. This soft commutating circuit implies that the conducting thyristor, i.e. the one to which the reverse bias must be supplied, is turned off by a very modest reverse bias voltage. This voltage is obtained by a resonant discharge of the precharged capacitor through an inductor and a diode connected in reverse across the conducting main thyristor. The forward voltage drop of the diode, therefore, appears as reverse voltage across the thyristor from the instant the capacitor discharge current rises above the value of the main current until the instant the capacitor discharge current drops below the value of the main current. During this interval, the thyristor is provided with soft reverse bias. It is immediately after this interval, but during the alternating current half cycle of interruption, that the net current which attempts to flow through the thyristor reverses again. That is, the capacitor discharge current falls below the value of the main current. However, with the thyristor now recovered and thus turned off and the diode blocking, the main current divides between the branch containing the resistive element and the commutating branch containing the capacitive element and the inductive element L. This soft commutating circuit removes one of the problems associated with the inductor. In this case, the inductor L no longer degrades the circuit, but is utilized in conjunction with the capacitor to tune the circuit to obtain the main current reversal. Furthermore, the other two drawbacks associated with hard biasing are also eliminated. First, the voltage inserted into the line is soft or of relatively low value. Thus, the circuit does not contribute significantly to the rate of increase of the fault current. Secondly, the resistive element utilized for current limiting, although directly in parallel with the thyristor switch, carries only negligible current. However, in overcoming the aforementioned drawbacks, other drawbacks appeared. One is the need for the utilization of a series of diodes stacked together for the purpose of carrying the discharge current of the capacitive element during the period of time when that current is larger than the main current to provide the previously described soft bias voltage. It is noted that in the prior art, these additional diode stacks are always present in the main current conduction path for the alternating current. Consequently, these stacks must be rated to continuously carry full load current and to support the system voltage plus transient overloads and thus constitute a significant cost item. Furthermore, the conduction losses in the diode may increase the switch losses by approximately 60% which is highly undesirable in high power applications. Therefore, it would be desirable if the utilization of the soft biasing principle but with elimination of the drawbacks associated therewith could be implemented. It would be further advantageous if the solution would utilize an existing circuit element to perform extra circuit functions above and beyond what was described in the prior art, thus providing a significant cost reduction. Furthermore, it would be advantageous if apparatus could be found which utilized the soft biasing technique in which the suppression of transients associated with a switching and commutating operation could be affected. Furthermore, it would be advantageous if a commutating circuit could be found in which repeated reversal of the capacitive discharge current could be permitted or denied as required. | {
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1. Field of the Invention
This invention relates to an aqueous cleaning and bleaching composition containing a stable, concentrated alkali metal hypochlorite composition.
2. Description of the Prior Art
It is known from U.S. Pat. No. 3,172,861 to combine a liquid alkali metal hypochlorite bleaching composition with a bleach-stable detergent which can be an alkylated diphenyl oxide sulfonic acid alkali metal salt and to obtain clear compositions which are storage-stable at room temperature and free of precipitate or cloudiness after 6 weeks to 4 months shelf-storage at room temperature. In the compositions disclosed therein it has been believed necessary to maintain the concentrations of ingredients proportionately low in order that the recognized tendency of organic materials to decompose in the presence of oxidizing agents will be minimized. In view of the disclosure contained in this reference therefor, it is unexpected that the applicants have discovered that hypochlorite concentrates containing an alkali metal hydroxide and an alkali metal chloride in addition to an alkali metal hypochlorite and an alkali metal salt of an alkylated diphenyl oxide sulfonic acid can be prepared which are clear, stable to storage at room temperature and at elevated temperatures and at low temperatures and upon dilution are more effective in oily soil removal than the compositions of the prior art.
While stable mixtures of sodium or calcium hypochlorite and a detergent together with compound such as alkali metal phosphates, silicates, carbonates or sulfates have been prepared in the dry state and utilized as cleaning compositions upon admixture with water, these dry compositions are intended to be mixed with water immediately prior to use and are neither stable in contact with water nor do they generally form clear aqueous solutions. Thus there is an unfulfilled need for an aqueous liquid concentrate containing an alkali metal hypochlorite, alkali and a detergent together with metal chelating agents and metal passivating agents which can be diluted with water prior to use to form a stable balanced detergent composition suitable for general purpose or hard surface cleaning. Unexpectedly, in the liquid concentrates of the invention, the presence of an equimolar amount of alkali metal chloride, based upon the alkali metal hypochlorite, does not adversely affect long-term storage stability or inhibit cleaning efficiency.
Other liquid detergent-bleach compositions are disclosed in U.S. Pat. No. 3,758,409, U.S. Pat. No. 3,929,661 and U.S. Pat. No. 3,560,389. Generally, such compositions contain structurally dissimilar detergents as compared to the detergent used in the compositions of the invention. | {
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The invention relates generally to pointer systems for computer systems, and more particularly to pointer systems that include a sensor system.
Several different types of devices have been used in pointer systems for computer displays. Common pointer systems include trackballs, light pens, and mice. A conventional mouse includes a roller ball that rotates as the mouse moves on a mouse pad. Rollers within a mouse aid in translating a ball""s movement into delta X and Y coordinates. These coordinates are relayed to a computer system and interpreted by a software routine (a driver), resulting in the desired movement of a pointer on a computer display.
Another type of pointer device is an optical mouse which includes optical sensors on the bottom of the mouse to detect the movement of the mouse. Optical mice utilize a special mouse pad surface with a specific pattern to identify movement of a mouse. The mouse pad used with an optical mouse is merely a reflective component.
One problem with a conventional roller ball mouse may be that a ball generally picks up dirt, dust, and other particles from a mouse pad that become impediments to the proper movement of a mouse. These impediments may impair the movement of a roller ball and the other mechanical parts inside a mouse. Removing the impediments frequently involves user intervention. The user manually removes a roller ball from a mouse and cleans both the roller ball and the rollers incorporated in the mouse. Additionally, a roller ball mouse may include several mechanical parts to translate ball rotation into indications of linear movement. These additional mechanical parts may increase the cost of manufacturing as well as the probability of failure of a pointer system.
Thus, it would be beneficial to provide a mechanism for pointer system functions without the use of a conventional roller ball in a mouse.
The invention includes a pointer system that utilizes a sensor system to determine movements of the pointer system. The pointer system includes a hand unit incorporating one sensor component operatively coupled to a movement surface with a plurality of sensors.
In one embodiment, the hand unit may be electrically coupled to the computer system. Each of the plurality of sensors attached to a movement surface may emit a distinct signal to be received by the sensor component of a hand unit.
In another embodiment, the movement surface may be electrically coupled to the computer system. The sensor component of a hand unit may emit a signal to be received by each of the plurality of sensors attached to a movement surface. | {
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The present invention relates to improvements in the field of drop cable clamps. More particularly, the invention is directed to an improved wedge clamp for holding a cable suspended from a support.
Applicant has already described in U.S. Pat. No. 3,960,461 a drop cable clamp for suspending a coaxial television cable from a support while providing a loose cable portion extending from the clamp. Such a drop clamp comprises a conical body member formed with a longitudinal outer groove having a depth smaller than the diameter of the cable for receiving the cable such as to leave a cable portion protruding therefrom, and a conical wedge sleeve for mounting over the body member and formed with a longitudinal slot for passing the cable therethrough. The conical body member is also provided at its smaller end with means for connecting it to the support. Thus, in use, the wedge sleeve is mounted over the body member with the slot in axial alignment with the groove, the cable is inserted in the groove through the slot and the sleeve is rotated over the body member to clamp the cable therebetween.
The drop cable clamp of the type described above is generally capable of sustaining a load up to about 500 pounds. However, when it is desired to hold a multi-wire cable such as a telephone aerial cable, suspended from a support, the increased number of wires in the cable adds to the weight of the cable so that the load may exceed 500 pounds and reach 750 pounds or more, causing the sleeve of the drop clamp to open up and/or the sidewall of the body member to collapse. In addition, the longer the suspended cable is, the greater is the pull exerted by the cable. Adverse weather conditions also contribute to increasing the pull exerted by the cable on the clamp, thus increasing the load sustained by the clamp. | {
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Chromatography analysis techniques may be used to analyze the separation of mixtures for various research and/or industrial purposes in industries such as oil and gas, pharmaceuticals, and biotechnology. Chromatography may be used to separate the components of a mixture and determine the proportions of each component in the mixture. High throughput chromatography may involve the use of filter plates containing multiple wells that may be analyzed at the same time using the chromatography test apparatus or that may be used to prepare concentrated solution(s) of a component or components.
For example, in the oil and gas industry, materials from a subterranean operation, such as drill cuttings or other particulate material, may be suspended or packed in a drilling fluid and may provide useful information about the subterranean formation from which they came. For example, such experiments examine the chemistries, performance, or characteristics of materials such as small amounts of the formation fluids (e.g., oil, water, etc.) of interest that are present in the formation. The permeability, porosity, rock composition, and/or other properties of the subterranean formation also may be of interest. Chromatography may be used to identify the properties of the materials and provide information for use in designing a subterranean operation and/or selecting materials for use in a subterranean operation. | {
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1. Field
Exemplary embodiments of the invention relate to a display device and a method of manufacturing the display device. More particularly, exemplary embodiments of the invention relate to a display device having improved brightness uniformity and thin thickness and a method of manufacturing the display device.
2. Description of the Related Art
A display device is classified into a liquid crystal display (“LCD”), an organic light emitting diode display (“OLED”), a plasma display panel (“PDP”), and an electrophoretic display, for example, in accordance with the light emitting manner thereof.
The display device generally includes a display panel, various frames supporting and accommodating the display panel, and various optical sheets improving optical characteristics of the display panel. In the display device, the display panel, the frames, and the optical sheets are sequentially stacked. In addition, the display panel includes a display part and a non-display part surrounding the display part, and the frame is disposed to cover the non-display part of the display panel. | {
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A communication system may be a facility that enables communication between two or more nodes or devices, such as fixed or mobile communication devices. Signals can be carried on wired or wireless carriers.
An example of a cellular communication system is an architecture that is being standardized by the 3rd Generation Partnership Project (3GPP). A recent development in this field is often referred to as the Long Term Evolution (LTE) of the Universal Mobile Telecommunications System (UMTS) radio-access technology. E-UTRA (evolved UMTS Terrestrial Radio Access) is the air interface of 3GPP's Long Term Evolution (LTE) upgrade path for mobile networks. In LTE, base stations or access points (APs), which are referred to as enhanced Node B (eNBs), provide wireless access within a coverage area or cell. In LTE, mobile devices, or mobile stations are referred to as user equipments (UE). LTE has included a number of improvements or developments.
5G New Radio (NR) development is part of a continued mobile broadband evolution process to meet the requirements of 5G, similar to earlier evolution of 3G & 4G wireless networks. A goal of 5G is to provide significant improvement in wireless performance, which may include new levels of data rate, latency, reliability, and security. 5G NR may also scale to efficiently connect the massive Internet of Things (IoT), and may offer new types of mission-critical services. | {
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For some time, as set forth in Patent Document 1 (Japanese Published Unexamined Patent Application 2013-44178), flush toilets have been known wherein in a wash-down type of flush toilet wherein a gravity feed storage tank is disposed as a water supply apparatus at the rear top portion of a flush toilet, the inside perimeter surface of the rim portion is formed to rise in an essentially plumb direction, and flush water is spouted from a rim spout port formed in the front region, to perform a flush as it circulates over the interior of the bowl portion. | {
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Fibroblast growth factors (FGFs) are known to play an important role in embryogenesis, tissue homeostasis, and metabolism via FGF receptor (FGFR) signals (Non Patent Literature 1). In humans, there are 22 FGFs (FGF1 to FGF14 and FGF16 to FGF23) and 4 FGF receptors (FGFR1 to FGFR4; hereinafter, collectively referred to as “FGFRs”) having a tyrosine kinase domain. These FGFRs are each composed of an extracellular region comprising a ligand binding site composed of 2 or 3 immunoglobulin-like domains (IgD1 to IgD3), a single-pass transmembrane region, and an intracellular region comprising the tyrosine kinase domain. FGFR1, FGFR2, and FGFR3 each have two splicing variants called IIIb and IIIc. These isoforms differ in the sequence of approximately 50 amino acids in the latter half of IgD3 and exhibit distinctive tissue distribution and ligand specificity. It is generally known that the IIIb isoform is expressed in epithelial cells, while the IIIc isoform is expressed in mesenchymal cells. The binding of FGFs to FGFRs induces the activation of many signaling pathways (Non Patent Literature 1). As a result, FGFs and their corresponding receptors control a wide range of cell functions including growth, differentiation, migration, and survival.
The abnormal activation of FGFRs is known to participate in particular types of malignant tumor development in humans (Non Patent Literature 1 and 2). Particularly, FGFR2 signal abnormalities such as the overexpression of FGFR2 and its ligand, receptor mutations or gene amplification, and isoform switching, have been found to be associated with cancer (Non Patent Literature 2, 3, 4, 5, 6 and 7).
As mentioned above, the possibility of FGFR2 as an excellent therapeutic target for cancer has been suggested. In fact, monoclonal antibodies against FGFR2 have been obtained and are under clinical trial (Non Patent Literatures 8, 9, 10, and 11).
For these reasons, the provision of methods capable of detecting expression of FGFR2 and its splicing variants is useful in the testing or diagnosis of FGFR2-related diseases such as cancer or of FGFR2 expression.
Many monoclonal antibodies which recognize human FGFR2 are known. However, very few of these known antibodies are capable of being used for immunohistological staining. For instance, only one clone known as 1G3 (Non Patent Literature 12) recognises denatured FGFR2 when fixed in formalin, which means it is capable of immunohistological staining. Neither antibody cross-reactivity to the denatured form of other FGFR families when fixed in formalin, nor selective recognition of the denatured human FGFR2 splicing variants IIIb and IIIc when fixed in formalin, have been reported.
A monoclonal antibody which selectively recognizes a denatured splicing variant IIIb of human FGFR2 fixed in formalin has been reported (Patent Literature 1). However, no monoclonal antibody which selectively recognizes a denatured human FGFR2 IIIc has been identified. | {
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In the prior art, there are known sealed and thermally insulative tanks intended to be fixed to a supporting structure and comprising a multi-layered structure consisting of one or more sealing membranes and one or more thermal insulation barriers each of which is interleaved between two sealing membranes or between a sealing membrane and the supporting structure.
One such tank is described in the document WO2014167228, for example. In that document, the sealing membrane of each wall of the tank includes a plurality of metal plates featuring series of corrugations perpendicular to one another. The corrugations therefore enable deformation of the sealing membranes because of the effect of thermal and mechanical loads generated by the fluid stored in the tank.
If the tank is mounted in the double hull of a ship, it generally has a polyhedron shape defined by two octagonal end walls connected to each other by a ceiling wall and a bottom wall that are horizontal, two vertical lateral walls, two upper oblique walls each connecting one of the lateral walls to the ceiling wall and two oblique lower walls each connecting one of the lateral walls to the bottom wall. The two series of corrugations of the sealing membrane of the end walls are respectively oriented horizontally and vertically while the two series of corrugations of the sealing membrane of the other walls are respectively oriented in the longitudinal direction of the tank and perpendicularly to the longitudinal direction of the tank.
At the level of each corner of the tank formed at the intersection between two of the eight walls connecting the two end walls and of each corner formed at the intersection between one of the end walls and one of the bottom, ceiling and laterals walls, one of the series of corrugations of each of the two adjacent walls extends in a direction perpendicular to the edge formed at the intersection between two said adjacent walls. The corrugations of the two adjacent walls therefore face one another and the sealing membrane of the corner arrangement features corrugations that assure continuity of the corrugations of the sealing membranes at the level of the corner zone between the two walls. This continuity of the corrugations therefore makes it possible to impart satisfactory flexibility to the sealing membrane at the level of the corner arrangement and to limit stress concentrations in that area.
However, this kind of continuity is not achieved at the level of the intersections between the end walls and the lower or upper oblique walls. In fact, the direction of the vertical corrugations and likewise that of the horizontal corrugations of the sealing member of each end wall are inclined at an angle of 45° relative to the edge formed at the intersection between the end wall and one of the oblique walls while the direction of the corrugations of said oblique wall is perpendicular to the edge. Thus none of the corrugations of the sealing membrane of the end walls is in line with the corrugations of the lower and upper oblique walls. The absence of any such continuity of the corrugations means that the corner arrangements between one of the oblique walls and one of the end walls constitute stress concentration areas and therefore constitute areas of weakness. | {
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The present invention relates to apparatus for adjusting a hair spring in which an appropriate length of the hair spring provided as part of an oscillating element is detected by electronic circuitry and in which the rest of the hair spring is automatically cut away.
One known type of apparatus for adjusting the frequency of, e.g., a balance wheel and for cutting a hair spring thereof, is described below. The oscillation output of the balance wheel is taken out, and the frequency is multiplied to drive a motor. On the other hand, an output frequency from a crystal oscillator is divided to a predetermined frequency, applied to drive another motor. Both the motors cause differential gears to rotate. The hair spring is conveyed in accordance with the rotation of a disc which is fixed to a shaft of the differential gears. When the numbers of revolutions of the motors coincide, an operator confirms the stop of the disc, and a switch of a cutting device is actuated by the operator to cut the hair spring. However, the apparatus is disadvantageous in that the operator need always confirm the stop of the disc. Besides, the mechanical structure occupies a large part of the apparatus and the two motors are included, so that the whole construction of the apparatus is large-sized. | {
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This invention relates to computer systems and methods used in manufacturing resource planning, and, more particularly, to a computer system and method for determining the daily demand for raw materials and other manufacturing resources used in a manufacturing process. The calculation of daily demand by the computer system and method of the present invention is based on anticipated (forecasted) or actual orders for a manufactured product and certain predetermined parameters associated with the manufacturing resources. The results of the computer system and method, i.e., the planned-for demand of manufacturing resources, when used to schedule and allocate manufacturing resources, provides sufficient availability of manufacturing resources to meet unanticipated demand for a manufactured product.
In the manufacturing or factory setting, customer orders for various items need to be processed and produced in a certain amount of time (e.g., by a promised shipping date). For every product ordered which is not already in finished goods inventory and therefore available to fill the customer order, a product must be manufactured. To manufacture the product, certain manufacturing resources (such as raw materials, machine or production line time, shift worker hours, and the like) used in a predetermined sequence of events (the manufacturing process) are required. In order to efficiently utilize the manufacturing resources of the manufacturing plant or factory, and ultimately to fulfill a multiplicity of customer orders, the manufacturer generally employs a system and method for scheduling the use of different resources at different dates and times. The resource schedules allow the manufacturer to plan for having sufficient resources available.
In traditional batch manufacturing methods for producing goods, raw materials are ordered well in advance and kept in a stockroom as raw material inventory. Such manufacturing methods typically use a scheduled batch manufacturing technique in which products are scheduled to be created based upon a weekly or monthly planning schedule. Usually these products are produced as subassemblies or fabricated parts that are scheduled based upon the weekly or monthly requirements for finished products. These subassemblies are then assembled into the final product to fill actual customer orders, or to be placed into finished goods inventory.
Once an assembly or fabricated part is scheduled to be produced, a work order is generated, and the parts required to manufacture the assembly or fabricated part are obtained from the stockroom based upon a planned manufacturing start date and order quantity. Subassembly parts are often produced in the same manner as the final product. Thus, after being produced, the subassemblies are stored until they are needed for a final assembly. Because of the length of time of each process, a large inventory of subassembly parts and finished goods is often needed to satisfy an unanticipated or fluctuating customer demand. This scheduled manufacturing process therefore requires a large amount of space for holding raw material inventory, subassembly parts inventory and finished goods inventory. Additionally, storing such large amounts of inventory results in additional costs related to loss and damage to raw materials, subassemblies and finished goods over time.
Computer software programs have been developed to efficiently accomplish many of the calculations used in batch manufacturing systems by materials planners in a manufacturing company to schedule and track raw materials inventory, batch subassemblies and fabricated parts. Typically, such computer software programs can calculate and determine, and even generate purchase orders, for obtaining the anticipated amount of raw materials required based on the planning schedule input by the materials planners. These computer software programs can also assist in the scheduling of manufacturing resources other than raw materials, such as the scheduling of manufacturing production lines and shift worker crews.
Other scheduling methods have been developed to assist in the planning of the acquisition of raw materials required in the manufacturing processes that utilize manufacturing methodologies other than batch manufacturing methods. Computer scheduling systems that employ these scheduling methods are generally referred to as materials requirement planning (MRP) systems. Typically, MRP scheduling systems assume an infinite capacity of machinery, shift worker hours, and the like, and the MRP system determines the amounts and types of raw materials that must be on hand at particular dates/times for a given manufacturing plant with given forecasted or actual orders.
Manufacturing resource planning (MRP II) systems, an improvement over the typical MRP systems, may also be used to schedule and allocate all kinds of manufacturing resources. MRP II systems generally also use customer orders and marketing forecasts to determine the quantity of manufacturing resources needed at any given time to produce anticipated customer orders. In MRP II systems, the number of days that it takes to manufacture a product from the time the initial manufactured components or subassemblies are produced until the final product is shipped is called the manufacturing lead time or pipeline. A long lead-time, caused by the subassembly manufacturing process, may make it difficult to react quickly to unanticipated customer orders. The lengthy process of long manufacturing lead times, queues for each subassembly, and frequent trips to the stockroom to obtain materials will introduce long periods of delay between manufacturing steps, and thus, a long period of time between the customer""s order and the completion and shipment of that order.
One of the more significant problems of these MRP II systems is that the production schedule is created well in advance, and cannot be altered easily. In addition, the computer software programs used in these processes generally lack the ability to easily adjust schedules when conditions change. If the manufacturing process is to become more flexible, the computer software programs used for scheduling should also become more flexible. In the typical MRP II system, however, the production quantity, or total demand on resources, is manually set by a master scheduler, and cannot easily be adjusted.
Therefore, prospective scheduling systems have been developed which identify where and when resource magnitude or timing constraints will be violated if a certain number of orders are received so that these violations may be resolved before they actually happen. However, relationships and constraints associated with products and processes must be accurately modeled in these systems if they are to predict future events with any degree of precision. Models can include process yield and probability factors, but cannot predict random events such as equipment failure, missing parts, or bad weather. Yet, random events must be considered and planned for in advance so that excess material and capacity stores can be used to prevent bottlenecks. The use of alternative resources can also prevent bottlenecks. In either case, timely recognition and response (i.e., scheduling around) is essential to maintaining productivity.
In any manufacturing environment, timely and precise resource plans and schedules are often a critical success factor. Material requirements planning systems enhanced with the above considerations can be used to determine future material requirements and potential shortages due to changing conditions and unexpected events, including unanticipated customer orders. The result of a successfully implemented system would be to reduce inventory and minimize material disruptions. However, even these kinds of material requirements planning systems function well only with definite and planned requirements (i.e., manufacturing systems in which products are built to meet forecasted amounts rather than actual customer orders), and where design changes (and therefore, changes in the manufacturing process and/or type and amount of raw materials) are infrequent.
Additionally, increased manufacturing flexibility, particularly in a factory that produces more than one product, creates a need for long term resource planning strategies based on production capacity and anticipated product mix. Similar scheduling methods may be applied to control other business operations including production capacity, distribution, equipment maintenance, and shop floor scheduling. Frequent adjustments to schedules may be required because small changes in requirements, status, products, processes or their constraints may result in dramatic changes to the requirements for many different resources.
It is thus apparent that there is a need for an improved system and method for automatically calculating the prospective total daily demand for manufacturing resources and automatically adjusting the demand, based on parameters relating to the resource, to accommodate unanticipated customer orders or other changes to the manufacturing process (including changes in the availability of raw materials). There is a further need for such a system that can allocate and schedule manufacturing resources to produce the maximum number of customer orders while minimizing the overhead and costs associated with maintaining excess resource inventory for capacity. The present invention meets these and other needs.
Generally speaking, in accordance with the present invention, an improved method and system to prospectively determine the daily demand for manufacturing resources in a manufacturing system is provided. More specifically, the method and system of the invention provides a projection of demand on manufacturing resources over time based on one or several of actual customer orders, future forecasts of customer orders, historical data of past customer shipments, current amounts of finished goods inventory, and predefined parameters related to the manufacturing resources.
The method and system is able to calculate when certain amounts of raw materials or other manufacturing resources are going to be needed based on when a customer order needs to be filled, and hence the system and method can additionally determine the date when the manufacturer needs to purchase or produce raw materials, refills, and the like (based on known supplier or manufacturing lead time), and plan to make those other resources available to produce the goods in time to meet a promised shipping date for an order to the customer. The invention therefore manages materials and other resources and may integrate the planning of manufacturing resources with an order acknowledgement system.
Furthermore, the method and system can allocate and schedule manufacturing resources, such as machine time or production line utilization, in a manner which minimizes waiting time of items to be fabricated, increases the productive use of the machine (i.e., decreases waste or leftover machine time) and maximizes the flexibility of the machine to support demand for several different products. For example, in a firing step of the factory process, it is ideal to place a maximum amount of items in a kiln each time the kiln is used. The system and method of the invention allows the kiln resource to be used (consumed) by more than one product at a time. The invention therefore provides efficient manufacturing resource plans that support customer demand requests over many products.
The system includes a database for storing predefined parameters, information about customer orders, and historical data. An input device is provided which allows an operator of the system to enter the parameters or other information. Alternatively, the input device may be linked to the output from various controlling mechanisms in the manufacturing process. An output device is provided to generate reports detailing the planned allocation of resources. In the case where raw materials are allocated for scheduled production, the output device may generate purchase orders. Alternatively, the output device may be linked to the input from various controlling mechanisms in the manufacturing process, or even linked to an ordering system of suppliers or customers.
The above and other aspects of the invention are accomplished in an improved method and system that determines the total demand for a manufacturing resource for each day over several time periods specified by the user of the system. For example, within the first time period, from the current date (i.e., today) up to a demand time fence (i.e., the manufacturing lead-time), the total demand may be altered, even though a quantity of products is already in production. The system of the invention utilizes minimum and maximum finished goods inventory targets to either supply additional products or consume excess products being made. Additionally, products with a delayed specific identity, i.e., generic finished goods orders, can be interchanged among related products within a generic finished goods order family prior to the step in which the product becomes unique.
For several periods beyond the demand time fence, called flex fence periods, the total demand for each day can vary by a percentage amount or a fixed number up and a percentage amount or a fixed number down (which percentage or number may be the same or may be different) determined by the user for each product. Each period can have a different percentage, for example, and each period can have a different number of days, however all days within a period use the same flex percentage for the period. The percentage amounts or fixed numbers represent planned-for excess capacity for which resources are made available in order to meet customer orders for the product that exceed forecasted amounts. The flex fences create available resource capacity that moves in the direction of solid customer order trends, and is determined by a number that includes weighted factors for one or more of current production amounts, future order forecasts and past customer shipment history.
Once the quantities within the flex periods have been determined, the system produces a plan for ordering raw materials and scheduling other manufacturing resources sufficient to build the total anticipated demand plus the flex fence demand. Thus the system creates the flexibility to fill customer orders up to the amounts determined by the upper flex fences.
If an order is received for a date beyond the demand time fence, and the order is larger than the total anticipated demand and the additional flex demand (called the high flex amount) for that date, the system and method can recalculate total demand for all days beyond the demand time fence date and prior to the order date to attempt to produce the total demand quantity necessary to fulfill the order in a process known as smoothing. In calculating the demand for manufacturing resources up to the flex fence amounts, the system uses an algorithm that adjusts the quantities in a manner that prevents the total demand quantity for any day from exceeding the amount of raw material and other resources that was planned to be available for that day. Therefore, unanticipated customer orders outside of the high flex amounts on the order date can be met, even though the manufacturer has only the flex amount of excess resource capacity and materials, by smoothing the demand over prior days.
The improved system and method of the invention also provides for intermediate reporting of the status of customer and finished goods replenishment orders at various points during the production pipeline. If a problem occurs, it is immediately recognized and reported so that the system can take an action to attempt to resolve the problem, such as by consuming demand for resources from other stores, e.g., from non-committed customer orders or marketing orders, available-to-promise amounts, finished goods inventory or finished goods replenishment orders.
The method and system of the invention may also solve a wide variety of resource management problems. Resources which may be managed include raw materials, machine or production line time, shift worker hours, other labor, space, power, or any other quantity whose constraint affects the ability to accept orders for the delivery of goods or services.
For example, in construction work, the scheduled use of resources may include construction workers with general or specialized skills, various single task or multi-purpose equipment, and materials requirements; in transportation, the efficient use of special or general purpose vehicles to transport people, materials, and equipment between a multitude of locations; in health care, the scheduled use of beds, operating rooms, general or specialized staff, and fixed or mobile equipment. Other uses of the system and method of the invention will readily be apparent to those who understand the embodiments disclosed herein.
Accordingly, it is an object of this invention to provide a system and method for planning, scheduling and allocating manufacturing resources in order to maximize manufacturing flexibility to meet unanticipated customer orders while minimizing the inventory costs and other costs associated with maintaining excess capacity of such resources.
Another object of the invention is to provide a system and method which may generate order acknowledgement projections based on whether sufficient manufacturing resources may be allocated in time to produce a customer order by a customer requested build completion date.
A further object is to provide a system and method which calculates when manufacturing resources are going to be needed and, hence, in what amount a manufacturer should buy raw materials, plan machinery time and schedule shift workers to operate the manufacturing line.
Yet another object is to provide a system and method which takes into account the capacity of each machine and staffing pool of the plant. To that end, each manufacturing resource is assigned a manageable amount of work and is not overloaded with assignments. In a like manner, reasonable amounts of the inventory of raw materials and subassemblies are calculated and maintained on hand in order to provide sufficient capacity to meet unanticipated demand, while minimizing the carrying costs and risk of damage or loss of such inventory.
Yet a further object of the invention is to provide a system and method that provides management of a company with detailed resource analysis information and plans.
Still yet another object of the invention is to provide a system and method that may modify order acknowledgement and resource planning projections each time new information is input.
Still other objects and advantages of the invention will in part be obvious and will in part be apparent from the following detailed specification.
The invention accordingly comprises the several steps and the relation of one or more such steps with respect to each of the others, and the system embodying features of construction, combinations of elements and arrangement of parts which are adapted to effect such steps, all as exemplified in the following detailed disclosure, and the scope of the invention will be indicated in the claims. | {
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The human body contains many joints that permit articulation of varying degrees between bones. Those that permit free articulation are referred to as diathroses. Examples include the hip, knee, elbow and shoulder. A variety of connective tissues are associated with the diathroses joints, including intra-articular cartilages that provide cushioning and smooth sliding surfaces, ligaments that provide flexible connections between bones and tendons that slide over joints and connect the muscles to provide motion. When connective tissues are compromised, joint pain and loss of function can result.
One example of compromised connective tissue is osteoarthritis of the knee or knee OA. The knee joint is formed by the articulation of the femur, patella, and tibia (FIGS. 1A and 1B). Like other freely articulating joints, the knee joint is enclosed by a fibrous joint capsule, lined by a synovial membrane. The inferior surface of the patella articulates with the femoral surface forming the patellofemoral joint. The distal end of the femur has two curved articular surfaces called the medial and lateral condyles. These surfaces articulate with the medial and lateral tibial condyles, forming the tibiofemoral joint, which flexes and extends the knee. Two fibrocartilagenous discs (i.e., menisci) lie between the tibial and femoral condyles to compensate for the incongruence of the articulating bones. Because the distal end of the femur is curved and asymmetric in shape, the knee joint not only flexes and extends like a hinge, but it also slides and rotates during flexion, resulting in a complex motion for the joint.
Knee OA is one of the most common causes of disability in the United States. OA is sometimes referred to as degenerative, or wear and tear, arthritis. OA is characterized by the breakdown of the articular cartilage within the joint. Over time, the cartilage may wear away entirely, resulting in bone-on-bone contact. Since bones, unlike cartilage, have many nerve cells, direct bone contact can be very painful to the OA sufferer. In addition to the pain and swelling, the OA sufferer can experience a progressive loss of mobility at the knee joint. This is due to loss of the joint space, where the articular cartilage has completely worn away. | {
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An endpoint, such as an access terminal, may use a system of communication networks to communicate packets with other endpoints during communication sessions. For example, an access terminal may subscribe to a network that maintains subscription information for the access terminal.
Certain known techniques may be used to make accounting records for these communication sessions. These known techniques, however, are not efficient in certain situations. In certain situations, it is generally desirable to be efficient. | {
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1. Field of the Invention
The present invention relates to the field of radio communication technologies. More particularly, the present invention relates to an apparatus and a method for feeding back data receiving status.
2. Description of the Related Art
A Long Term Evolution (LTE) system transmits data based on Hybrid Automatic Repeat Request (HARQ), i.e., a data receiver will send receiving status feedback information of Acknowledgement (ACK) or Non-Acknowledgement (NACK) according to the corresponding data receiving status. Scheduling information for dynamic downlink data transmission is transmitted through a Physical Downlink Control Channel (PDCCH), whereas except for Semi-Persistent Scheduling (SPS), initial transmission scheduling information for downlink data does not need to be transmitted through the PDCCH, and only at the time of retransmission of the downlink data, the scheduling information needs to be transmitted through the PDCCH.
For an LTE Time Division Duplexing (TDD) system, when the number of downlink subframes is larger than that of uplink subframes, receiving status feedback information for the data of multiple downlink subframes needs to be transmitted collectively in the same uplink subframe. One of the methods for the feeding back is to perform an “AND” operation on the receiving status feedback information for the downlink subframes that transmit data, so as to obtain receiving status feedback information of one bit for each code word. Because the downlink data transmission is scheduled dynamically through a PDCCH, and User Equipment (UE) may not be able to receive a PDCCH transmitted from a base station, there may be inconsistencies between the receiver and transmitter in the method of performing an “AND” operation according to code word. To address this problem, a Downlink Assignment Index (DAI) is used in the LTE TDD system to indicate the serial number of the current downlink subframe in the radio frame that transmits the PDCCH, so that the UE can detect whether a PDCCH in the downlink subframes has been lost. For a radio frame with 4 downlink subframes, the value of the DAI may be 1, 2, 3 and 4.
There is, however, a problem with the above method, i.e., a case in which the last several PDCCHs are lost cannot be detected. In the LTE TDD, therefore, it is specified that the UE needs to feed back receiving status feedback information on a receiving status feeding-back channel corresponding to the last one downlink subframe that receives a PDCCH, so that the base station can get aware of whether the UE has lost the PDCCHs of the last several downlink subframes from the channel on which the UE feeds back the receiving status feedback information.
In a Long Term Evolution-Advanced (LTE-A) system, a Carrier Aggregation (CA) technology has been used to support a higher transmission rate, in which two or more Component Carriers (CC) are aggregated to obtain a larger working bandwidth. For example, to support a bandwidth of 100 MHz, 5 CCs of 20 MHz may be aggregated. Based on CA, the base station transmits downlink data to the UE on two or more CCs. Correspondingly, the UE also needs to support the receiving status feedback information for the downlink data received from the two or more CCs.
According to the current results of discussions on LTE-A, at most 4 bits of ACK/NACK transmission can be supported based on the technology of channel selection. In LTE-A Frequency Division Duplexing (FDD), the method of channel selection actually supports only two CCs and at most 2 bits of ACK/NACK information can be fed back on each CC. Taking a 4-bit table as an example, for a Primary CC (PCC) and a Secondary CC (SCC) employing cross-CC scheduling, the two ACK/NCK channels are obtained by scheduling PDCCHs for downlink data transmission. For example, assuming the minimum CCE index of PDCCH is n, the two ACK/NACK channels may be obtained through mapping by using an LTE method from CCE indexes n and n+1. For a SCC not employing cross-CC scheduling, the two ACK/NACK channels are configured by the higher layer, and the flexibility in assignment may be increased through an ACK/NACK Resource Indicator (ARI). According to the current results of discussions, a 4-bit mapping table as shown in FIG. 3 is employed in an FDD system. Here, ACK/NACK channels 1 and 2 correspond to the two ACK/NACK bits of a PCC sequentially and ACK/NACK channels 3 and 4 correspond to the two ACK/NACK bits of a SCC sequentially. In the table of FIG. 3, the feature that the two ACK/NACK channels always are present at the same time on or absent at the same time from the same CC is utilized to optimize the performance. Another 4-bit mapping table is as shown in FIG. 12. Here, only when some ACK/NACK information is ACK, the ACK/NACK channel corresponding thereto is selected for transmission. The only exception is that to take full advantage of the feedback capabilities of M (M is equal to 2, 3 or 4) ACK/NACK channels, when the first piece of ACK/NACK information is NACK and the remaining pieces of ACK/NACK information are all NACK or Discontinuous Reception (DRX), a Quadrature Phase-Shift Keying (QPSK) constellation point of the first ACK/NACK channel may be used for the indication. The method as illustrated in FIG. 12 may be applied to the scenario in which the 4 ACK/NACK bits and the corresponding ACK/NACK channels are all independent of one another.
In the tables, N denotes NACK, A denotes ACK, D denotes DRX and the symbol “/” denotes “or”.
For an LTE-A TDD system, in a case of supporting CA, the UE needs to feed back significantly more bits of receiving status feedback information than in single carrier transmission. For example, when a radio frame has 4 downlink subframes for transmitting data and 5 CCs, assuming Multiple Input Multiple Output (MIMO) data transmission is configured for the UE, 40 bits of receiving status feedback information need to be fed back. Apparently, if the method of feeding back receiving status feedback information for single carrier is also used, many uplink overheads will be occupied and the uplink coverage area will be reduced. Moreover, all the uplink control channels currently supported in an LTE system cannot support so large an amount of receiving status feedback information. If it needs to support 40 bits of feedback, the structure of feeding-back channels needs to be redefined, which significantly increases the complexity of standardization.
Therefore, a need exists for an apparatus and a method for feeding back data receiving status, so as to reduce the uplink overheads occupied by the receiving status feedback information and increase the uplink coverage area. | {
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1. Field of the Invention
The present invention relates to an internal combustion engine system which uses a blended fuel of gasoline and ethanol, and can switch back and forth between spark ignition combustion and homogeneous charge compression ignition combustion.
2. Description of the Related Art
In recent years, in order to improve fuel efficiency and reduce the emission of an internal combustion engine, a compression ignition internal combustion engine represented by a homogeneous charge compression ignition internal combustion engine has been studied. However, the above described homogeneous charge compression ignition internal combustion engine has a problem that the engine has a narrow stably-operatable region, because the engine easily causes knocking when a high load is required, and easily causes misfire when a low load is required.
In order to solve the above described problem, a homogeneous charge compression ignition internal combustion engine has been conventionally known which is an internal combustion engine using gasoline, and can switch back and forth between spark ignition combustion and homogeneous charge compression ignition combustion (cf. Japanese Patent Laid-Open No. 2002-130006 and Japanese Patent Laid-Open No. 2001-152919, for instance).
The above described homogeneous charge compression ignition internal combustion engine usually conducts the above described homogeneous charge compression ignition combustion, and conducts the above described spark ignition combustion only when a requested load is higher than usual or lower than usual. The above described spark ignition combustion has an advantage of being capable of forcefully igniting fuel with a spark at the optimal timing, but has a disadvantage of greatly decreasing thermal efficiency when using a single fuel, because of needing to delay ignition timing to later timing than the optimal timing for avoiding knocking when a high load is required.
On the other hand, it has been known to use a blended fuel of gasoline and ethanol as a fuel for an internal combustion engine. It has been known that the above described blended fuel can provide a so-called carbon neutral effect because the blended fuel uses ethanol obtained by fermenting and distilling plants, for instance, farm products such as sugarcane and corn. The above described carbon neutral effect means that the combustion of ethanol obtained from plants does not theoretically increase the amount of emitted carbon dioxide after all, because the plant of a raw material in itself has already absorbed carbon dioxide, and even when the ethanol obtained from the plant is combusted, it emits carbon dioxide in an equal amount to what the plant has already absorbed.
Accordingly, a blended fuel of gasoline and ethanol can reduce an amount of emitted carbon dioxide and contribute to the prevention of global warming, by being used for automotive fuel.
However, the above described blended fuel has a problem that the blended fuel cannot sufficiently develop the above described carbon neutral effect, because even though the ethanol uses plants, the ethanol also makes fossil fuel consumed in the production process and the distribution process. The above described blended fuel has also a problem of needing a higher cost than general gasoline fuel and making the movable distance of the automobile shorter than that of an automobile using the general gasoline fuel, when both automobiles have the same capacity of the fuel tank, because the ethanol has a heating value per unit volume in an amount of only a little over 60% of the general gasoline fuel.
As for a method of using the above described blended fuel, a technology has been already known which includes adding water to the blended fuel to separate the blended fuel into gasoline and ethanol, and using gasoline and ethanol each independently (cf. Japanese Patent Laid-Open No. 58-96155). However, the technology is a method of separating ethanol from the above described blended fuel, further reforming the separated ethanol into gas consisting of hydrogen and carbon monoxide, and using the reformed gas, and accordingly does not sufficiently use the blended fuel efficiently.
For this reason, the internal combustion engine is demanded which can efficiently use a blended fuel of gasoline and ethanol. | {
"pile_set_name": "USPTO Backgrounds"
} |
This invention relates in general to apparatus for sensing displacement or position of an object, and in particular to apparatus which utilizes a flexible moveable band or other moveable element to convert a physical measure of displacement and position of an object into an electrical signal representing such measure.
In the operation of various mechanical and electro-mechanical systems, it is necessary to monitor the position and displacement of either some element of the system or some object which is not part of the system. For example, in robotic systems (a technology whose use is dramatically increasing) it is almost always necessary to monitor and control the movement and position of various component parts of the systems, such as an arm, fingers or other grasping elements, etc. Such monitoring and control yields the dexterity and precision required for a robotic system to carry out its functions.
Prior art mechanisms for sensing position and displacement have most often utilized a direct connection between the article or object whose position or displacement was to be monitored, and some type of gauge, needle or other visual indicator. Movement of the article or object would thus cause a corresponding movement of the gauge or needle. As expected, such mechanisms have typically been large and cumbersome and have lacked precision in carrying out the monitoring function. Further, since some type of sliding action of some part of the measuring mechanism typically was involved, friction was present which, of course, resulted in wear.
Although electronic apparatus for measuring position and displacement has come into greater use in recent years and has at least partially solved the bulkiness and imprecision problems of the prior art mechanisms, such apparatus has been complicated in design and, as a result of such complication, generally lacking in reliability. Also, the contact friction and attendant wear generally remained. | {
"pile_set_name": "USPTO Backgrounds"
} |
This invention relates to thermally developable materials containing certain backside conductive layers. In particular, the invention relates to thermographic and photothermographic materials containing metal antimonate conductive particles in backside conductive layers that are buried beneath a protective overcoat. The invention also relates to methods of imaging the thermally developable materials.
Silver-containing thermographic and photothermographic imaging materials (that is, thermally developable imaging materials) that are imaged and/or developed using heat and without liquid processing have been known in the art for many years.
Silver-containing thermographic imaging materials are non-photosensitive materials that are used in a recording process wherein images are generated by the use of thermal energy. These materials generally comprise a support having disposed thereon (a) a relatively or completely non-photosensitive source of reducible silver ions, (b) a reducing composition (usually including a developer) for the reducible silver ions, and (c) a suitable hydrophilic or hydrophobic binder.
In a typical thermographic construction, the image-forming layers are based on silver salts of long chain fatty acids. Typically, the preferred non-photosensitive reducible silver source is a silver salt of a long chain aliphatic carboxylic acid having from 10 to 30 carbon atoms. The silver salt of behenic acid or mixtures of acids of similar molecular weight are generally used. At elevated temperatures, the silver of the silver carboxylate is reduced by a reducing agent for silver ion such as methyl gallate, hydroquinone, substituted-hydroquinones, hindered phenols, catechols, pyrogallol, ascorbic acid, and ascorbic acid derivatives, whereby an image of elemental silver is formed. Some thermographic constructions are imaged by contacting them with the thermal head of a thermographic recording apparatus such as a thermal printer or thermal facsimile. In such constructions, an anti-stick layer is coated on top of the imaging layer to prevent sticking of the thermographic construction to the thermal head of the apparatus utilized. The resulting thermographic construction is then heated to an elevated temperature, typically in the range of from about 60 to about 225xc2x0 C., resulting in the formation of an image.
Silver-containing photothermographic imaging materials are photosensitive materials that are used in a recording process wherein an image is formed by imagewise exposure of the photothermographic material to specific electromagnetic radiation (for example, X-radiation, or ultraviolet, visible, or infrared radiation) and developed by the use of thermal energy. These materials, also known as xe2x80x9cdry silverxe2x80x9d materials, generally comprise a support having coated thereon: (a) a photocatalyst (that is, a photosensitive compound such as silver halide) that upon such exposure provides a latent image in exposed grains that are capable of acting as a catalyst for the subsequent formation of a silver image in a development step, (b) a relatively or completely non-photosensitive source of reducible silver ions, (c) a reducing composition (usually including a developer) for the reducible silver ions, and (d) a hydrophilic or hydrophobic binder. The latent image is then developed by application of thermal energy.
In such materials, the photosensitive catalyst is generally a photographic type photosensitive silver halide that is considered to be in catalytic proximity to the non-photosensitive source of reducible silver ions. Catalytic proximity requires intimate physical association of these two components either prior to or during the thermal image development process so that when silver atoms (Ag0)n, also known as silver specks, clusters, nuclei or latent image, are generated by irradiation or light exposure of the photosensitive silver halide, those silver atoms are able to catalyze the reduction of the reducible silver ions within a catalytic sphere of influence around the silver atoms [D. H. Klosterboer, Imaging Processes and Materials, (Neblette""s Eighth Edition), J. Sturge, V. Walworth, and A. Shepp, Eds., Van Nostrand-Reinhold, New York, 1989, Chapter 9, pp. 279-291]. It has long been understood that silver atoms act as a catalyst for the reduction of silver ions, and that the photosensitive silver halide can be placed in catalytic proximity with the non-photosensitive source of reducible silver ions in a number of different ways (see, for example, Research Disclosure, June 1978, item 17029). Other photosensitive materials, such as titanium dioxide, cadmium sulfide, and zinc oxide have also been reported to be useful in place of silver halide as the photocatalyst in photothermographic materials [see for example, Shepard, J. Appl. Photog. Eng. 1982, 8(5), 210-212, Shigeo et al., Nippon Kagaku Kaishi, 1994, 11, 992-997, and FR 2,254,047 (Robillard)].
The photosensitive silver halide may be made xe2x80x9cin-situ,xe2x80x9d for example by mixing an organic or inorganic halide-containing source with a source of reducible silver ions to achieve partial metathesis and thus causing the in-situ formation of silver halide (AgX) grains throughout the silver source [see, for example, U.S. Pat. No. 3,457,075 (Morgan et al.)]. In addition, photosensitive silver halides and sources of reducible silver ions can be coprecipitated [see Yu. E. Usanov et al., J. Imag. Sci. Tech. 1996, 40, 104]. Alternatively, a portion of the reducible silver ions can be completely converted to silver halide, and that portion can be added back to the source of reducible silver ions (see Yu. E. Usanov et al., International Conference on Imaging Science, Sep. 7-11, 1998, pp. 67-70).
The silver halide may also be xe2x80x9cpreformedxe2x80x9d and prepared by an xe2x80x9cex-situ xe2x80x9d process whereby the silver halide (AgX) grains are prepared and grown separately. With this technique, one has the possibility of controlling the grain size, grain size distribution, dopant levels, and composition much more precisely, so that one can impart more specific properties to both the silver halide grains and the photothermographic material. The preformed silver halide grains may be introduced prior to and be present during the formation of the source of reducible silver ions. Co-precipitation of the silver halide and the source of reducible silver ions provides a more intimate mixture of the two materials [see for example U.S. Pat. No. 3,839,049 (Simons)]. Alternatively, the preformed silver halide grains may be added to and physically mixed with the source of reducible silver ions.
The non-photosensitive source of reducible silver ions is a material that contains reducible silver ions. Typically, the preferred non-photosensitive source of reducible silver ions is a silver salt of a long chain aliphatic carboxylic acid having from 10 to 30 carbon atoms, or mixtures of such salts. Such acids are also known as xe2x80x9cfatty acidsxe2x80x9d or xe2x80x9cfatty carboxylic acidsxe2x80x9d. Silver salts of other organic acids or other organic compounds, such as silver imidazoles, silver tetrazoles, silver benzotriazoles, silver benzotetrazoles, silver benzothiazoles and silver acetylides may also be used. U.S. Pat. No. 4,260,677 (Winslow et al.) discloses the use of complexes of various inorganic or organic silver salts.
In photothermographic materials, exposure of the photographic silver halide to light produces small clusters containing silver atoms (Ag0)n. The imagewise distribution of these clusters, known in the art as a latent image, is generally not visible by ordinary means. Thus, the photosensitive material must be further developed to produce a visible image. This is accomplished by the reduction of silver ions that are in catalytic proximity to silver halide grains bearing the silver-containing clusters of the latent image. This produces a black-and-white image. The non-photosensitive silver source is catalytically reduced to form the visible black-and-white negative image while much of the silver halide, generally, remains as silver halide and is not reduced.
In photothermographic materials, the reducing agent for the reducible silver ions, often referred to as a xe2x80x9cdeveloper,xe2x80x9d may be any compound that, in the presence of the latent image, can reduce silver ion to metallic silver and is preferably of relatively low activity until it is heated to a temperature sufficient to cause the reaction. A wide variety of classes of compounds have been disclosed in the literature that function as developers for photothermographic materials. At elevated temperatures, the reducible silver ions are reduced by the reducing agent. In photothermographic materials, upon heating, this reaction occurs preferentially in the regions surrounding the latent image. This reaction produces a negative image of metallic silver having a color that ranges from yellow to deep black depending upon the presence of toning agents and other components in the imaging layer(s).
The imaging arts have long recognized that the field of photothermography is clearly distinct from that of photography. Photothermographic materials differ significantly from conventional silver halide photographic materials that require processing with aqueous processing solutions.
As noted above, in photothermographic imaging materials, a visible image is created by heat as a result of the reaction of a developer incorporated within the material. Heating at 50xc2x0 C. or more is essential for this dry development. In contrast, conventional photographic imaging materials require processing in aqueous processing baths at more moderate temperatures (from 30xc2x0 C. to 50xc2x0 C.) to provide a visible image.
In photothermographic materials, only a small amount of silver halide is used to capture light and a non-photosensitive source of reducible silver ions (for example a silver carboxylate) is used to generate the visible image using thermal development. Thus, the imaged photosensitive silver halide serves as a catalyst for the physical development process involving the non-photosensitive source of reducible silver ions and the incorporated reducing agent. In contrast, conventional wet-processed, black-and-white photographic materials use only one form of silver (that is, silver halide) that, upon chemical development, is itself at least partially converted into the silver image, or that upon physical development requires addition of an external silver source (or other reducible metal ions that form black images upon reduction to the corresponding metal). Thus, photothermographic materials require an amount of silver halide per unit area that is only a fraction of that used in conventional wet-processed photographic materials.
In photothermographic materials, all of the xe2x80x9cchemistryxe2x80x9d for imaging is incorporated within the material itself. For example, such materials include a developer (that is, a reducing agent for the reducible silver ions) while conventional photographic materials usually do not. Even in so-called xe2x80x9cinstant photography,xe2x80x9d the developer chemistry is physically separated from the photosensitive silver halide until development is desired. The incorporation of the developer into photothermographic materials can lead to increased formation of various types of xe2x80x9cfogxe2x80x9d or other undesirable sensitometric side effects. Therefore, much effort has gone into the preparation and manufacture of photothermographic materials to minimize these problems during the preparation of the photothermographic emulsion as well as during coating, use, storage, and post-processing handling.
Moreover, in photothermographic materials, the unexposed silver halide generally remains intact after development and the material must be stabilized against further imaging and development. In contrast, silver halide is removed from conventional photographic materials after solution development to prevent further imaging (that is in the aqueous fixing step).
In photothermographic materials, the binder is capable of wide variation and a number of binders (both hydrophilic and hydrophobic) are useful. In contrast, conventional photographic materials are limited almost exclusively to hydrophilic colloidal binders such as gelatin.
Because photothermographic materials require dry thermal processing, they present distinctly different problems and require different materials in manufacture and use, compared to conventional, wet-processed silver halide photographic materials. Additives that have one effect in conventional silver halide photographic materials may behave quite differently when incorporated in photothermographic materials where the underlying chemistry is significantly more complex. The incorporation of such additives as, for example, stabilizers, antifoggants, speed enhancers, supersensitizers, and spectral and chemical sensitizers in conventional photographic materials is not predictive of whether such additives will prove beneficial or detrimental in photothermographic materials. For example, it is not uncommon for a photographic antifoggant useful in conventional photographic materials to cause various types of fog when incorporated into photothermographic materials, or for supersensitizers that are effective in photographic materials to be inactive in photothermographic materials.
These and other distinctions between photothermographic and photographic materials are described in Imaging Processes and Materials (Neblette""s Eighth Edition), noted above, Unconventional Imaging Processes, E. Brinckman et al. (Eds.), The Focal Press, London and New York, 1978, pp. 74-75, in Zou et al., J. Imaging Sci. Technol. 1996, 40, pp. 94-103, and in M. R. V. Sahyun, J. Imaging Sci. Technol. 1998, 42, 23.
Many of the chemicals used to make supports or supported layers in thermally developable materials have electrically insulating properties, and electrostatic charges frequently build up on the materials during manufacture, packaging, and use. The accumulated charges can cause various problems. For example, in photothermographic materials containing photosensitive silver halides, accumulated electrostatic charge can generate light to which the silver halides are sensitive. This may result in imaging defects that are a particular problem where the images are used for medical diagnosis.
Build-up of electrostatic charge can also cause sheets of imageable material to stick together causing misfeeds and jamming within processing equipment. Additionally, accumulated electrostatic charge can attract dust or other particulate matter to the imageable material, thereby requiring more cleaning means so transport through the processing equipment and image quality of the material are not diminished.
Build-up of electrostatic charge also makes handling of developed sheets of imaged material more difficult. For example, a radiologist desires a static free sheet for viewing on the light boxes. This problem can be particularly severe when reviewing an imaged film that has been stored for a lengthy period of time because many antistatic materials loose their effectiveness over time.
In general, electrostatic charge is related to surface resistivity (measured in ohm/sq) and charge level. While electrostatic charge control agents (or antistatic agents) can be included in any layer of an imaging material, the accumulation of electrostatic charge can be prevented by reducing the surface resistivity or by lowering the charge level. This is usually done by including charge control agents in surface layers. Such surface layers may include what are known as xe2x80x9cprotectivexe2x80x9d overcoats or various backing layers in imaging materials. In thermographic and photothermographic materials, charge control agents may be incorporated into backing layers (such as antihalation layers of photothermographic materials) that are on the opposite side of the support as the imaging layers.
A wide variety of charge control agents, both inorganic and organic, have been devised and used for electrostatic charge control and numerous publications describe such agents. Some charge control agents are designed to increase surface layer conductivity while others are designed to control the generation of surface electrostatic charge.
U.S. Pat. No. 5,340,676 (Anderson et al.) describes the use of various metal oxides in conductive layers of various types of imaging elements. U.S. Published Application 2001-0055490 (Oyamada) describes the use of similar metal oxides dispersed in one or more binders on the backside layers of thermally developable materials.
Fine particle metal antimonates are used in conductive layers of imaging elements including thermal imaging elements described in U.S. Pat. No. 5,368,995 (Christian et al.) and U.S. Pat. No. 5,457,013 (Christian et al.). Various binders can be used in these conductive layers that can be located in various locations in the elements.
U.S. Pat. No. 5,731,119 (Eichorst et al.) describes the use of acicular metal oxides in conductive layers and further describes an antistatic composition containing granular zinc antimonate in a polyurethane binder.
U.S. Pat. No. 6,355,405 (Ludemann et al.) describes thermally developable materials that include adhesion-promoting layers on either side of the support. These adhesion-promoting layers are usually very thin, include specific mixtures of polymers to provide the adhesion function, and are also known as xe2x80x9ccarrierxe2x80x9d layers. These layers can have a variety of other functions and may include materials that may improve coatability or adhesion, antihalation dyes, crosslinking agents (such as diisocyanates), surfactants and shelf-aging promoters.
Despite the considerable research and knowledge in the art relating to the use of various conductive compositions and imaging materials, there remains a need for conductive compositions that can be used on the backside of thermally developable imaging materials underneath the protective overcoats to provide improved shelf keeping properties and high conductivity.
The present invention provides a thermally developable material that comprises a support having on one side thereof, one or more thermally developable imaging layers comprising a binder and in reactive association, a non-photosensitive source of reducible silver ions, and a reducing agent composition for the non-photosensitive source reducible silver ions, and
having disposed on the backside of the support:
a) a first layer comprising a film-forming polymer, and
b) interposed between the support and the first layer and directly adhering the first layer to the support, a non-imaging backside conductive layer comprising non-acicular metal antimonate particles in a mixture of two or more polymers that include a first polymer serving to promote adhesion of the conductive layer directly to the support, and a second polymer that is different than and forms a single phase mixture with the first polymer,
wherein the film-forming polymer of the first layer and the second polymer of the conductive layer are the same or different polyvinyl acetal resins, polyester resins, cellulosic polymers, maleic anhydride-ester copolymers, or vinyl polymers.
Thus, in some embodiments, this invention provides a photothermographic material that comprises a support having on one side thereof, one or more thermally developable imaging layers comprising a binder and in reactive association, a photosensitive silver halide, a non-photosensitive source of reducible silver ions, and a reducing composition for the non-photosensitive source reducible silver ions, and
having disposed on the backside of the support:
a) a first layer comprising a film-forming polymer, and
b) interposed between the support and the first layer and directly adhering the first layer to the support, a non-imaging backside conductive layer comprising non-acicular metal antimonate particles in a mixture of two or more polymers that include a first polymer serving to promote adhesion of the backside conductive layer directly to the support, and a second polymer that is different than and forms a single phase mixture with the first polymer,
wherein the film-forming polymer of the first layer and the second polymer of the backside conductive layer are the same or different polyvinyl acetal resins, polyester resins, cellulosic polymers, maleic anhydride-ester copolymers, or vinyl polymers.
In one preferred embodiment, the present invention provides a black-and-white photothermographic material that comprises a transparent polymeric support having on one side thereof one or more thermally developable imaging layers comprising predominantly one or more hydrophobic binders including at least polyvinyl butyral, and in reactive association, a preformed photosensitive silver bromide or silver iodobromide present as tabular and/or cubic grains, a non-photosensitive source of reducible silver ions that includes one or more silver aliphatic carboxylates at least one of which is silver behenate, a reducing agent composition for the non-photosensitive source reducible silver ions comprising a hindered phenol or mixture thereof, and a protective layer disposed over the one or more thermally developable imaging layers, and
having disposed on the backside of the support:
a) a backside protective layer comprising a film-forming polymer that is cellulose acetate butyrate, and
b) interposed between the support and the backside protective layer and directly adhering the backside protective layer to the support, a non-imaging backside conductive layer comprising non-acicular metal antimonate particles in a mixture of two or more polymers that include a first polymer serving to promote adhesion of the backside conductive layer directly to the support, and a second polymer that is different than and forms a single phase mixture with the first polymer,
wherein the first polymer of the backside conductive layer is a polyester and the second polymer of the backside conductive layer is cellulose acetate butyrate, and
the non-acicular metal antimonate particles are composed of ZnSb2O6 and comprise from about 40 to about 55% by weight and are present in the backside conductive layer in an amount of from about 0.05 to about 2 g/m .
In another preferred embodiment, the present invention provides a black-and-white thermographic material that comprises a transparent polymeric support having on one side thereof one or more thermally developable imaging layers comprising predominantly one or more hydrophobic binders including at least polyvinyl butyral, and in reactive association, a non-photosensitive source of reducible silver ions that includes one or more silver aliphatic carboxylates at least one of which is silver behenate, a reducing agent composition for the non-photosensitive source reducible silver ions comprising an aromatic di- and tri-hydroxy compound having at least two hydroxy groups in ortho- or para-relationship on the same aromatic nucleus or mixture thereof, and a protective layer disposed over the one or more thermally developable imaging layers, and
having disposed on the backside of the support:
a) a backside protective layer comprising a film-forming polymer that is cellulose acetate butyrate, and
b) interposed between the support and the backside protective layer and directly adhering the backside protective layer to the support, a non-imaging backside conductive layer comprising non-acicular metal antimonate particles in a mixture of two or more polymers that include a first polymer serving to promote adhesion of the backside conductive layer directly to the support, and a second polymer that is different than and forms a single phase mixture with the first polymer,
wherein the first polymer of the backside conductive layer is a polyester and the second polymer of the backside conductive layer is polyvinyl butyral or cellulose acetate butyrate and
the non-acicular metal antimonate particles are composed of ZnSb2O6 and comprise from about 40 to about 55% by weight of the buried backside conductive layer and are present in the conductive layer in an amount of from about 0.05 to about 2 g/m2.
The present invention provides a thermally developable material that comprises a support having on one side thereof, one or more thermally developable imaging layers comprising a binder and in reactive association, a non-photosensitive source of reducible silver ions, and a reducing agent composition for the non-photosensitive source reducible silver ions, and
having disposed on the backside of the support:
a) a first layer comprising a film-forming polymer,
b) a second layer directly adhered to the support, comprising a mixture of two or more polymers that includes a first polymer serving to promote adhesion of the second layer directly to the support, and a second polymer that is different than and forms a single phase mixture with the first polymer, and
c) interposed between the first layer and the second layer, a non-imaging backside conductive layer comprising non-acicular metal antimonate particles in a polymer serving to promote adhesion of the backside conductive layer directly to the first and second layers,
wherein the film-forming polymer of the first layer, the polymer of the conductive layer, and the second polymer of the second layer are the same or different polyvinyl acetal resins, polyester resins, cellulosic polymers, maleic anhydride-ester copolymers, or vinyl polymers.
The present invention provides a thermally developable material that comprises a support having on one side thereof, one or more thermally developable imaging layers comprising a binder and in reactive association, a non-photosensitive source of reducible silver ions, and a reducing agent composition for the non-photosensitive source reducible silver ions, and
having disposed on the backside of the support:
a) a first layer comprising a film-forming polymer,
b) a second layer directly adhered to the support, comprising a first polymer, and
c) interposed between the first layer and the second layer, a non-imaging backside conductive layer comprising non-acicular metal antimonate particles in a mixture of two or more polymers that includes the first polymer that serves to promote adhesion to the second layer, and a second polymer that is different than and forms a single phase mixture with the first polymer, and serves to promote adhesion to the first layer,
wherein the film-forming polymer of the first layer and one of the two or more polymers of the backside conductive layer are the same or different polyvinyl acetal resins, polyester resins, cellulosic polymers, maleic anhydride-ester copolymers, or vinyl polymers.
Further, the present invention provides a method of forming a visible image comprising:
a) imagewise exposing a photothermographic material of the present invention to electromagnetic radiation to form a latent image,
b) simultaneously or sequentially, heating the exposed photothermographic material to develop the latent image into a visible image.
In embodiments wherein the thermally developable material of the present invention is a thermographic material, a method of forming a visible image comprises thermal imaging of the thermally developable material.
In some embodiments wherein the thermographic or photothermographic material comprises a transparent support, the image-forming method further comprises:
c) positioning the exposed and heat-developed photothermographic material with the visible image thereon between a source of imaging radiation and an imageable material that is sensitive to the imaging radiation, and
d) thereafter exposing the imageable material to the imaging radiation through the visible image in the exposed and heat-developed photothermographic material to provide an image in the imageable material.
The present invention provides a number of advantages with the use of specific metal antimonates on the backside of the thermally developable materials. More specifically, the backside conductive layer is located underneath other layers such as an outermost protective layer so the conductive layer provides both conductivity as well as adhesion while the other layers can be designed with other properties. Since the conductive layer is xe2x80x9cburiedxe2x80x9d under the other layers, it is protected from dirt, dust, and fingerprints. The other layer (identified herein as the xe2x80x9cfirstxe2x80x9d layer) can be composed of different but xe2x80x9ccompatiblexe2x80x9d polymers and provide antihalation, physical and chemical protection and improved film transport.
Moreover, we have found that if the backside conductive layer is xe2x80x9cburied,xe2x80x9d the efficiency of the metal antimonate particles is improved. That is, fewer conductive particles are needed than when they are incorporated into the outermost layer. Also, by controlling the thickness of, or the amount of the metal antimonate in this xe2x80x9cburiedxe2x80x9d layer, the conductivity of the layer can be more readily adjusted. Additionally, when the backside conductive layer is xe2x80x9cburied,xe2x80x9d lower Dmin values can be obtained. Furthermore, use of metal antimonate particles in a xe2x80x9cburiedxe2x80x9d backside conductive layer has been found to reduce penetration of superposed layers into the coating slot of the xe2x80x9cburiedxe2x80x9d backside conductive layer during slide coating.
The thermally developable materials of this invention include both thermographic and photothermographic materials. While the following discussion will often be directed primarily to the preferred photothermographic embodiments, it would be readily understood by one skilled in the imaging arts that thermographic materials can be similarly constructed (using one or more imaging layers) and used to provide black-and-white or color images using non-photosensitive silver salts, reducing compositions, binders, and other components known to be useful in such embodiments. In both thermographic and photothermographic materials, the non-acicular metal antimonate particles described herein are generally incorporated into a separate conductive (xe2x80x9cantistaticxe2x80x9d) layer on at least the backside and optionally on both sides of the support.
The thermographic and photothermographic materials of this invention can be used in black-and-white or color thermography or photothermography and in electronically generated black-and-white or color hardcopy recording. They can be used in microfilm applications, in radiographic imaging (for example digital medical imaging), X-ray radiography, and in industrial radiography. Furthermore, the absorbance of these thermographic and photothermographic materials between 350 and 450 nm is desirably low (less than 0.5), to permit their use in the graphic arts area (for example, imagesetting and phototypesetting), in the manufacture of printing plates, in contact printing, in duplicating (xe2x80x9cdupingxe2x80x9d), and in proofing.
The thermographic and photothermographic materials of this invention are particularly useful for medical imaging of human or animal subjects in response to visible or X-radiation. Such applications include, but are not limited to, thoracic imaging, mammography, dental imaging, orthopedic imaging, general medical radiography, therapeutic radiography, veterinary radiography, and auto-radiography. When used with X-radiation, the photothermographic materials of this invention may be used in combination with one or more phosphor intensifying screens, with phosphors incorporated within the photothermographic emulsion, or with a combination thereof. The materials of this invention are also useful for non-medical uses of visible or X-radiation (such as X-ray lithography and industrial radiography).
The photothermographic materials of this invention can be made sensitive to radiation of any suitable wavelength. Thus, in some embodiments, the materials are sensitive at ultraviolet, visible, infrared or near infrared wavelengths, of the electromagnetic spectrum. In preferred embodiments, the materials are sensitive to radiation greater than 700 nm (and generally up to 1150 xcexcm). In other embodiments they are sensitive to X-radiation. Increased sensitivity to a particular region of the spectrum is imparted through the use of various sensitizing dyes.
The photothermographic materials of this invention are also useful for non-medical uses of visible or X-radiation (such as X-ray lithography and industrial radiography). In such imaging applications, it is often desirable that the photothermographic materials be xe2x80x9cdouble-sided.xe2x80x9d
In the photothermographic materials of this invention, the components needed for imaging can be in one or more thermally developable layers on one side (xe2x80x9cfrontsidexe2x80x9d) of the support. The layer(s) that contain the photosensitive photocatalyst (such as a photosensitive silver halide in photothermographic materials) or non-photosensitive source of reducible silver ions, or both, are referred to herein as photothermographic emulsion layer(s). The photocatalyst and the non-photosensitive source of reducible silver ions are in catalytic proximity (that is, in reactive association with each other) and preferably are in the same emulsion layer.
Similarly, in the thermographic materials of this invention, the components needed for imaging can be in one or more layers. The layer(s) that contain the non-photosensitive source of reducible silver ions are referred to herein as thermographic emulsion layer(s).
Where the materials contain imaging layers on one side of the support only, various non-imaging layers are usually disposed on the xe2x80x9cbacksidexe2x80x9d (non-emulsion or non-imaging side) of the materials, including at least one conductive layer described herein, and optionally antihalation layer(s), protective layers, and transport enabling layers.
In such instances, various non-imaging layers can also be disposed on the xe2x80x9cfrontsidexe2x80x9d or imaging or emulsion side of the support, including protective topcoat layers, primer layers, interlayers, opacifying layers, antistatic layers, antihalation layers, acutance layers, auxiliary layers, and other layers readily apparent to one skilled in the art.
For some applications it may be useful that the photothermographic materials be xe2x80x9cdouble-sidedxe2x80x9d and have photothermographic coatings on both sides of the support. In such constructions each side can also include one or more protective topcoat layers, primer layers, interlayers, antistatic layers, acutance layers, auxiliary layers, anti-crossover layers, and other layers readily apparent to one skilled in the art.
When the thermographic and photothermographic materials of this invention are heat-developed as described below in a substantially water-free condition after, or simultaneously with, imagewise exposure, a silver image (preferably a black-and-white silver image) is obtained.
As used herein:
In the descriptions of the photothermographic materials of the present invention, xe2x80x9caxe2x80x9d or xe2x80x9canxe2x80x9d component refers to xe2x80x9cat least onexe2x80x9d of that component (for example, the specific metal antimonates in the backside conductive layer).
The term xe2x80x9cpolymerxe2x80x9d when referring to polymeric materials is defined to include homopolymers, copolymers and terpolymers.
Heating in a substantially water-free condition as used herein, means heating at a temperature of from about 50xc2x0 C. to about 250xc2x0 C. with little more than ambient water vapor present. The term xe2x80x9csubstantially water-free conditionxe2x80x9d means that the reaction system is approximately in equilibrium with water in the air and water for inducing or promoting the reaction is not particularly or positively supplied from the exterior to the material. Such a condition is described in T. H. James, The Theory of the Photographic Process, Fourth Edition, Eastman Kodak Company, Rochester, N.Y., 1977, p. 374.
xe2x80x9cPhotothermographic material(s)xe2x80x9d means a construction comprising at least one photothermographic emulsion layer or a photothermographic set of layers, wherein the photosensitive silver halide and the source of reducible silver ions are in one layer and the other essential components or desirable additives are distributed, as desired, in the same layer or in an adjacent coating layer, as well as any supports, topcoat layers, image-receiving layers, blocking layers, antihalation layers, subbing or priming layers. These materials also include multilayer constructions in which one or more imaging components are in different layers, but are in xe2x80x9creactive associationxe2x80x9d so that they readily come into contact with each other during imaging and/or development. For example, one layer can include the non-photosensitive source of reducible silver ions and another layer can include the reducing composition, but the two reactive components are in reactive association with each other.
xe2x80x9cThermographic materialsxe2x80x9d are similarly defined except that no photosensitive silver halide is present.
When used in photothermography, the term, xe2x80x9cimagewise exposingxe2x80x9d or xe2x80x9cimagewise exposurexe2x80x9d means that the material is imaged using any exposure means that provides a latent image using electromagnetic radiation. This includes, for example, by analog exposure where an image is formed by projection onto the photosensitive material as well as by digital exposure where the image is formed one pixel at a time such as by modulation of scanning laser radiation.
When used in thermography, the term, xe2x80x9cimagewise exposingxe2x80x9d or xe2x80x9cimagewise exposurexe2x80x9d means that the material is imaged using any means that provides an image using heat. This includes, for example, by analog exposure where an image is formed by differential contact heating through a mask using a thermal blanket or infrared heat source, as well as by digital exposure where the image is formed one pixel at a time such as by modulation of thermal print-heads.
xe2x80x9cCatalytic proximityxe2x80x9d or xe2x80x9creactive associationxe2x80x9d means that the materials are in the same layer or in adjacent layers so that they readily come into contact with each other during thermal imaging and development.
xe2x80x9cEmulsion layer,xe2x80x9d xe2x80x9cimaging layer,xe2x80x9d xe2x80x9cthermographic emulsion layer,xe2x80x9d or xe2x80x9cphotothermographic emulsion layer,xe2x80x9d means a layer of a thermographic or photothermographic material that contains the photosensitive silver halide (when used) and/or non-photosensitive source of reducible silver ions. It can also mean a layer of the thermographic or photothermographic material that contains, in addition to the photosensitive silver halide (when used) and/or non-photosensitive source of reducible ions, additional essential components and/or desirable additives. These layers are usually on what is known as the xe2x80x9cfrontsidexe2x80x9d of the support.
xe2x80x9cPhotocatalystxe2x80x9d means a photosensitive compound such as silver halide that, upon exposure to radiation, provides a compound that is capable of acting as a catalyst for the subsequent development of the image-forming material.
Some of the materials used herein are provided as a solution or dispersion. The term xe2x80x9cactive ingredientxe2x80x9d or xe2x80x9cactive solidsxe2x80x9d means the amount or the percentage of the desired material contained in a sample. All amounts listed herein are the amount of active ingredient added unless otherwise specified.
xe2x80x9cUltraviolet region of the spectrumxe2x80x9d refers to that region of the spectrum less than or equal to 410 nm, and preferably from about 100 nm to about 410 nm, although parts of these ranges may be visible to the naked human eye. More preferably, the ultraviolet region of the spectrum is the region of from about 190 to about 405 nm.
xe2x80x9cVisible region of the spectrumxe2x80x9d refers to that region of the spectrum of from about 400 nm to about 700 nm.
xe2x80x9cShort wavelength visible region of the spectrumxe2x80x9d refers to that region of the spectrum of from about 400 nm to about 450 nm.
xe2x80x9cRed region of the spectrumxe2x80x9d refers to that region of the spectrum of from about 600 nm to about 700 nm.
xe2x80x9cInfrared region of the spectrumxe2x80x9d refers to that region of the spectrum of from about 700 nm to about 1400 nm.
xe2x80x9cNon-photosensitivexe2x80x9d means not intentionally light sensitive.
The sensitometric terms xe2x80x9cphotospeed,xe2x80x9d xe2x80x9cspeed,xe2x80x9d or xe2x80x9cphotographic speedxe2x80x9d (also known as sensitivity), absorbance, contrast, Dmin, and Dmax have conventional definitions known, in the imaging arts. In photothermographic materials, Dmin is considered herein as image density achieved when the photothermographic material is thermally developed without prior exposure to radiation. It is the average of eight lowest density values on the exposed side of the fiducial mark. In thermographic materials, Dmin is considered herein as image density in the non-thermally imaged areas of the thermographic material.
The sensitometric term absorbance is another term for optical density (OD).
xe2x80x9cTransparentxe2x80x9d means capable of transmitting visible light or imaging radiation without appreciable scattering or absorption.
As used herein, the phrase xe2x80x9corganic silver coordinating ligandxe2x80x9d refers to an organic molecule capable of forming a bond with a silver atom. Although the compounds so formed are technically silver coordination compounds they are also often referred to as silver salts.
The terms xe2x80x9cdouble-sidedxe2x80x9d and xe2x80x9cdouble-faced coatingxe2x80x9d are used to define photothermographic materials having one or more of the same or different thermally developable emulsion layers disposed on both sides (front and back) of the support.
The term xe2x80x9cburied layerxe2x80x9d means that there is at least one other layer disposed over the backside conductive layer(s).
In the compounds described herein, no particular double bond geometry (for example, cis or trans) is intended by the structures drawn. Similarly, in compounds having alternating single and double bonds and localized charges are drawn as a formalism. In reality, both electron and charge delocalization exists throughout the conjugated chain.
As is well understood in this art, for the chemical compounds herein described, substitution is not only tolerated, but is often advisable and various substituents are anticipated on the compounds used in the present invention unless otherwise stated. Thus, when a compound is referred to as xe2x80x9chaving the structurexe2x80x9d of a given formula, any substitution that does not alter the bond structure of the formula or the shown atoms within that structure is included within the formula, unless such substitution is specifically excluded by language (such as xe2x80x9cfree of carboxy-substituted alkylxe2x80x9d). For example, where a benzene ring structure is shown (including fused ring structures), substituent groups may be placed on the benzene ring structure, but the atoms making up the benzene ring structure may not be replaced.
As a means of simplifying the discussion and recitation of certain substituent groups, the term xe2x80x9cgroupxe2x80x9d refers to chemical species that may be substituted as well as those that are not so substituted. Thus, the term xe2x80x9cgroup,xe2x80x9d such as xe2x80x9calkyl groupxe2x80x9d is intended to include not only pure hydrocarbon alkyl chains, such as methyl, ethyl, n-propyl, t-butyl, cyclohexyl, iso-octyl, and octadecyl, but also alkyl chains bearing substituents known in the art, such as hydroxyl, alkoxy, phenyl, halogen atoms (F, Cl, Br, and I), cyano, nitro, amino, and carboxy. For example, alkyl group includes ether and thioether groups (for example CH3xe2x80x94CH2xe2x80x94CH2xe2x80x94Oxe2x80x94CH2xe2x80x94 and CH3xe2x80x94CH2xe2x80x94CH2xe2x80x94Sxe2x80x94CH2xe2x80x94), haloalkyl, nitroalkyl, alkylcarboxy, carboxyalkyl, carboxamido, hydroxyalkyl, sulfoalkyl, and other groups readily apparent to one skilled in the art. Substituents that adversely react with other active ingredients, such as very strongly electrophilic or oxidizing substituents, would, of course, be excluded by the ordinarily skilled artisan as not being inert or harmless.
Research Disclosure is a publication of Kenneth Mason Publications Ltd., Dudley House, 12 North Street, Emsworth, Hampshire PO10 7DQ England. It is also available from Emsworth Design Inc., 147 West 24th Street, New York, N.Y. 10011.
Other aspects, advantages, and benefits of the present invention are apparent from the detailed description, examples, and claims provided in this application.
As noted above, the photothermographic materials of the present invention include one or more photocatalysts in the photothermographic emulsion layer(s). Useful photocatalysts are typically silver halides such as silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromoiodide, silver chlorobromide, and others readily apparent to one skilled in the art. Mixtures of silver halides can also be used in any suitable proportion. Silver bromide and silver bromoiodide are more preferred, with the latter silver halide generally having up to 10 mol % silver iodide. Typical techniques for preparing and precipitating silver halide grains are described in Research Disclosure, 1978, item 17643.
In some embodiments of aqueous-based photothermographic materials, higher amounts of iodide may be present in homogeneous photosensitive silver halide grains, and particularly from about 20 mol % up to the saturation limit of iodide as described, for example, in copending and commonly assigned U.S. Ser. No. 10/246,265 (filed Sep. 18, 2002 by Maskasky and Scaccia).
The shape of the photosensitive silver halide grains used in the present invention is in no way limited. The silver halide grains may have any crystalline habit including, but not limited to, cubic, octahedral, tetrahedral, orthorhombic, rhombic, dodecahedral, other polyhedral, tabular, laminar, twinned, or platelet morphologies and may have epitaxial growth of crystals thereon. If desired, a mixture of these crystals can be employed. Silver halide grains having cubic and tabular morphology are preferred.
The silver halide grains may have a uniform ratio of halide throughout. They may have a graded halide content, with a continuously varying ratio of, for example, silver bromide and silver iodide or they may be of the core-shell type, having a discrete core of one or more silver halides, and a discrete shell of one or more different silver halides. Core-shell silver halide grains useful in photothermographic materials and methods of preparing these materials are described for example in U.S. Pat. No. 5,382,504 (Shor et al.), incorporated herein by reference. Iridium and/or copper doped core-shell and non-core-shell grains are described in U.S. Pat. No. 5,434,043 (Zou et al.) and U.S. Pat. No. 5,939,249 (Zou), both incorporated herein by reference.
The photosensitive silver halide can be added to (or formed within) the emulsion layer(s) in any fashion as long as it is placed in catalytic proximity to the non-photosensitive source of reducible silver ions.
It is preferred that the silver halides be preformed and prepared by an ex-situ process. The silver halide grains prepared ex-situ may then be added to and physically mixed with the non-photosensitive source of reducible silver ions.
It is more preferable to form the source of reducible silver ions in the presence of ex-situ-prepared silver halide. In this process, the source of reducible silver ions, such as a long chain fatty acid silver carboxylate (commonly referred to as a silver xe2x80x9csoapxe2x80x9d), is formed in the presence of the preformed silver halide grains. Co-precipitation of the reducible source of silver ions in the presence of silver halide provides a more intimate mixture of the two materials [see, for example U.S. Pat. No. 3,839,049 (Simons)]. Materials of this type are often referred to as xe2x80x9cpreformed soaps.xe2x80x9d
The silver halide grains used in the imaging formulations can vary in average diameter of up to several micrometers (xcexcm) depending on their desired use. Preferred silver halide grains are those having an average particle size of from about 0.01 to about 1.5 xcexcm, more preferred are those having an average particle size of from about 0.03 to about 1.0 xcexcm, and most preferred are those having an average particle size of from about 0.05 to about 0.8 xcexcm. Those of ordinary skill in the art understand that there is a finite lower practical limit for silver halide grains that is partially dependent upon the wavelengths to which the grains are spectrally sensitized. Such a lower limit, for example, is typically from about 0.01 to about 0.005 xcexcm.
The average size of the photosensitive doped silver halide grains is expressed by the average diameter if the grains are spherical, and by the average of the diameters of equivalent circles for the projected images if the grains are cubic or in other non-spherical shapes.
Grain size may be determined by any of the methods commonly employed in the art for particle size measurement. Representative methods are described by in xe2x80x9cParticle Size Analysis,xe2x80x9d ASTM Symposium on Light Microscopy, R. P. Loveland, 1955, pp. 94-122, and in C. E. K. Mees and T. H. James, The Theory of the Photographic Process, Third Edition, Macmillan, New York, 1966, Chapter 2. Particle size measurements may be expressed in terms of the projected areas of grains or approximations of their diameters. These will provide reasonably accurate results if the grains of interest are substantially uniform in shape.
Preformed silver halide emulsions used in the material of this invention can be prepared by aqueous or organic processes and can be unwashed or washed to remove soluble salts. In the latter case, the soluble salts can be removed by ultrafiltration, by chill setting and leaching, or by washing the coagulum [for example, by the procedures described in U.S. Pat. No. 2,618,556 (Hewitson et al.), U.S. Pat. No. 2,614,928 (Yutzy et al.), U.S. Pat. No. 2,565,418 (Yackel), U.S. Pat. No. 3,241,969 (Hart et al.), and U.S. Pat. No. 2,489,341 (Waller et al.)].
It is also effective to use an in-situ process in which a halide-containing compound is added to an organic silver salt to partially convert the silver of the organic silver salt to silver halide. The halogen-containing compound can be inorganic (such as zinc bromide or lithium bromide) or organic (such as N-bromosuccinimide).
Mixtures of both preformed and in-situ generated silver halide may be used if desired.
Additional methods of preparing these silver halide and organic silver salts and manners of blending them are described in Research Disclosure, June 1978, item 17029, U.S. Pat. No. 3,700,458 (Lindholm), U.S. Pat. No. 4,076,539 (Ikenoue et al.), JP 49-013224 A, (Fuji), 50-017216 A (Fuji), and 51-042529 A (Fuji).
In some instances, it may be helpful to prepare the photosensitive silver halide grains in the presence of a hydroxytetraazaindene (such as 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene or an N-heterocyclic compound comprising at least one mercapto group (such as 1-phenyl-5-mercaptotetrazole) to provide increased photospeed. Details of this procedure are provided in U.S. Pat. No. 6,413,710B1 (Shor et al.), that is incorporated herein by reference.
The one or more light-sensitive silver halides used in the photothermographic materials of the present invention are preferably present in an amount of from about 0.005 to about 0.5 mole, more preferably from about 0.01 to about 0.25 mole, and most preferably from about 0.03 to about 0.15 mole, per mole of non-photosensitive source of reducible silver ions.
The photosensitive silver halides used in photothermographic features of the invention may be employed without modification. However, one or more conventional chemical sensitizers may be used in the preparation of the photosensitive silver halides to increase photospeed. Such compounds may contain sulfur, tellurium, or selenium, or may comprise a compound containing gold, platinum, palladium, ruthenium, rhodium, iridium, or combinations thereof, a reducing agent such as a tin halide or a combination of any of these. The details of these materials are provided for example, in T. H. James, The Theory of the Photographic Process, Fourth Edition, Eastman Kodak Company, Rochester, N.Y., 1977, Chapter 5, pp. 149-169. Suitable conventional chemical sensitization procedures are also described in U.S. Pat. No. 1,623,499 (Sheppard et al.), U.S. Pat. No. 2,399,083 (Waller et al.), U.S. Pat. No. 3,297,447 (McVeigh), U.S. Pat. No. 3,297,446 (Dunn), U.S. Pat. No. 5,049,485 (Deaton), U.S. Pat. No. 5,252,455 (Deaton), U.S. Pat. No. 5,391,727 (Deaton), U.S. Pat. No. 5,912,111 (Lok et al.), U.S. Pat. No. 5,759,761 (Lushington et al.), U.S. Pat. No. 6,296,998 (Eikenberry et al), and EP 0 915 371 A1 (Lok et al.), all of which are incorporated herein by reference.
In addition, mercaptotetrazoles and tetraazindenes as described in U.S. Pat. No. 5,691,127 (Daubendiek et al.), incorporated herein by reference, can be used as suitable addenda for tabular silver halide grains.
When used, sulfur sensitization is usually performed by adding a sulfur sensitizer and stirring the emulsion at an appropriate temperature for a predetermined time. Various sulfur compounds can be used. Some examples of sulfur sensitizers include thiosulfates, thioureas, thioamides, thiazoles, rhodanines, phosphine sulfides, thiohydantoins, 4-oxo-oxazolidine-2-thiones, dipolysulfides, mercapto compounds, polythionates, and elemental sulfur.
Certain tetrasubstituted thiourea compounds are also useful in the present invention. Such compounds are described, for example in U.S. Pat. No. 6,296,998 (Eikenberry et al.), U.S. Pat. No. 6,322,961 (Lam et al.) and U.S. Pat. No. 6,368,779 (Lynch et al.). Also useful are the tetrasubstituted middle chalcogen (that is, sulfur, selenium, and tellurium) thiourea compounds disclosed in U.S. Pat. No. 4,810,626 (Burgmaier et al.). All of the above patents are incorporated herein by reference.
The amount of the sulfur sensitizer to be added varies depending upon various conditions such as pH, temperature and grain size of silver halide at the time of chemical ripening, it is preferably from 10xe2x88x927 to 10xe2x88x922 mole per mole of silver halide, and more preferably from 10xe2x88x926 to 10xe2x80x34 mole.
In one preferred embodiment, chemical sensitization is achieved by oxidative decomposition of a sulfur-containing spectral sensitizing dye in the presence of a photothermographic emulsion. Such sensitization is described in U.S. Pat. No. 5,891,615 (Winslow et al.), incorporated herein by reference.
Still other useful chemical sensitizers include certain selenium-containing compounds. When used, selenium sensitization is usually performed by adding a selenium sensitizer and stirring the emulsion at an appropriate temperature for a predetermined time. Some specific examples of useful selenium compounds can be found in U.S. Pat. No. 5,158,892 (Sasaki et al.), U.S. Pat. No. 5,238,807 (Sasaki et al.), U.S. Pat. No. 5,942,384 (Arai et al.) and in co-pending and commonly assigned U.S. Ser. No. 10/082,516 (filed Feb. 25, 2002 by Lynch, Opatz, Gysling, and Simpson). All of the above documents are incorporated herein by reference.
Still other useful chemical sensitizers include certain tellurium-containing compounds. When used, tellurium sensitization is usually performed by adding a tellurium sensitizer and stirring the emulsion at an appropriate temperature for a predetermined time. Tellurium compounds for use as chemical sensitizers can be selected from those described in J. Chem. Soc,. Chem. Commun. 1980, 635, ibid., 1979, 1102, ibid., 1979, 645, J. Chem. Soc. Perkin. Trans, 1980, 1, 2191, The Chemistry of Organic Selenium and Tellurium Compounds, S. Patai and Z. Rappoport, Eds., Vol. 1 (1986), and Vol. 2 (1987), U.S. Pat. No. 1,623,499 (Sheppard et al.), U.S. Pat. No. 3,320,069 (Illingsworth), U.S. Pat. No. 3,772,031 (Berry et al.), U.S. Pat. No. 5,215,880 (Kojima et al.), U.S. Pat. No. 5,273,874 (Kojima et al.), U.S. Pat. No. 5,342,750 (Sasaki et al.), U.S. Pat. No. 5,677,120 (Lushington et al.), British Pat. No. 235,211 (Sheppard), British Pat. No. 1,121,496 (Halwig), British Pat. No. 1,295,462 (Hilson et al.), British Pat. No. 1,396,696 (Simons), JP-04-271341 A (Morio et al.), in co-pending and commonly assigned U.S. Published Application 2002-0164549 (Lynch et al.), and in co-pending and commonly assigned U.S. Ser. No. 09/923,039 (filed Aug. 6, 2001 by Gysling, Dickinson, Lelental, and Boettcher). All of the above documents are incorporated herein by reference.
The amount of the selenium or tellurium sensitizer used in the present invention varies depending on silver halide grains used or chemical ripening conditions. However, it is generally from 10xe2x88x928 to 10xe2x88x922 mole per mole of silver halide, preferably on the order of from 10xe2x88x927 to 10xe2x88x923 mole.
Noble metal sensitizers for use in the present invention include gold, platinum, palladium and iridium. Gold sensitization is particularly preferred.
When used, the gold sensitizer used for the gold sensitization of the silver halide emulsion used in the present invention may have an oxidation number of 1 or 3, and may be a gold compound commonly used as a gold sensitizer. U.S. Pat. No. 5,858,637 (Eshelman et al.) describes various Au (I) compounds that can be used as chemical sensitizers. Other useful gold compounds can be found in U.S. Pat. No. 5,759,761 (Lushington et al.). Useful combinations of gold (I) complexes and rapid sulfiding agents are described in U.S. Pat. No. 6,322,961 (Lam et al.). Combinations of gold (III) compounds and either sulfur- or tellurium-containing compounds are useful as chemical sensitizers and are described in U.S. Pat. No. 6,423,481 (Simpson et al.). All of the above references are incorporated herein by reference.
Reduction sensitization may also be used. Specific examples of compounds useful in reduction sensitization include, but are not limited to, stannous chloride, hydrazine ethanolamine, and thioureaoxide. Reduction sensitization may be performed by ripening the grains while keeping the emulsion at pH 7 or above, or at pAg 8.3 or less.
The chemical sensitizers can be used in making the silver halide emulsions in conventional amounts that generally depend upon the average size of the silver halide grains. Generally, the total amount is at least 10xe2x88x9210 mole per mole of total silver, and preferably from about 10xe2x88x928 to about 10xe2x88x922 mole per mole of total silver. The upper limit can vary depending upon the compound(s) used, the level of silver halide, and the average grain size and grain morphology, and would be readily determinable by one of ordinary skill in the art.
The photosensitive silver halides used in the photothermographic features of the invention may be spectrally sensitized with various spectral sensitizing dyes that are known to enhance silver halide sensitivity to ultraviolet, visible, and/or infrared radiation. Non-limiting examples of sensitizing dyes that can be employed include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxanol dyes. Cyanine dyes, merocyanine dyes and complex merocyanine dyes are particularly useful. Spectral sensitizing dyes are chosen for optimum photosensitivity, stability, and synthetic ease. They may be added at any stage in chemical finishing of the photothermographic emulsion.
Suitable sensitizing dyes such as those described in U.S. Pat. No. 3,719,495 (Lea), U.S. Pat. No. 4,396,712 (Kinoshita et al.), U.S. Pat. No. 4,439,520 (Kofron et al.), U.S. Pat. No. 4,690,883 (Kubodera et al.), U.S. Pat. No. 4,840,882 (Iwagaki et al.), U.S. Pat. No. 5,064,753 (Kohno et al.), U.S. Pat. No. 5,281,515 (Delprato et al.), U.S. Pat. No. 5,393,654 (Burrows et al), U.S. Pat. No. 5,441,866 (Miller et al.), U.S. Pat. No. 5,508,162 (Dankosh), U.S. Pat. No. 5,510,236 (Dankosh), U.S. Pat. No. 5,541,054 (Miller et al.), JP 2000-063690 (Tanaka et al.), JP 2000-112054 (Fukusaka et al.), JP 2000-273329 (Tanaka et al.), JP 2001-005145 (Arai), JP 2001-064527 (Oshiyama et al.), and JP 2001-154305 (Kita et al.), can be used in the practice of the invention. All of the publications noted above are incorporated herein by reference. A summary of generally useful spectral sensitizing dyes is contained in Research Disclosure, item 308119, Section IV, December, 1989. Additional classes of dyes useful for spectral sensitization, including sensitization at other wavelengths are described in Research Disclosure, 1994, item 36544, section V.
Teachings relating to specific combinations of spectral sensitizing dyes also include U.S. Pat. No. 4,581,329 (Sugimoto et al.), U.S. Pat. No. 4,582,786 (Ikeda et al.), U.S. Pat. No. 4,609,621 (Sugimoto et al.), U.S. Pat. No. 4,675,279 (Shuto et al.), U.S. Pat. No. 4,678,741 (Yamada et al.), U.S. Pat. No. 4,720,451 (Shuto et al.), U.S. Pat. No. 4,818,675 (Miyasaka et al.), U.S. Pat. No. 4,945,036 (Arai et al.), and U.S. Pat. No. 4,952,491 (Nishikawa et al.). All of the above publications are incorporated herein by reference.
Specific examples of useful spectral sensitizing dyes for the photothermographic materials of this invention include, for example, 2-[[5-chloro-3-(3-sulfopropyl)-2(3H)-benzothiazolylidene]methyl]-1-(3-sulfopropyl)-naphtho[1,2-d]thiazolium, inner salt, N,N-diethylethanamine salt (1:1), 2-[[5,6-dichloro-1-ethyl-1,3-dihydro-3-(3-sulfopropyl)-2H-benzimidazol-2-ylidene]methyl]-5-phenyl-3-(3-sulfopropyl)-benzoxazolium, inner salt, potassium salt, 5-chloro-2-[[5-chloro-3-(3-sulfopropyl)-2(3H)-benzothiazolylidene]methyl]-3-(3-sulfopropyl)-benzothiazolium, inner salt, N,N-diethylethanamine salt (1:1), and 5-phenyl-2-((5-phenyl-3-(3-sulfopropyl)-2(3H)-benzoxazolylidene)methyl)-3-(3-sulfopropyl)-benzothiazolium, inner salt, N,N-diethylethanamine salt(1:1).
Also useful are spectral sensitizing dyes that decolorize by the action of light or heat. Such dyes are described in U.S. Pat. No. 4,524,128 (Edwards et al.), JP 2001-109101 (Adachi), JP 2001-154305 (Kita et al.), and JP 2001-183770 (Hanyu et al.).
Spectral sensitizing dyes may be used singly or in combination. The dyes are selected for the purpose of adjusting the wavelength distribution of the spectral sensitivity, and for the purpose of supersensitization. When using a combination of dyes having a supersensitizing effect, it is possible to attain much higher sensitivity than the sum of sensitivities that can be achieved by using each dye alone. It is also possible to attain such supersensitizing action by the use of a dye having no spectral sensitizing action by itself, or a compound that does not substantially absorb visible light. Diaminostilbene compounds are often used as supersensitizers.
An appropriate amount of spectral sensitizing dye added is generally about 10xe2x88x9210 to 10xe2x88x921 mole, and preferably, about 10xe2x88x927 to 10xe2x88x922 mole per mole of silver halide.
The non-photosensitive source of reducible silver ions used in the thermographic and photothermographic materials of this invention can be any metal-organic compound that contains reducible silver (1+) ions. Such compounds are generally silver salts of silver coordinating ligands. Preferably, it is an organic silver salt that is comparatively stable to light and forms a silver image when heated to 50xc2x0 C. or higher in the presence of an exposed photocatalyst (such as silver halide, when used in a photothermographic material) and a reducing composition.
Silver salts of organic acids including silver salts of long-chain carboxylic acids are preferred. The chains typically contain 10 to 30, and preferably 15 to 28, carbon atoms. Suitable organic silver salts include silver salts of organic compounds having a carboxylic acid group. Examples thereof include a silver salt of an aliphatic carboxylic acid or a silver salt of an aromatic carboxylic acid. Preferred examples of the silver salts of aliphatic carboxylic acids include silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caprate, silver myristate, silver palmitate, silver maleate, silver fumarate, silver tartarate, silver furoate, silver linoleate, silver butyrate, silver camphorate, and mixtures thereof. Preferably, at least silver behenate is used alone or in mixtures with other silver salts.
Representative examples of useful silver salts of aromatic carboxylic acid and other carboxylic acid group-containing compounds include, but are not limited to, silver benzoate, silver substituted-benzoates (such as silver 3,5-dihydroxy-benzoate, silver o-methylbenzoate, silver m-methylbenzoate, silver p-methylbenzoate, silver 2,4-dichlorobenzoate, silver acetamidobenzoate, silver p-phenylbenzoate), silver tannate, silver phthalate, silver terephthalate, silver salicylate, silver phenylacetate, and silver pyromellitate.
Silver salts of aliphatic carboxylic acids containing a thioether group as described in U.S. Pat. No. 3,330,663 (Weyde et al.) are also useful. Soluble silver carboxylates comprising hydrocarbon chains incorporating ether or thioether linkages, or sterically hindered substitution in the xcex1-(on a hydrocarbon group) or ortho-(on an aromatic group) position, and displaying increased solubility in coating solvents and affording coatings with less light scattering can also be used. Such silver carboxylates are described in U.S. Pat. No. 5,491,059 (Whitcomb). Mixtures of any of the silver salts described herein can also be used if desired.
Silver salts of dicarboxylic acids are also useful. Such acids may be aliphatic, aromatic, or heterocyclic. Examples of such acids include, for example, phthalic acid, glutamic acid, or homo-phthalic acid.
Silver salts of sulfonates are also useful in the practice of this invention. Such materials are described for example in U.S. Pat. No. 4,504,575 (Lee). Silver salts of sulfosuccinates are also useful as described for example in EP 0 227 141 A1 (Leenders et al.).
Moreover, silver salts of acetylenes can also be used as described, for example in U.S. Pat. No. 4,761,361 (Ozaki et al.) and U.S. Pat. No. 4,775,613 (Hirai et al.).
Silver salts of compounds containing mercapto or thione groups and derivatives thereof can also be used. Preferred examples of these compounds include, but are not limited to, a heterocyclic nucleus containing 5 or 6 atoms in the ring, at least one of which is a nitrogen atom, and other atoms being carbon, oxygen, or sulfur atoms. Such heterocyclic nuclei include, but are not limited to, triazoles, oxazoles, thiazoles, thiazolines, imidazoles, diazoles, pyridines, and triazines. Representative examples of these silver salts include, but are not limited to, a silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver salt of 5-carboxylic-1-methyl-2-phenyl-4-thiopyridine, a silver salt of mercaptotriazine, a silver salt of 2-mercaptobenzoxazole, silver salts as described in U.S. Pat. No. 4,123,274 (Knight et al.) (for example, a silver salt of a 1,2,4-mercaptothiazole derivative, such as a silver salt of 3-amino-5-benzylthio-1,2,4-thiazole), and a silver salt of thione compounds [such as a silver salt of 3-(2-carboxyethyl)-4-methyl4-thiazoline-2-thione as described in U.S. Pat. No. 3,785,830 (Sullivan et al.)].
Examples of other useful silver salts of mercapto or thione substituted compounds that do not contain a heterocyclic nucleus include but are not limited to, a silver salt of thioglycolic acids such as a silver salt of an S-alkylthioglycolic acid (wherein the alkyl group has from 12 to 22 carbon atoms), a silver salt of a dithiocarboxylic acid such as a silver salt of a dithioacetic acid, and a silver salt of a thioamide.
In some embodiments, a silver salt of a compound containing an imino group is preferred, especially in aqueous-based imaging formulations. Preferred examples of these compounds include, but are not limited to, silver salts of benzotriazole and substituted derivatives thereof (for example, silver methylbenzotriazole and silver 5-chlorobenzotriazole), silver salts of 1,2,4-triazoles or 1-H-tetrazoles such as phenylmercaptotetrazole as described in U.S. Pat. No. 4,220,709 (deMauriac), and silver salts of imidazoles and imidazole derivatives as described in U.S. Pat. No. 4,260,677 (Winslow et al.). Particularly useful silver salts of this type are the silver salts of benzotriazole and substituted derivatives thereof. A silver salt of a benzotriazole is often used in aqueous-based thermographic and photothermographic formulations.
Organic silver salts that are particularly useful in organic solvent-based photothermographic materials include silver carboxylates (both aliphatic and aromatic carboxylates), silver triazolates, silver sulfonates, silver sulfosuccinates, and silver acetylides. Silver salts of long-chain aliphatic carboxylic acids containing 15 to 28, carbon atoms and silver salts are particularly preferred.
It is also convenient to use silver half soaps. A preferred example of a silver half soap is an equimolar blend of silver carboxylate and carboxylic acid, which analyzes for about 14.5% by weight solids of silver in the blend and which is prepared by precipitation from an aqueous solution of an ammonium or an alkali metal salt of a commercially available fatty carboxylic acid, or by addition of the free fatty acid to the silver soap. For transparent films a silver carboxylate full soap, containing not more than about 15% of free fatty carboxylic acid and analyzing for about 22% silver, can be used. For opaque thermographic and photothermographic materials, different amounts can be used.
The methods used for making silver soap emulsions are well known in the art and are disclosed in Research Disclosure, April 1983, item 22812, Research Disclosure, October 1983, item 23419, U.S. Pat. No. 3,985,565 (Gabrielsen et al.) and the references cited above.
Non-photosensitive sources of reducible silver ions can also be provided as core-shell silver salts such as those described in U.S. Pat. No. 6,355,408 (Whitcomb et al.), that is incorporated herein by reference. These silver salts include a core comprised of one or more silver salts and a shell having one or more different silver salts.
Another useful source of non-photosensitive reducible silver ions in the practice of this invention are the silver dimer compounds that comprise two different silver salts as described in copending and commonly assigned U.S. Pat. No. 6,472,131 (Whitcomb), that is incorporated herein by reference. Such non-photosensitive silver dimer compounds comprise two different silver salts, provided that when the two different silver salts comprise straight-chain, saturated hydrocarbon groups as the silver coordinating ligands, those ligands differ by at least 6 carbon atoms.
Still other useful sources of non-photosensitive reducible silver ions in the practice of this invention are the silver core-shell compounds comprising a primary core comprising one or more photosensitive silver halides, or one or more non-photosensitive inorganic metal salts or non-silver containing organic salts, and a shell at least partially covering the primary core, wherein the shell comprises one or more non-photosensitive silver salts, each of which silver salts comprises a organic silver coordinating ligand. Such compounds are described in copending and commonly assigned U.S. Ser. No. 10/208,603 (filed Jul. 30, 2002 by Bokhonov, Burleva, Whitcomb, Howlader, and Leichter), that is incorporated herein by reference.
As one skilled in the art would understand, the non-photosensitive source of reducible silver ions can include various mixtures of the various silver salt compounds described herein, in any desirable proportions.
When used in photothermographic materials, the photocatalyst and the non-photosensitive source of reducible silver ions must be in catalytic proximity (that is, reactive association). It is preferred that these reactive components be present in the same emulsion layer.
The one or more non-photosensitive sources of reducible silver ions are preferably present in an amount of about 5% by weight to about 70% by weight, and more preferably, about 10% to about 50% by weight, based on the total dry weight of the emulsion layers. Stated another way, the amount of the sources of reducible silver ions is generally present in an amount of from about 0.001 to about 0.2 mol/m2 of the dry photothermographic material, and preferably from about 0.01 to about 0.05 mol/m2 of that material.
The total amount of silver (from all silver sources) in the thermographic and photothermographic materials is generally at least 0.002 mol/m2 and preferably from about 0.01 to about 0.05 mol/m2.
When used in a photothermographic material, the reducing agent (or reducing agent composition comprising two or more components) for the source of reducible silver ions can be any material, preferably an organic material, that can reduce silver (1+) ion to metallic silver.
Conventional photographic developers can be used as reducing agents, including aromatic di- and tri-hydroxy compounds (such as hydroquinones, gallatic acid and gallic acid derivatives, catechols, and pyrogallols), aminophenols (for example, N-methylaminophenol), p-phenylenediamines, alkoxynaphthols (for example, 4-methoxy-1-naphthol), pyrazolidin-3-one type reducing agents (for example PHENIDONE(copyright)), pyrazolin-5-ones, polyhydroxy spiro-bis-indanes, indan-1,3-dione derivatives, hydroxytetrone acids, hydroxytetronimides, hydroxylamine derivatives such as for example those described in U.S. Pat. No. 4,082,901 (Laridon et al.), hydrazine derivatives, hindered phenols, amidoximes, azines, reductones (for example, ascorbic acid and ascorbic acid derivatives), leuco dyes, and other materials readily apparent to one skilled in the art.
When a silver benzotriazole silver source is used, ascorbic acid reducing agents are preferred. An xe2x80x9cascorbic acidxe2x80x9d reducing agent (also referred to as a developer or developing agent) means ascorbic acid, complexes, and derivatives thereof. Ascorbic acid developing agents are described in a considerable number of publications in photographic processes, including U.S. Pat. No. 5,236,816 (Purol et al.) and references cited therein. Useful ascorbic acid developing agents include ascorbic acid and the analogues, isomers and derivatives thereof. Such compounds include, but are not limited to, D- or L-ascorbic acid, sugar-type derivatives thereof (such as sorboascorbic acid, xcex3-lactoascorbic acid, 6-desoxy-L-ascorbic acid, L-rhamnoascorbic acid, imino-6-desoxy-L-ascorbic acid, glucoascorbic acid, fucoascorbic acid, glucoheptoascorbic acid, maltoascorbic acid, L-arabosascorbic acid), sodium ascorbate, potassium ascorbate, isoascorbic acid (or L-erythroascorbic acid), and salts thereof (such as alkali metal, ammonium or others known in the art), endiol type ascorbic acid, an enaminol type ascorbic acid, a thioenol type ascorbic acid, and an enamin-thiol type ascorbic acid, as described for example in U.S. Pat. No. 5,498,511 (Yamashita et al.), EP 0 585 792 A1 (Passarella et al.), EP 0 573 700 A1 (Lingier et al.), EP 0 588 408A1 (Hieronymus et al.), U.S. Pat. No. 5,089,819 (Knapp), U.S. Pat. No. 5,278,035 (Knapp), U.S. Pat. No. 5,384,232 (Bishop et al.), U.S. Pat. No. 5,376,510 (Parker et al.), Japanese Kokai 7-56286 (Toyoda), U.S. Pat. No. 2,688,549 (James et al.), and Research Disclosure, item 37152, March 1995. D-, L-, or D,L-ascorbic acid (and alkali metal salts thereof) or isoascorbic acid (or alkali metal salts thereof) are preferred. Mixtures of these developing agents can be used if desired.
When a silver carboxylate silver source is used in a photothermographic material, hindered phenol reducing agents are preferred. In some instances, the reducing agent composition comprises two or more components such as a hindered phenol developer and a co-developer that can be chosen from the various classes of co-developers and reducing agents described below. Ternary developer mixtures involving the further addition of contrast enhancing agents are also useful. Such contrast enhancing agents can be chosen from the various classes of reducing agents described below. Hindered phenol reducing agents are preferred (alone or in combination with one or more high-contrast co-developing agents and co-developer contrast enhancing agents).
xe2x80x9cHindered phenol reducing agentsxe2x80x9d are compounds that contain only one hydroxy group on a given phenyl ring and have at least one additional substituent located ortho to the hydroxy group. Hindered phenol reducing agents may contain more than one hydroxy group as long as each hydroxy group is located on different phenyl rings. Hindered phenol reducing agents include, for example, binaphthols (that is dihydroxybinaphthyls), biphenols (that is dihydroxybiphenyls), bis(hydroxynaphthyl)methanes, bis(hydroxyphenyl)methanes (that is bisphenols), hindered phenols, and hindered naphthols, each of which may be variously substituted.
Representative binaphthols include, but are not limited, to 1,1xe2x80x2-bi-2-naphthol, 1,1xe2x80x2-bi-4-methyl-2-naphthol and 6,6xe2x80x2-dibromo-bi-2-naphthol. For additional compounds see U.S. Pat. No. 3,094,417 (Workman) and U.S. Pat. No. 5,262,295 (Tanaka et al.), both incorporated herein by reference.
Representative biphenols include, but are not limited, to 2,2xe2x80x2-dihydroxy-3,3xe2x80x2-di-t-butyl-5,5-dimethylbiphenyl, 2,2xe2x80x2-dihydroxy-3,3xe2x80x2,5,5xe2x80x2-tetra-t-butylbiphenyl, 2,2xe2x80x2-dihydroxy-3,3xe2x80x2-di-t-butyl-5,5xe2x80x2-dichlorobiphenyl, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-4-methyl-6-n-hexylphenol, 4,4xe2x80x2-dihydroxy-3,3xe2x80x2,5,5xe2x80x2-tetra-t-butylbiphenyl and 4,4xe2x80x2-dihydroxy-3,3xe2x80x2,5,5xe2x80x2-tetra-methylbiphenyl. For additional compounds see U.S. Pat. No. 5,262,295 (noted above).
Representative bis(hydroxynaphthyl)methanes include, but are not limited to, 4,4xe2x80x2-methylenebis(2-methyl-1-naphthol). For additional compounds see U.S. Pat. No. 5,262,295 (noted above).
Representative bis(hydroxyphenyl)methanes include, but are not limited to, bis(2-hydroxy-3-t-butyl-5-methylphenyl)methane (CAO-5), 1,1xe2x80x2-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane (NONOX(copyright) or PERMANAX WSO), 1,1xe2x80x2-bis(3,5-di-t-butyl4-hydroxyphenyl)methane, 2,2xe2x80x2-bis(4-hydroxy-3-methylphenyl)propane, 4,4xe2x80x2-ethylidene-bis(2-t-butyl-6-methylphenol), 2,2xe2x80x2-isobutylidene-bis(4,6-dimethylphenol) (LOWINOX(copyright) 221B46), and 2,2xe2x80x2-bis(3,5-dimethyl-4-hydroxyphenyl)propane. For additional compounds see U.S. Pat. No. 5,262,295 (noted above).
Representative hindered phenols include, but are not limited to, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methylphenol, 2,4-di-t-butylphenol, 2,6-dichlorophenol, 2,6-dimethylphenol and 2-t-butyl-6-methylphenol.
Representative hindered naphthols include, but are not limited to, 1-naphthol, 4-methyl-1-naphthol, 4-methoxy-1-naphthol, 4-chloro-1-naphthol and 2-methyl-1-naphthol. For additional compounds see U.S. Pat. No. 5,262,295 (noted above).
Mixtures of hindered phenol reducing agents can be used if desired.
More specific alternative reducing agents that have been disclosed in dry silver systems including amidoximes such as phenylamidoxime, 2-thienylamidoxime and p-phenoxyphenylamidoxime, azines (for example, 4-hydroxy-3,5-dimethoxybenzaldehydrazine), a combination of aliphatic carboxylic acid aryl hydrazides and ascorbic acid [such as 2,2xe2x80x2-bis(hydroxymethyl)-propionyl-xcex2-phenyl hydrazide in combination with ascorbic acid], a combination of polyhydroxybenzene and hydroxylamine, a reductone and/or a hydrazine [for example, a combination of hydroquinone and bis(ethoxyethyl)hydroxylamine], piperidinohexose reductone or formyl-4-methylphenylhydrazine, hydroxamic acids (such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid, and o-alaninehydroxamic acid), a combination of azines and sulfonamidophenols (for example, phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol), xcex1-cyanophenylacetic acid derivatives (such as ethyl xcex1-cyano-2-methylphenylacetate and ethyl xcex1-cyanophenylacetate), bis-o-naphthols [such as 2,2xe2x80x2-dihydroxyl-1-binaphthyl, 6,6xe2x80x2-dibromo-2,2xe2x80x2-dihydroxy-1,1xe2x80x2-binaphthyl, and bis(2-hydroxy-1-naphthyl)-methane], a combination of bis-o-naphthol and a 1,3-dihydroxybenzene derivative (for example, 2,4-dihydroxybenzophenone or 2,4-dihydroxyacetophenone), 5-pyrazolones such as 3-methyl-1-phenyl-5-pyrazolone, reductones (such as dimethylaminohexose reductone, anhydrodihydro-aminohexose reductone and anhydrodihydro-piperidone-hexose reductone), sulfonamidophenol reducing agents (such as 2,6-dichloro-4-benzenesulfonamido-phenol, and p-benzenesulfonamidophenol), indane-1,3-diones (such as 2-phenylindane-1,3-dione), chromans (such as 2,2-dimethyl-7-t-butyl-6-hydroxychroman), 1,4-dihydropyridines (such as 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine), ascorbic acid derivatives (such as 1-ascorbylpalmitate, ascorbylstearate and unsaturated aldehydes and ketones), and 3-pyrazolidones.
An additional class of reducing agents that can be used as developers are substituted hydrazines including the sulfonyl hydrazides described in U.S. Pat. No. 5,464,738 (Lynch et al.). Still other useful reducing agents are described, for example, in U.S. Pat. No. 3,074,809 (Owen), U.S. Pat. No. 3,094,417 (Workman), U.S. Pat. No. 3,080,254 (Grant, Jr.), and U.S. Pat. No. 3,887,417 (Klein et al.). Auxiliary reducing agents may be useful as described in U.S. Pat. No. 5,981,151 (Leenders et al.). All of these patents are incorporated herein by reference.
Useful co-developer reducing agents can also be used as described for example, in U.S. Pat. No. 6,387,605 (Lynch et al.), that is incorporated herein by reference. Examples of these compounds include, but are not limited to, 2,5-dioxo-cyclopentane carboxaldehydes, 5-(hydroxymethylene)-2,2-dimethyl-1,3-dioxane-4,6-diones, 5-(hydroxymethylene)-1,3-dialkylbarbituric acids, and 2-(ethoxymethylene)-1H-indene-1,3 (2H)-diones.
Additional classes of reducing agents that can be used as co-developers are trityl hydrazides and formyl phenyl hydrazides as described in U.S. Pat. No. 5,496,695 (Simpson et al.), 2-substituted malondialdehyde compounds as described in U.S. Pat. No. 5,654,130 (Murray), and 4-substituted isoxazole compounds as described in U.S. Pat. No. 5,705,324 (Murray). Additional developers are described in U.S. Pat. No. 6,100,022 (Inoue et al.). All of the patents above are incorporated herein by reference.
Yet another class of co-developers includes substituted acrylonitrile compounds that are described in U.S. Pat. No. 5,635,339 (Murray) and U.S. Pat. No. 5,545,515 (Murray et al.), both incorporated herein by reference. Examples of such compounds include, but are not limited to, the compounds identified as HET-01 and HET-02 in U.S. Pat. No. 5,635,339 (noted above) and CN-01 through CN-13 in U.S. Pat. No. 5,545,515 (noted above). Particularly useful compounds of this type are (hydroxymethylene)cyanoacetates and their metal salts.
Various contrast enhancing agents can be used in some photothermographic materials with specific co-developers. Examples of useful contrast enhancing agents include, but are not limited to, hydroxylamines (including hydroxylamine and alkyl- and aryl-substituted derivatives thereof), alkanolamines and ammonium phthalamate compounds as described for example, in U.S. Pat. No. 5,545,505 (Simpson), hydroxamic acid compounds as described for example, in U.S. Pat. No. 5,545,507 (Simpson et al.), N-acylhydrazine compounds as described for example, in U.S. Pat. No. 5,558,983 (Simpson et al.), and hydrogen atom donor compounds as described in U.S. Pat. No. 5,637,449 (Harring et al.). All of the patents above are incorporated herein by reference.
When used with a silver carboxylate silver source in a thermographic material, preferred reducing agents are aromatic di- and tri-hydroxy compounds having at least two hydroxy groups in ortho- orpara-relationship on the same aromatic nucleus. Examples are hydroquinone and substituted hydroquinones, catechols, pyrogallol, gallic acid and gallic acid esters (for example, methyl gallate, ethyl gallate, propyl gallate), and tannic acid.
Particularly preferred are reducing catechol-type reducing agents having no more than two hydroxy groups in an ortho-relationship. Preferred catechol-type reducing agents include, for example, catechol, 3-(3,4-dihydroxy-phenyl)-propionic acid, 2,3-dihydroxy-benzoic acid, 2,3-dihydroxy-benzoic acid esters, 3,4-dihydroxy-benzoic acid, and 3,4-dihydroxy-benzoic acid esters.
One particularly preferred class of catechol-type reducing agents are benzene compounds in which the benzene nucleus is substituted by no more than two hydroxy groups which are present in 2,3-position on the nucleus and have in the 1-position of the nucleus a substituent linked to the nucleus by means of a carbonyl group. Compounds of this type include 2,3-dihydroxy-benzoic acid, methyl 2,3-dihydroxy-benzoate, and ethyl 2,3-dihydroxy-benzoate.
Another particularly preferred class of catechol-type reducing agents are benzene compounds in which the benzene nucleus is substituted by no more than two hydroxy groups which are present in 3,4-position on the nucleus and have in the 1-position of the nucleus a substituent linked to the nucleus by means of a carbonyl group. Compounds of this type include, for example, 3,4-dihydroxy-benzoic acid, methyl 3,4-dihydroxy-benzoate, ethyl 3,4-dihydroxybenzoate, 3,4-dihydroxy-benzaldehyde, and phenyl-(3,4-dihydroxyphenyl)ketone. Such compounds are described, for example, in U.S. Pat. No. 5,582,953 (Uyttendaele et al.).
Still another particularly useful class of reducing agents are polyhydroxy spiro-bis-indane compounds described as photographic tanning agents in U.S. Pat. No. 3,440,049 (Moede). Examples include 3,3,3xe2x80x2,3xe2x80x2-tetramethyl-5,6,5xe2x80x2,6xe2x80x2-tetrahydroxy-1,1xe2x80x2-spiro-bis-indane (called indane I) and 3,3,3xe2x80x2,3xe2x80x2-tetramethyl-4,6,7,4xe2x80x2,6xe2x80x2,7xe2x80x2-hexahydroxy-1,1xe2x80x2-spiro-bis-indane (called indane II).
Aromatic di- and tri-hydroxy reducing agents can also be used in combination with hindered phenol reducing agents either together or in or in combination with one or more high contrast co-developing agents and co-developer contrast-enhancing agents).
The reducing agent (or mixture thereof) described herein is generally present as 1 to 10% (dry weight) of the emulsion layer. In multilayer constructions, if the reducing agent is added to a layer other than an emulsion layer, slightly higher proportions, of from about 2 to 15 weight % may be more desirable. Any co-developers may be present generally in an amount of from about 0.001% to about 1.5% (dry weight) of the emulsion layer coating.
For color imaging materials (for example, monochrome, dichrome, or full color images), one or more reducing agents can be used that can be oxidized directly or indirectly to form or release one or more dyes.
The dye-forming or releasing compound may be any colored, colorless, or lightly colored compound that can be oxidized to a colored form, or to release a preformed dye when heated, preferably to a temperature of from about 80xc2x0 C. to about 250xc2x0 C. for a duration of at least 1 second. When used with a dye- or image-receiving layer, the dye can diffuse through the imaging layers and interlayers into the image-receiving layer of the photothermographic material.
Leuco dyes or xe2x80x9cblockedxe2x80x9d leuco dyes are one class of dye-forming compounds (or xe2x80x9cblockedxe2x80x9d dye-forming compounds) that form and release a dye upon oxidation by silver ion to form a visible color image in the practice of the present invention. Leuco dyes are the reduced form of dyes that are generally colorless or very lightly colored in the visible region (optical density of less than 0.2). Thus, oxidation provides a color change that is from colorless to colored, an optical density increase of at least 0.2 units, or a substantial change in hue.
Representative classes of useful leuco dyes include, but are not limited to, chromogenic leuco dyes (such as indoaniline, indophenol, or azomethine dyes), imidazole leuco dyes such as 2-(3,5-di-t-butyl-4-hydroxyphenyl)-4,5-diphenylimidazole as described for example in U.S. Pat. No. 3,985,565 (Gabrielson et al.), dyes having an azine, diazine, oxazine, or thiazine nucleus such as those described for example in U.S. Pat. No. 4,563,415 (Brown et al.), U.S. Pat. No. 4,622,395 (Bellus et al.), U.S. Pat. No. 4,710,570 (Thien), and U.S. Pat. No. 4,782,010 (Mader et al.), and benzlidene leuco compounds as described for example in U.S. Pat. No. 4,932,792 (Grieve et al.), all incorporated herein by reference. Further details about the chromogenic leuco dyes noted above can be obtained from U.S. Pat. No. 5,491,059 (noted above, Column 13) and references noted therein.
Another useful class of leuco dyes includes what are known as xe2x80x9caldazinexe2x80x9d and xe2x80x9cketazinexe2x80x9d leuco dyes that are described for example in U.S. Pat. No. 4,587,211 (Ishida et al.) and U.S. Pat. No. 4,795,697 (Vogel et al.), both incorporated herein by reference.
Still another useful class of dye-releasing compounds includes those that release diffusible dyes upon oxidation. These are known as preformed dye release (PDR) or redox dye release (RDR) compounds. In such compounds, the reducing agents release a mobile preformed dye upon oxidation. Examples of such compounds are described in U.S. Pat. No. 4,981,775 (Swain), incorporated herein by reference.
Further, other useful image-forming compounds are those in which the mobility of a dye moiety changes as a result of an oxidation-reduction reaction with silver halide, or a nonphotosensitive silver salt at high temperature, as described for example in JP 59-165,054 (Fuji).
Still further, the reducing agent can be a compound that releases a conventional photographic dye forming color coupler or developer upon oxidation as is known in the photographic art.
The dyes that are formed or released can be the same in the same or different imaging layers. A difference of at least 60 nm in reflective maximum absorbance is preferred. More preferably, this difference is from about 80 to about 100 nm. Further details about the various dye absorbance are provided in U.S. Pat. No. 5,491,059 (noted above, Col. 14).
The total amount of one or more dye- forming or releasing compound that can be incorporated into the photothermographic materials of this invention is generally from about 0.5 to about 25 weight % of the total weight of each imaging layer in which they are located. Preferably, the amount in each imaging layer is from about 1 to about 10 weight %, based on the total dry layer weight. The useful relative proportions of the leuco dyes would be readily known to a skilled worker in the art.
The thermographic and photothermographic materials of this invention can also contain other additives such as shelf-life stabilizers, antifoggants, contrast enhancers, development accelerators, acutance dyes, post-processing stabilizers or stabilizer precursors, thermal solvents (also known as melt formers), and other image-modifying agents as would be readily apparent to one skilled in the art.
To further control the properties of photothermographic materials, (for example, contrast, Dmin, speed, or fog), it may be preferable to add one or more heteroaromatic mercapto compounds or heteroaromatic disulfide compounds of the formulae Arxe2x80x94Sxe2x80x94M1 and Arxe2x80x94Sxe2x80x94Sxe2x80x94Ar, wherein M1 represents a hydrogen atom or an alkali metal atom and Ar represents a heteroaromatic ring or fused heteroaromatic ring containing one or more of nitrogen, sulfur, oxygen, selenium, or tellurium atoms. Preferably, the heteroaromatic ring comprises benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline, or quinazolinone. Compounds having other heteroaromatic rings and compounds providing enhanced sensitization at other wavelengths are also envisioned to be suitable. For example, heteroaromatic mercapto compounds are described as supersensitizers for infrared photothermographic materials in EP 0 559 228B1 (Philip Jr. et al.), incorporated herein by reference.
The heteroaromatic ring may also carry substituents. Examples of preferred substituents are halo groups (such as bromo and chloro), hydroxy, amino, carboxy, alkyl groups (for example, of 1 or more carbon atoms and preferably 1 to 4 carbon atoms), and alkoxy groups (for example, of 1 or more carbon atoms and preferably of 1 to 4 carbon atoms).
Heteroaromatic mercapto compounds are most preferred. Examples of preferred heteroaromatic mercapto compounds are 2-mercaptobenzimidazole, 2-mercapto-5-methylbenzimidazole, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, and mixtures thereof.
If used, a heteroaromatic mercapto compound is generally present in an emulsion layer in an amount of at least about 0.0001 mole per mole of total silver in the emulsion layer. More preferably, the heteroaromatic mercapto compound is present within a range of about 0.001 mole to about 1.0 mole, and most preferably, about 0.005 mole to about 0.2 mole, per mole of total silver.
The photothermographic materials of the present invention can be further protected against the production of fog and can be stabilized against loss of sensitivity during storage. While not necessary for the practice of the invention, it may be advantageous to add mercury (2+) salts to the emulsion layer(s) as an antifoggant. Preferred mercury (2+) salts for this purpose are mercuric acetate and mercuric bromide. Other useful mercury salts include those described in U.S. Pat. No. 2,728,663 (Allen).
Other suitable antifoggants and stabilizers that can be used alone or in combination include thiazolium salts as described in U.S. Pat. No. 2,131,038 (Staud) and U.S. Pat. No. 2,694,716 (Allen), azaindenes as described in U.S. Pat. No. 2,886,437 (Piper), triazaindolizines as described in U.S. Pat. No. 2,444,605 (Heimbach), the urazoles described in U.S. Pat. No. 3,281,135 (Anderson), sulfocatechols as described in U.S. Pat. No. 3,235,652 (Kennard), the oximes described in GB 623,448 (Carrol et al.), polyvalent metal salts as described in U.S. Pat. No. 2,839,405 (Jones), thiuronium salts as described in U.S. Pat. No. 3,220,839 (Herz), palladium, platinum, and gold salts as described in U.S. Pat. No. 2,566,263 (Trirelli) and U.S. Pat. No. 2,597,915 (Damshroder), compounds having xe2x80x94SO2CBr3 groups as described for example in U.S. Pat. No. 5,594,143 (Kirk et al.) and U.S. Pat. No. 5,374,514 (Kirk et al.), and 2-(tribromomethylsulfonyl)quinoline compounds as described in U.S. Pat. No. 5,460,938 (Kirk et al.).
Stabilizer precursor compounds capable of releasing stabilizers upon application of heat during development can also be used. Such precursor compounds are described in for example, U.S. Pat. No. 5,158,866 (Simpson et al.), U.S. Pat. No. 5,175,081 (Krepski et al.), U.S. Pat. No. 5,298,390 (Sakizadeh et al.), and U.S. Pat. No. 5,300,420 (Kenney et al.).
In addition, certain substituted-sulfonyl derivatives of benzotriazoles (for example alkylsulfonylbenzotriazoles and arylsulfonylbenzotriazoles) have been found to be useful stabilizing compounds (such as for post-processing print stabilizing), as described in U.S. Pat. No. 6,171,767 (Kong et al.).
Furthermore, other specific useful antifoggants/stabilizers are described in more detail in U.S. Pat. No. 6,083,681 (Lynch et al.), incorporated herein by reference.
Other antifoggants are hydrobromic acid salts of heterocyclic compounds (such as pyridinium hydrobromide perbromide) as described, for example, in U.S. Pat. No. 5,028,523 (Skoug), benzoyl acid compounds as described, for example, in U.S. Pat. No. 4,784,939 (Pham), substituted propenenitrile compounds as described, for example, in U.S. Pat. No. 5,686,228 (Murray et al.), silyl blocked compounds as described, for example, in U.S. Pat. No. 5,358,843 (Sakizadeh et al.), vinyl sulfones as described, for example, in U.S. Pat. No. 6,143,487 (Philip, Jr. et al.), diisocyanate compounds as described, for example, in EP 0 600 586A1 (Philip, Jr. et al.), and tribromomethylketones as described, for example, in EP 0 600 587A1 (Oliffet al.).
Preferably, the photothermographic materials of this invention include one or more polyhalo antifoggants that include one or more polyhalo substituents including but not limited to, dichloro, dibromo, trichloro, and tribromo groups. The antifoggants can be aliphatic, alicyclic or aromatic compounds, including aromatic heterocyclic and carbocyclic compounds.
Particularly useful antifoggants are polyhalo antifoggants, such as those having a xe2x80x94SO2C(Xxe2x80x2)3 group wherein Xxe2x80x2 represents the same or different halogen atoms.
Advantageously, the photothermographic materials of this invention also include one or more thermal solvents (or melt formers). Representative examples of such compounds include, but are not limited to, salicylanilide, phthalimide, N-hydroxyphthalimide, N-potassium-phthalimide, succinimide, N-hydroxy-1,8-naphthalimide, phthalazine, 1-(2H)-phthalazinone, 2-acetylphthalazinone, benzanilide, dimethylurea, D-sorbitol, and benzenesulfonamide. Combinations of these compounds can also be used including a combination of succinimide and dimethylurea. Known thermal solvents are disclosed, for example, in U.S. Pat. No. 3,438,776 (Yudelson), U.S. Pat. No. 5,250,386 (Aono et al.), U.S. Pat. No. 5,368,979 (Freedman et al.), U.S. Pat. No. 5,716,772 (Taguchi et al.), and U.S. Pat. No. 6,013,420 (Windender).
It is often advantageous to include a base-release agent or base precursor in the photothermographic materials according to the invention to provide improved and more effective image development. A base-release agent or base precursor as employed herein is intended to include compounds which upon heating in the photothermographic material provide a more effective reaction between the described photosensitive silver halide, and the image-forming combination comprising a silver salt and the silver halide developing agent. Representative base-release agents or base precursors include guanidinium compounds, such as guanidinium trichloroacetate, and other compounds that are known to release a base but do not adversely affect photographic silver halide materials, such as phenylsulfonyl acetates. Further details are provided in U.S. Pat. No. 4,123,274 (Knight et al.).
A range of concentration of the base-release agent or base precursor is useful in the described photothermographic materials. The optimum concentration of base-release agent or base precursor will depend upon such factors as the desired image, particular components in the photothermographic material, and processing conditions.
The use of xe2x80x9ctonersxe2x80x9d or derivatives thereof that improve the image are highly desirable components of the thermographic and photothermographic materials of this invention. Toners are compounds that when added to the imaging layer shift the color of the developed silver image from yellowish-orange to brown-black or blue-black. Generally, one or more toners described herein are present in an amount of about 0.01 % by weight to about 10%, and more preferably about 0.1% by weight to about 10% by weight, based on the total dry weight of the layer in which it is included. Toners may be incorporated in the photothermographic emulsion layer or in an adjacent layer.
Such compounds are well known materials in the photothermographic art, as shown in U.S. Pat. No. 3,080,254 (Grant, Jr.), U.S. Pat. No. 3,847,612 (Winslow), U.S. Pat. No. 4,123,282 (Winslow), U.S. Pat. No. 4,082,901 (Laridon et al.), U.S. Pat. No. 3,074,809 (Owen), U.S. Pat. No. 3,446,648 (Workman), U.S. Pat. No. 3,844,797 (Willems et al.), U.S. Pat. No. 3,951,660 (Hagemann et al.), U.S. Pat. No. 5,599,647 (Defieuw et al.) and GB 1,439,478 (AGFA).
Examples of toners include, but are not limited to, phthalimide and N-hydroxyphthalimide, cyclic imides (such as succinimide), pyrazoline-5-ones, quinazolinone, 1-phenylurazole, 3-phenyl-2-pyrazoline-5-one, and 2,4-thiazolidinedione, naphthalimides (such as N-hydroxy-1,8-naphthalimide), cobalt complexes [such as hexaaminecobalt(3+) trifluoroacetate], mercaptans (such as 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole), N-(aminomethyl)aryldicarboximides (such as (N,N-dimethylaminomethyl)phthalimide), and N-(dimethylaminomethyl)naphthalene-2,3-dicarboximide, a combination of blocked pyrazoles, isothiuronium derivatives, and certain photobleach agents [such as a combination of N,Nxe2x80x2-hexamethylene-bis(1-carbamoyl-3,5-dimethylpyrazole), 1,8-(3,6-diazaoctane)bis(isothiuronium)trifluoroacetate, and 2-(tribromomethylsulfonyl benzothiazole)], merocyanine dyes {such as 3-ethyl-5-[(3-ethyl-2-benzothiazolinylidene)-1-methyl-ethylidene]-2-thio-2,4-o-azolidinedione}, phthalazine and derivatives thereof [such as those described in U.S. Pat. No. 6,146,822 (Asanuma et al.)], phthalazinone and phthalazinone derivatives, or metal salts or these derivatives [such as 4-(1-naphthyl)phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone, and 2,3-dihydro-1,4-phthalazinedione], a combination of phthalazine (or derivative thereof) plus one or more phthalic acid derivatives (such as phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, and tetrachlorophthalic anhydride), quinazolinediones, benzoxazine or naphthoxazine derivatives, rhodium complexes functioning not only as tone modifiers but also as sources of halide ion for silver halide formation in-situ [such as ammonium hexachlororhodate (3+), rhodium bromide, rhodium nitrate, and potassium hexachlororhodate (3+)], benzoxazine-2,4-diones (such as 1,3-benzoxazine-2,4-dione, 8-methyl-1,3-benzoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,4-dione), pyrimidines and asym-triazines (such as 2,4-dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine and azauracil) and tetraazapentalene derivatives [such as 3,6-dimercapto-1,4-diphenyl-1H,4H-2,3a,5,6a-tetraazapentalene and 1,4-di-(o-chlorophenyl)-3,6-dimercapto-1H,4H-2,3a,5,6a-tetraazapentalene].
Phthalazines and phthalazine derivatives [such as those described in U.S. Pat. No. 6,146,822 (noted above), incorporated herein by reference], phthalazinone, and phthalazinone derivatives are particularly useful toners.
Additional useful toners are substituted and unsubstituted mercaptotriazoles as described for example in U.S. Pat. No. 3,832,186 (Masuda et al.), U.S. Pat. No. 6,165,704 (Miyake et al.), U.S. Pat. No. 5,149,620 (Simpson et al.), and copending and commonly assigned U.S. Ser. No. 10/193,443 (filed Jul. 11, 2002 by Lynch, Zou, and Ulrich) and U.S. Ser. No. 10/192,944 (filed Jul. 11, 2002 by Lynch, Ulrich, and Zou), all of which are incorporated herein by reference.
The photothermographic materials of this invention can also include one or more image stabilizing compounds that are usually incorporated in a xe2x80x9cbacksidexe2x80x9d layer. Such compounds can include, but are not limited to, phthalazinone and its derivatives, pyridazine and its derivatives, benzoxazine and benzoxazine derivatives, benzothiazine dione and its derivatives, and quinazoline dione and its derivatives, particularly as described in copending and commonly assigned U.S. Ser. No. 10/041,386 (filed Jan. 8, 2002 by Kong). Other useful backside image stabilizers include, but are not limited to, anthracene compounds, coumarin compounds, benzophenone compounds, benzotriazole compounds, naphthalic acid imide compounds, pyrazoline compounds, or compounds described for example, in U.S. Pat. No. 6,465,162 (Kong et al.) and GB 1,565,043 (Fuji Photo). All of these patents and patent applications are incorporated herein by reference.
The photosensitive silver halide (when used), the non-photosensitive source of reducible silver ions, the reducing agent composition described above, and any other imaging layer additives used in the present invention are generally added to one or more binders that are either hydrophilic or hydrophobic. Thus, either aqueous or organic solvent-based formulations can be used to prepare the thermally developable materials of this invention. Mixtures of either or both types of binders can also be used. It is preferred that the binder be selected from hydrophobic polymeric materials such as, for example, natural and synthetic resins that are sufficiently polar to hold the other ingredients in solution or suspension.
Examples of typical hydrophobic binders include, but are not limited to, polyvinyl acetals, polyvinyl chloride, polyvinyl acetate, cellulose acetate, cellulose acetate butyrate, polyolefins, polyesters, polystyrenes, polyacrylonitrile, polycarbonates, methacrylate copolymers, maleic anhydride ester copolymers, butadiene-styrene copolymers, and other materials readily apparent to one skilled in the art. Copolymers (including terpolymers) are also included in the definition of polymers. The polyvinyl acetals (such as polyvinyl butyral and polyvinyl formal) and vinyl copolymers (such as polyvinyl acetate and polyvinyl chloride) are particularly preferred. Particularly suitable binders are polyvinyl butyral resins that are available as BUTVAR(copyright) B79 and PIOLOFORM(copyright) BS-18 or PIOLOFORM(copyright) BL-16. Aqueous dispersions (or latexes) of hydrophobic binders may also be used.
Examples of useful hydrophilic binders include, but are not limited to, proteins and protein derivatives, gelatin and gelatin-like derivatives (hardened or unhardened, including alkali- and acid-treated gelatins, acetylated gelatin, oxidized gelatin, phthalated gelatin, and deionized gelatin), cellulosic materials such as hydroxymethyl cellulose and cellulosic esters, acrylamide/methacrylamide polymers, acrylic/methacrylic polymers polyvinyl pyrrolidones, polyvinyl alcohols, poly(vinyl lactams), polymers of sulfoalkyl acrylate or methacrylates, hydrolyzed polyvinyl acetates, polyacrylamides, polysaccharides (such as dextrans and starch ethers), and other synthetic or naturally occurring vehicles commonly known for use in aqueous-based photographic emulsions (see for example, Research Disclosure, item 38957, noted above). Cationic starches can be used as a peptizer for tabular silver halide grains as described in U.S. Pat. No. 5,620,840 (Maskasky) and U.S. Pat. No. 5,667,955 (Maskasky).
Hardeners for various binders may be present if desired. Useful hardeners are well known and include diisocyanate compounds as described for example, in EP 0 600 586 B1 (Philip, Jr. et al.) and vinyl sulfone compounds as described in U.S. Pat. No. 6,143,487 (Philip, Jr. et al.), and EP 0 640 589 (Gathmann et al.), aldehydes and various other hardeners as described in U.S. Pat. No. 6,190,822 (Dickerson et al.). The hydrophilic binders used in the photothermographic materials are generally partially or fully hardened using any conventional hardener. Useful hardeners are well known and are described, for example, in T. H. James, The Theory of the Photographic Process, Fourth Edition, Eastman Kodak Company, Rochester, N.Y., 1977, Chapter 2, pp. 77-8.
Where the proportions and activities of the thermographic and photothermographic materials require a particular developing time and temperature, the binder(s) should be able to withstand those conditions. When a hydrophobic binder is used, it is preferred that the binder does not decompose or lose its structural integrity at 120xc2x0 C. for 60 seconds. When a hydrophilic binder is used, it is preferred that the binder does not decompose or lose its structural integrity at 150xc2x0 C. for 60 seconds. It is more preferred that it does not decompose or lose its structural integrity at 177xc2x0 C. for 60 seconds.
The polymer binder(s) is used in an amount sufficient to carry the components dispersed therein. The effective range of amount of polymer can be appropriately determined by one skilled in the art. Preferably, a binder is used at a level of about 10% by weight to about 90% by weight, and more preferably at a level of about 20% by weight to about 70% by weight, based on the total dry weight of the layer in which it is included.
It is particularly useful in the thermally developable materials of this invention to use predominantly (more than 50% by weight of total binder weight) hydrophobic binders in both imaging and non-imaging layers on the side of the support having the imaging layer(s).
The thermally developable materials of this invention comprise a polymeric support that is preferably a flexible, transparent film that has any desired thickness and is composed of one or more polymeric materials, depending upon their use. The supports are generally transparent (especially if the material is used as a photomask) or at least translucent, but in some instances, opaque supports may be useful. They are required to exhibit dimensional stability during thermal development and to have suitable adhesive properties with overlying layers. Useful polymeric materials for making such supports include, but are not limited to, polyesters (such as polyethylene terephthalate and polyethylene naphthalate), cellulose acetate and other cellulose esters, polyvinyl acetal, polyolefins (such as polyethylene and polypropylene), polycarbonates, and polystyrenes (and polymers of styrene derivatives). Preferred supports are composed of polymers having good heat stability, such as polyesters and polycarbonates. Polyethylene terephthalate film is a particularly preferred support. Various support materials are described, for example, in Research Disclosure, 1979, item 18431. A method of making dimensionally stable polyester films is described in Research Disclosure, 1999, item 42536.
It is also useful to use supports comprising dichroic mirror layers wherein the dichroic mirror layer reflects radiation at least having the predetermined range of wavelengths to the emulsion layer and transmits radiation having wavelengths outside the predetermined range of wavelengths. Such dichroic supports are described in U.S. Pat. No. 5,795,708 (Boutet), incorporated herein by reference.
It is further useful to use transparent, multilayer, polymeric supports comprising numerous alternating layers of at least two different polymeric materials. Such multilayer polymeric supports preferably reflect at least 50% of actinic radiation in the range of wavelengths to which the photothermographic sensitive material is sensitive, and provide photothermographic materials having increased speed. Such transparent, multilayer, polymeric supports are described in WO 02/21208 (Simpson et al.), incorporated herein by reference.
Opaque supports can also be used, such as dyed polymeric films and resin-coated papers that are stable to high temperatures.
Support materials can contain various colorants, pigments, antihalation or acutance dyes if desired. For example, the support can contain conventional blue dyes that differ in absorbance from colorants in the various frontside or backside layers, for example as described in U.S. Pat. No. 6,248,442 (Van Achere et al.). Support materials may be treated using conventional procedures (such as corona discharge) to improve adhesion of overlying layers, or subbing or other adhesion-promoting layers can be used. Useful subbing layer formulations include those conventionally used for photographic materials such as vinylidene halide polymers.
Support materials may also be treated or annealed to reduce shrinkage and promote dimensional stability.
An organic-based formulation for the thermographic and photothermographic emulsion layer(s) can be prepared by dissolving and dispersing the binder, the photocatalyst (when used), the source of non-photosensitive silver ions, the reducing composition, toner(s), and optional addenda in an organic solvent, such as toluene, 2-butanone (methyl ethyl ketone), acetone, or tetrahydrofuran.
Alternatively, the desired imaging components can be formulated with a hydrophilic binder (such as gelatin, a gelatin-derivative, or a latex) in water or water-organic solvent mixtures to provide aqueous-based coating formulations.
Thermographic and photothermographic materials of the invention can contain plasticizers and lubricants such as poly(alcohols) and diols of the type described in U.S. Pat. No. 2,960,404 (Milton et al.), fatty acids or esters such as those described in U.S. Pat. No. 2,588,765 (Robijns) and U.S. Pat. No. 3,121,060 (Duane), and silicone resins such as those described in GB 955,061 (DuPont). The materials can also contain matting agents such as starch, titanium dioxide, zinc oxide, silica, and polymeric beads including beads of the type described in U.S. Pat. No. 2,992,101 (Jelley et al.) and U.S. Pat. No. 2,701,245 (Lynn). Polymeric fluorinated surfactants may also be useful in one or more layers of the imaging materials for various purposes, such as improving coatability and optical density uniformity as described in U.S. Pat. No. 5,468,603 (Kub).
U.S. Pat. No. 6,436,616 (Geisler et al.) describes various means of modifying photothermographic materials to reduce what is known as the xe2x80x9cwoodgrainxe2x80x9d effect, or uneven optical density. This effect can be reduced or eliminated by several means, including treatment of the support, adding matting agents to the topcoat, using acutance dyes in certain layers or other procedures described in the noted publication.
The thermographic and photothermographic materials of this invention can be constructed of one or more layers on the imaging side of the support. Single layer materials should contain the photocatalyst, the non-photosensitive source of reducible silver ions, the reducing agent composition, the binder, as well as optional materials such as toners, acutance dyes, coating aids, and other adjuvants.
Two-layer constructions comprising a single imaging layer coating containing all the ingredients and a surface protective topcoat are generally found on the frontside of the materials of this invention. However, two-layer constructions containing photocatalyst and non-photosensitive source of reducible silver ions in one imaging layer (usually the layer adjacent to the support) and the reducing composition and other ingredients in the second imaging layer or distributed between both layers are also envisioned.
Layers to promote adhesion of one layer to another in thermographic and photothermographic materials are also known, as described for example in U.S. Pat. No. 5,891,610 (Bauer et al.), U.S. Pat. No. 5,804,365 (Bauer et al.), and U.S. Pat. No. 4,741,992 (Przezdziecki). Adhesion can also be promoted using specific polymeric adhesive materials as described for example in U.S. Pat. No. 5,928,857 (Geisler et al.).
Layers to reduce emissions from the film may also be present, including the polymeric barrier layers described in U.S. Pat. No. 6,352,819 (Kenney et al.), U.S. Pat. No. 6,352,820 (Bauer et al.), and U.S. Pat. No. 6,420,102B1 (Bauer et al.), all incorporated herein by reference.
Thermographic and photothermographic formulations described herein can be coated by various coating procedures including wire wound rod coating, dip coating, air knife coating, curtain coating, slide coating, or extrusion coating using hoppers of the type described in U.S. Pat. No. 2,681,294 (Beguin). Layers can be coated one at a time, or two or more layers can be coated simultaneously by the procedures described in U.S. Pat. No. 2,761,791 (Russell), U.S. Pat. No. 4,001,024 (Dittman et al.), U.S. Pat. No. 4,569,863 (Keopke et al.), U.S. Pat. No. 5,340,613 (Hanzalik et al.), U.S. Pat. No. 5,405,740 (LaBelle), U.S. Pat. No. 5,415,993 (Hanzalik et al.), U.S. Pat. No. 5,525,376 (Leonard), U.S. Pat. No. 5,733,608 (Kessel et al.), U.S. Pat. No. 5,849,363 (Yapel et al.), U.S. Pat. No. 5,843,530 (Jerry et al.), U.S. Pat. No. 5,861,195 (Bhave et al.), and GB 837,095 (Ilford). A typical coating gap for the emulsion layer can be from about 10 to about 750 xcexcm, and the layer can be dried in forced air at a temperature of from about 20xc2x0 C. to about 100xc2x0 C. It is preferred that the thickness of the layer be selected to provide maximum image densities greater than about 0.2, and more preferably, from about 0.5 to 5.0 or more, as measured by a MacBeth Color Densitometer Model TD 504.
When the layers are coated simultaneously using various coating techniques, a xe2x80x9ccarrierxe2x80x9d layer formulation comprising a single-phase mixture of the two or more polymers described above may be used. Such formulations are described in U.S. Pat. No. 6,355,405 (Ludemann et al.), incorporated herein by reference.
Mottle and other surface anomalies can be reduced in the materials of this invention by incorporation of a fluorinated polymer as described for example in U.S. Pat. No. 5,532,121 (Yonkoski et al.) or by using particular drying techniques as described, for example in U.S. Pat. No. 5,621,983 (Ludemann et al.).
Preferably, two or more layers are simultaneously applied to a film support using slide coating. The first and second fluids used to coat these layers can be the same or different solvents (or solvent mixtures).
While the first and second layers can be coated on one side of the film support, manufacturing methods can also include forming on the opposing or backside of said polymeric support, one or more additional layers, including the required conductive layer, and optionally an antihalation layer or a layer containing a matting agent (such as silica), or a combination of such layers.
It is also contemplated that the photothermographic materials of this invention can include emulsion layers on both sides of the support. Such constructions can further include at least one infrared radiation absorbing heat-bleachable compositions as an antihalation underlayer beneath at least one emulsion layer.
To promote image sharpness, photothermographic materials according to the present invention can contain one or more layers containing acutance and/or antihalation dyes. These dyes are chosen to have absorption close to the exposure wavelength and are designed to absorb scattered light. One or more antihalation compositions may be incorporated into one or more antihalation layers according to known techniques, as an antihalation backing layer, as an antihalation underlayer, or as an antihalation overcoat. Additionally, one or more antihalation or acutance dyes may be incorporated into one or more frontside layers such as the photothermographic emulsion layer, carrier layer, primer layer, underlayer, or topcoat layer according to known techniques. It is preferred that the photothermographic materials of this invention contain an antihalation composition on the backside of the support, and more preferably in the backside topcoat layer.
Dyes useful as antihalation and acutance dyes include squaraine dyes described in U.S. Pat. No. 5,380,635 (Gomez et al.), U.S. Pat. No. 6,063,560 (Suzuki et al.), and EP 1 083 459A1 (Kimura), the indolenine dyes described in EP 0 342 810A1 (Leichter), and the cyanine dyes described in copending and commonly assigned U.S. Ser. No. 10/01 1,892 (filed Dec. 5, 2001 by Hunt, Kong, Ramsden, and LaBelle). All of the above references are incorporated herein by reference.
It is also useful in the present invention to employ compositions including acutance or antihalation dyes that will decolorize or bleach with heat during processing. Dyes and constructions employing these types of dyes are described in, for example, U.S. Pat. No. 5,135,842 (Kitchin et al.), U.S. Pat. No. 5,266,452 (Kitchin et al.), U.S. Pat. No. 5,314,795 (Helland et al.), U.S. Pat. No. 6,306,566, (Sakurada et al.), U.S. Published Application 2001-0001704 (Sakurada et al.), JP Kokai 2001-142175 (Hanyu et al.), and JP Kokai 2001-183770 (Hanye et al.). Also useful are bleaching compositions described in JP Kokai 11-302550 (Fujiwara), JP Kokai 2001-109101 (Adachi), JP Kokai 2001-51371 (Yabuki et al.), and JP Kokai 2000-029168 (Noro). All of the above publications are incorporated herein by reference.
Particularly useful heat-bleachable backside antihalation compositions can include an infrared radiation absorbing compound such as an oxonol dyes and various other compounds used in combination with a hexaarylbiimidazole (also known as a xe2x80x9cHABIxe2x80x9d), or mixtures thereof. Such HABI compounds are well known in the art, such as U.S. Pat. No. 4,196,002 (Levinson et al.), U.S. Pat. No. 5,652,091 (Perry et al.), and U.S. Pat. No. 5,672,562 (Perry et al.), all incorporated herein by reference. Examples of such heat-bleachable compositions are described for example in U.S. Pat. No. 6,455,210 (Irving et al.), U.S. Ser. No. 09/875,772 (filed Jun. 6, 2001 by Goswami, Ramsden, Zielinski, Baird, Weinstein, Helber, and Lynch), and U.S. Ser. No. 09/944,573 (filed Aug. 31, 2001 by Ramsden and Baird), all incorporated herein by reference.
Under practical conditions of use, the compositions are heated to provide bleaching at a temperature of at least 90xc2x0 C. for at least 0.5 seconds. Preferably, bleaching is carried out at a temperature of from about 1 00xc2x0 C. to about 200xc2x0 C. for from about 5 to about 20 seconds. Most preferred bleaching is carried out within 20 seconds at a temperature of from about 110xc2x0 C. to about 130xc2x0 C.
In some embodiments, the photothermographic materials of this invention comprise one or more acutance dyes in the one or more thermally developable imaging layers. In some embodiments the photothermographic materials comprise one or more antihalation dyes in the one or more non-imaging layers on the imaging side of the support. In some embodiments, the photothermographic materials of this invention comprise one or more antihalation dyes in the backside layer on the support, and more preferably in the backside topcoat layer. Such non-imaging layers include, for example, carrier layers, primer layers, barrier layers, or topcoat layers.
Some materials of the present invention may have an optical density at a wavelength close to that of the exposure of from about 0.2 to about 3 on the imaging side of the support, and an optical density of up to 2 on the backside of the support, as measured using a conventional spectrophotometer.
In preferred embodiments, the thermally developable materials of this invention include a surface protective layer on the same side of the support as the one or more thermally-developable layers and a conductive layer on the back side of the support underneath a protective layer that can also include an antihalation composition.
The essential feature of the present invention is the presence of at least one conductive layer on the backside (non-imaging side) of the support that includes one or more specific non-acicular metal antimonate particles having a composition represented by the following Structure I or II:
M+2Sb+52O6xe2x80x83xe2x80x83(I)
wherein M is zinc, nickel, magnesium, iron, copper, manganese, or cobalt,
Ma+3Sb+5O4xe2x80x83xe2x80x83(II)
wherein Ma is indium, aluminum, scandium, chromium, iron, or gallium.
Thus, these particles are generally metal oxides that are doped with antimony.
Preferably, the non-acicular metal antimonate particles are composed of ZnSb2O6. Several conductive metal antimonates are commercially available from Nissan Chemical America Corporation including the preferred ZnSb2O6 non-acicular particles that are available as a 40% (solids) organosol dispersion under the tradename CELNAX(copyright) CX-Z401M.
Alternatively, the metal antimonate particles can be prepared using methods described for example in U.S. Pat. No. 5,457,013 (noted above) and references cited therein.
The metal antimonate particles in the backside conductive layer are predominately (more than 40% by weight of total particles) in the form of non-acicular particles as opposed to xe2x80x9cacicularxe2x80x9d particles. By xe2x80x9cnon-acicularxe2x80x9d particles is meant not needlelike, that is, not acicular. Thus, the shape of the metal antimonate particles can be granular, spherical, ovoid, cubic, rhombic, tabular, tetrahedral, octahedral, icosahedral, truncated cubic, truncated rhombic, or any other non-needle like shape.
Generally, these metal particles have an average diameter of from about 15 to about 20 nm as measured across the largest particle dimension using the BET method.
The non-acicular metal antimonate particles generally comprise from about 40 to about 55% (preferably from about 40 to about 50%) by weight of the buried backside conductive layer. Another way of defining the amount of particles is that they are generally present in the backside conductive layer in an amount of from about 0.05 to about 2 g/m2. Mixtures of different types of non-acicular metal antimonate particles can be used if desired.
The non-acicular metal antimonate particles are also generally present in an amount sufficient to provide a backside surface resistivity measured at 70xc2x0 F. (21.1xc2x0 C.) and 20% relative humidity of 4xc3x971012 ohms/sq or less, a static decay time of 0.02 seconds, or a wet electrode resistivity of 1xc3x971012 ohms/sq or less and preferably 1xc3x971010 ohms/sq or less as measured using the techniques and procedures described herein.
An essential aspect of the present invention is the fact that the conductive metal antimonate particles are present in one or more backside conductive layers that are xe2x80x9cburiedxe2x80x9d on the backside of the support, meaning that there is at least one other layer disposed over the backside conductive layer(s). Moreover, the relationship of the backside conductive layer(s), and the layer or layers immediately adjacent is important because the types of polymers and binders in these layers are designed to provide excellent adhesion to one another as well as acceptably dispersing the conductive metal antimonate particles and/or or layer components, and are readily coated simultaneously or separately.
The xe2x80x9cburiedxe2x80x9d backside conductive layer may also be relatively thin in comparison to other layers on the backside, and in such instances, it can have a dry thickness of less than 2 xcexcm, and preferably a dry thickness of from about 0.06 to about 2 xcexcm. Because of these useful features, the xe2x80x9cburiedxe2x80x9d backside conductive layer is useful as a xe2x80x9ccarrierxe2x80x9d layer. The term xe2x80x9ccarrier layerxe2x80x9d is often used when multiple layers are coated using slide coating and the buried backside conductive layer is a thin layer adjacent to the support.
In one preferred embodiment, the backside conductive layer is directly disposed on the support without the use of primer or subbing layers, or other adhesion-promoting means such as support surface treatments. Thus, the support can be used in an xe2x80x9cuntreatedxe2x80x9d and xe2x80x9cuncoatedxe2x80x9d form when a buried backside conductive layer is used.
The layer directly disposed over the conductive layers is known herein as a xe2x80x9cfirstxe2x80x9d layer and can be known as a xe2x80x9cprotectivexe2x80x9d layer that can be the outermost topcoat layer or have further layer(s) disposed thereon. This first layer comprises a film-forming polymer. The backside conductive layer immediately underneath comprises the non-acicular metal antimonate particles in a mixture of two or more polymers that includes a xe2x80x9cfirstxe2x80x9d polymer serving to promote adhesion of the backside conductive layer directly to the polymeric support, and a xe2x80x9csecondxe2x80x9d polymer that is different than and forms a single phase mixture with the first polymer.
It is preferred that film-forming polymer of the first layer and the second polymer of the backside conductive layer are the same or different polyvinyl acetal resins, polyester resins, cellulosic polymers, maleic anhydrideester copolymers, or vinyl polymers. It is more preferred that the film-forming polymer of the first layer and the second polymer of the backside conductive layer is a polyvinyl acetal such as polyvinyl butyral or cellulose ester such as cellulose acetate butyrate. It is preferred that the xe2x80x9cfirstxe2x80x9d polymer of the backside conductive layer is a polyester resin. It is most preferred that the backside conductive layer use a single phase mixture of a polyester resin as a xe2x80x9cfirstxe2x80x9d polymer and cellulose acetate butyrate as a xe2x80x9csecondxe2x80x9d polymer.xe2x80x9d
It is preferred to use a mixture of polymers, that is, a first polymer that promotes adhesion to the support and a second polymer that promotes adhesion to the first layer. For example, when the support is a polyester film, and the backside conductive layer contains a polyvinyl acetal or a cellulose ester, then a preferred mixture of polymers in that conductive layer is a single phase mixture of a polyester resin and a polyvinyl acetal such as polyvinyl butyral or cellulose ester such as cellulose acetate butyrate.
In another embodiment, the buried backside conductive layer is disposed between a xe2x80x9cfirstxe2x80x9d layer and a xe2x80x9csecondxe2x80x9d layer directly adhering the support. In this embodiment, the xe2x80x9cfirstxe2x80x9d layer is directly above the backside conductive layer and is known herein as a xe2x80x9cfirstxe2x80x9d layer, a xe2x80x9cprotectivexe2x80x9d layer, or a xe2x80x9cprotective topcoatxe2x80x9d layer. It can be the outermost topcoat layer or have further layer(s) disposed thereon. This first layer comprises a film-forming polymer. The conductive layer immediately beneath the first layer comprises the non-acicular metal antimonate particles in a polymer that serves to promote adhesion of the backside conductive layer to the first layer as well as to a xe2x80x9csecondxe2x80x9d layer immediately beneath it. This second layer is directly adhered to the polymeric support. The second layer directly adhered to the support comprises a mixture of two or more polymers. The first polymer serves to promote adhesion of the second layer directly to the polymeric support. The second polymer serves to promote adhesion of the second layer to the backside conductive layer.
It is preferred that the film-forming polymer of the first layer, the polymer of the backside conductive layer, and the second polymer of the second layer are the same or different polyvinyl acetal resins, polyester resins, cellulosic ester polymers, maleic anhydride-ester copolymers, or vinyl polymers. A preferred polymer is cellulose acetate butyrate.
It is preferred that the second, adhesion-promoting, layer use a single phase mixture of a polyester resin as a xe2x80x9cfirstxe2x80x9d polymer and a polyvinyl acetal such as polyvinyl butyral or cellulose ester such as cellulose acetate butyrate as a xe2x80x9csecondxe2x80x9d polymer.xe2x80x9d
In another embodiment, the buried backside conductive layer is disposed between a xe2x80x9cfirstxe2x80x9d layer and a xe2x80x9csecondxe2x80x9d layer directly adhering to the support. In this embodiment, the first layer is directly above the backside conductive layer is known herein as a xe2x80x9cfirstxe2x80x9d layer, a xe2x80x9cprotectivexe2x80x9d layer, or a xe2x80x9cprotective topcoatxe2x80x9d layer. It can be the outermost topcoat layer or have further layer(s) disposed thereon. This first layer comprises a film-forming polymer. The conductive layer immediately beneath the first layer comprises the non-acicular metal antimonate particles in a mixture of two or more polymers, a xe2x80x9cfirstxe2x80x9d polymer that serves to promote adhesion of the conductive layer to the second layer, and a xe2x80x9csecondxe2x80x9d polymer that serves to promote adhesion of the conductive layer to the first layer.
It is preferred that the film-forming polymer of the first layer, and the xe2x80x9csecondxe2x80x9d polymer of the backside conductive layer are the same or different polyvinyl acetal resins, polyester resins, cellulosic ester polymers, maleic anhydride-ester copolymers, or vinyl polymers. A preferred polymer is cellulose acetate butyrate.
It is preferred that the polymer of second, adhesion-promoting, layer and the xe2x80x9cfirstxe2x80x9d polymer of the backside conductive layer are the same or different polyester resins.
Representative xe2x80x9cfirstxe2x80x9d polymers can be chosen from one or more of the following classes: polyvinyl acetals (such as polyvinyl butyral, polyvinyl acetal, and polyvinyl formal), cellulosic ester polymers (such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, hydroxymethyl cellulose, cellulose nitrate, and cellulose acetate butyrate), polyesters, polycarbonates, epoxies, rosin polymers, polyketone resin, vinyl polymers (such as polyvinyl chloride, polyvinyl acetate, polystyrene, polyacrylonitrile, and butadiene-styrene copolymers), acrylate and methacrylate polymers, and maleic anhydride ester copolymers. The polyvinyl acetals, polyesters, cellulosic ester polymers, and vinyl polymers such as polyvinyl acetate and polyvinyl chloride are particularly preferred, and the polyvinyl acetals, polyesters, and cellulosic ester polymers are more preferred. Polyester resins are most preferred. Thus, the adhesion-promoting polymers are generally hydrophobic in nature.
Representative xe2x80x9csecondxe2x80x9d polymers include polyvinyl acetals, cellulosic polymers, vinyl polymers (as defined above for the xe2x80x9cfirstxe2x80x9d polymer), acrylate and methacrylate polymers, and maleic anhydride-ester copolymers. The most preferred xe2x80x9csecondxe2x80x9d polymers are polyvinyl acetals and cellulosic ester polymers (such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, hydroxymethyl cellulose, cellulose nitrate, and cellulose acetate butyrate). Cellulose acetate butyrate is a particularly preferred second polymer. Of course, mixtures of these second polymers can be used in the backside conductive layer. These second polymers are also soluble or dispersible in the organic solvents described above.
It is preferred that the xe2x80x9cfirstxe2x80x9d and xe2x80x9csecondxe2x80x9d polymers are compatible with each other or are of the same polymer class. One skilled in the art would readily understand from the teaching herein which polymers are xe2x80x9ccompatible withxe2x80x9d or xe2x80x9cof the same classxe2x80x9d as those film-forming polymers. For example, it is most preferred to use a single phase mixture of a polyester resin as a xe2x80x9cfirstxe2x80x9d polymer and a cellulose ester such as cellulose acetate butyrate as a xe2x80x9csecondxe2x80x9d polymer.xe2x80x9dMany of the film-forming polymers useful in the first layer are described in other places herein (for example, binders used in imaging layers and or other conventional backside layers).
The backside conductive layers are generally coated out of one or more miscible organic solvents including, but not limited to, methyl ethyl ketone (2-butanone, MEK), acetone, toluene, tetrahydrofuran, ethyl acetate, ethanol, methanol, or any mixture of any two or more of these solvents.
The backside conductive layers described herein can be coated by various coating procedures such as those described above for the thermographic and photothermographic imaging layers. Such procedures include wire wound rod coating, dip coating, air knife coating, curtain coating, slide coating, roll coating, reverse roll coating, gravure coating, or extrusion coating
The weight ratio of xe2x80x9cfirstxe2x80x9d polymer to xe2x80x9csecondxe2x80x9d polymer in the backside conductive layer is generally from about 10:90 to about 40:60 , and preferably from about 10:90 to about 30:70. A most preferred polymer combination is of polyester and cellulose acetate butyrate having a weight ratio of about 20:80.
The backside conductive layer can also include still other polymers that are not defined herein as first or second polymers. These additional polymers can be either hydrophobic or hydrophilic. Some hydrophilic polymers that may be present include, but are not limited to, proteins or polypeptides such as gelatin and gelatin derivatives, polysaccharides, gum arabic, dextrans, polyacrylamides (including polymethacrylamides), polyvinyl pyrrolidones and others that would be readily apparent to one skilled in the art.
The polymers in the backside conductive layer generally comprise at least 0.1 weight % (preferably at least 0.2 weight %) of the total wet coating weight of the layer. The maximum amount of such polymers is generally 40 weight %, and preferably up to 20 weight %, based on total wet coating weight.
As noted above, in preferred embodiments, the backside conductive layer is a relatively thin xe2x80x9cburiedxe2x80x9d layer that provides desired benefits (that is, sensitometric and physical properties) beyond the necessary conductivity. Typically, the backside conductive layer has a dry thickness up to 2 xcexcm and preferably up to 1 xcexcm. The minimum dry thickness is generally at least 0.06 xcexcm and preferably at least 0.15 xcexcm. More preferably, the dry thickness is between 0.15 xcexcm and0.50xcexcm.
Other components of the backside conductive layer include materials that may improve coatability or adhesion, crosslinking agents (such as diisocyanates), surfactants and shelf-aging promoters.
The backside conductive layer may also include other addenda commonly added to such formulations including, but not limited to, shelf life extenders, antihalation dyes, colorants to control tint and tone, UV absorbing materials, to improve light-box stability, and coating aids such as surfactants to achieve high quality coatings, all in conventional amounts. It is also useful to add inorganic matting agents such as the polysilicic acid particles as described in U.S. Pat. No. 4,828,971 (Przezdziecki), poly(methyl methacrylate) beads as described in U.S. Pat. No. 5,310,640 (Markin et al.), or polymeric cores surrounded by a layer of colloidal inorganic particles as described in U.S. Pat. No. 5,750,328 (Melpolder et al.).
In one preferred embodiment, the xe2x80x9cfirstxe2x80x9d backside layer (usually referred to as a protective or topcoat layer) includes an antihalation composition, such as those antihalation compositions described above.
The thermally developable materials of this invention can also include one or more antistatic or conductive layers on the frontside of the support. Such layers may contain metal antimonates as described above, or other conventional antistatic agents known in the art for this purpose such as soluble salts (for example, chlorides or nitrates), evaporated metal layers, or ionic polymers such as those described in U.S. Pat. No. 2,861,056 (Minsk) and U.S. Pat. No. 3,206,312 (Sterman et al.), or insoluble inorganic salts such as those described in U.S. Pat. No. 3,428,451 (Trevoy), electroconductive underlayers such as those described in U.S. Pat. No. 5,310,640 (Markin et al.), electronically-conductive metal antimonate particles such as those described above and in U.S. Pat. No. 5,368,995 (Christian et al.), electrically-conductive metal-containing particles dispersed in a polymeric binder such as those described in EP 0 678 776A1 (Melpolder et al.), and fluorochemicals that are described in numerous publications.
When particles are added to a coating layer, streaking can become a problem. Streaks can be caused by particles getting caught on the lips of a coating slot, causing flow instability, disturbing coating flow, and resulting in streaks. Streaks can also be formed by a denser liquid from an upper coating slot displacing a less dense liquid from a lower coating slot or even by flowing into an incompletely filled lower coating slot. In very thin layers formed from low-viscosity liquids, such as those used as carrier layers in slide coating, flow rates, and coating slot heights need to be adjusted carefully to prevent such penetration (see, for example, E. B. Gutoff and E. D. Cohen xe2x80x9cCoating and Drying Defects,xe2x80x9d John Wiley and Sons, New York, 1995, p. 135).
The addition of metal antimonate particles to carrier layers used in slide coating procedures has been found to reduce streaking. The size of the metal antimonate particles appears to be too small to cause the flow instabilities seen with the larger particles normally used in coating. Moreover, the addition of metal antimonate particles to the carrier layer increases the density of the carrier layer without increasing its viscosity or otherwise reducing its usefulness as a carrier layer. Penetration of the denser upper layer into the coating slot of the lower layer is reduced or prevented by this increase in density. Penetration is most reduced when sufficient metal antimonate particles are present to increases the density of the lower layer so that it is equal to or greater then the density of the solution coated above it.
The thermally developable materials of the present invention can be imaged in any suitable manner consistent with the type of material using any suitable imaging source (typically some type of radiation or electronic signal for photothermographic materials and a source of thermal energy for thermographic materials). In some embodiments, the materials are sensitive to radiation in the range of from about at least 300 nm to about 1400 nm, and preferably from about 300 nm to about 850 nm. In other embodiments, the materials are sensitive to radiation at 700 nm or greater (such as from about 750 to about 950 nm).
Imaging can be achieved by exposing the photothermographic materials of this invention to a suitable source of radiation to which they are sensitive, including ultraviolet radiation, visible light, near infrared radiation and infrared radiation to provide a latent image. Suitable exposure means are well known and include sources of radiation, including: incandescent or fluorescent lamps, xenon flash lamps, lasers, laser diodes, light emitting diodes, infrared lasers, infrared laser diodes, infrared light-emitting diodes, infrared lamps, or any other ultraviolet, visible, or infrared radiation source readily apparent to one skilled in the art, and others described in the art, such as in Research Disclosure, September, 1996, item 38957. Particularly useful infrared exposure means include laser diodes, including laser diodes that are modulated to increase imaging efficiency using what is known as multi-longitudinal exposure techniques as described in U.S. Pat. No. 5,780,207 (Mohapatra et al.). Other exposure techniques are described in U.S. Pat. No. 5,493,327 (McCallum et al.).
Thermal development conditions will vary, depending on the construction used but will typically involve heating the imagewise exposed material at a suitably elevated temperature. Thus, the latent image can be developed by heating the exposed material at a moderately elevated temperature of, for example, from about 50xc2x0 C. to about 250xc2x0 C. (preferably from about 80xc2x0 C. to about 200xc2x0 C. and more preferably from about 100xc2x0 C. to about 200xc2x0 C.) for a sufficient period of time, generally from about 1 to about 120 seconds. Heating can be accomplished using any suitable heating means such as a hot plate, a steam iron, a hot roller or a heating bath.
In some methods, the development is carried out in two steps. Thermal development takes place at a higher temperature for a shorter time (for example at about 150xc2x0 C. for up to 10 seconds), followed by thermal diffusion at a lower temperature (for example at about 80xc2x0 C.) in the presence of a transfer solvent.
When imaging thermographic materials of this invention, the image may be xe2x80x9cwrittenxe2x80x9d simultaneously with development at a suitable temperature using a thermal stylus, a thermal print head or a laser, or by heating while in contact with a heat-absorbing material. The thermographic materials may include a dye (such as an IR-absorbing dye) to facilitate direct development by exposure to laser radiation. The dye converts absorbed radiation to heat.
The thermographic and photothermographic materials of the present invention are sufficiently transmissive in the range of from about 350 to about 450 nm in non-imaged areas to allow their use in a method where there is a subsequent exposure of an ultraviolet or short wavelength visible radiation sensitive imageable medium. For example, imaging the materials and subsequent development affords a visible image. The heat-developed thermographic and photothermographic materials absorbs ultraviolet or short wavelength visible radiation in the areas where there is a visible image and transmit ultraviolet or short wavelength visible radiation where there is no visible image. The heat-developed materials may then be used as a mask and positioned between a source of imaging radiation (such as an ultraviolet or short wavelength visible radiation energy source) and an imageable material that is sensitive to such imaging radiation, such as a photopolymer, diazo material, photoresist, or photosensitive printing plate. Exposing the imageable material to the imaging radiation through the visible image in the exposed and heat-developed photothermographic material provides an image in the imageable material. This method is particularly useful where the imageable medium comprises a printing plate and the photothermographic material serves as an imagesetting film.
The present invention also provides a method for the formation of a visible image (usually a black-and-white image) by first exposing to electromagnetic radiation and thereafter heating the inventive photothermographic material. In one embodiment, the present invention provides a method comprising:
a) imagewise exposing the photothermographic material of this invention to electromagnetic radiation to which the photocatalyst (for example, a photosensitive silver halide) of the material is sensitive, to form a latent image, and
b) simultaneously or sequentially, heating the exposed material to develop the latent image into a visible image.
The photothermographic material may be exposed in step A using any source of radiation, to which it is sensitive, including ultraviolet radiation, visible light, infrared radiation or any other infrared radiation source readily apparent to one skilled in the art.
The present invention also provides a method for the formation of a visible image (usually a black-and-white image) by thermal imaging of the inventive thermographic material. In one embodiment, the present invention provides a method comprising:
A) thermal imaging of the thermographic material of this invention to form a visible image.
This visible image prepared from either a thermographic or photothermographic material can also be used as a mask for exposure of other photosensitive imageable materials, such as graphic arts films, proofing films, printing plates and circuit board films, that are sensitive to suitable imaging radiation (for example, UV radiation). This can be done by imaging an imageable material (such as a photopolymer, a diazo material, a photoresist, or a photosensitive printing plate) through the heat-developed thermographic or photothermographic material. Thus, in some other embodiments wherein the thermographic or photothermographic material comprises a transparent support, the image-forming method further comprises:
c) positioning the exposed and heat-developed thermographic or photothermographic material between a source of imaging radiation and an imageable material that is sensitive to the imaging radiation, and
d) exposing the imageable material to the imaging radiation through the visible image in the exposed and heat-developed photothermographic material to provide an image in the imageable material.
The following examples are provided to illustrate the practice of the present invention and the invention is not meant to be limited thereby.
All materials used in the following examples are readily available from standard commercial sources, such as Aldrich Chemical Co. (Milwaukee Wis.) unless otherwise specified. All percentages are by weight unless otherwise indicated. The following additional terms and materials were used.
ACRYLOID(copyright) A-21 is an acrylic copolymer available from Rohm and Haas (Philadelphia, Pa.).
ALBACAR 5970 is a 1.9 xcexcm precipitated calcium carbonate. It is available from Specialty Minerals, Inc. (Bethlehem, Pa.).
BUTVAR(copyright) B-79 is a polyvinyl butyral resin available from Solutia, Inc. (St. Louis, Mo.).
CAB 171-15S and CAB 381-20 are cellulose acetate butyrate resins available from Eastman Chemical Co. (Kingsport, Tenn.).
CELNAX(copyright) CX-Z401M is a 40% organosol dispersion of non-acicular zinc antimonate particles in methanol. It was obtained from Nissan Chemical America Corporation (Houston, Tex.).
L-9342 is a perfluorinated organic antistatic agent described as Compound 1 of U.S. Pat. No. 4,975,363 (Cavallo et al.). It was obtained from 3M Company (St. Paul, Minn.).
MEK is methyl ethyl ketone (or 2-butanone).
PERMANAX WSO (or NONOX(copyright)) is 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane [CAS RN=7292-14-0] and is available from St-Jean PhotoChemicals, Inc. (Quebec, Canada).
PIOLOFORM(copyright) BL-16 and PIOLOFORM(copyright) BN-18 are polyvinyl butyral resins available from Wacker Polymer Systems (Adrian, Mich.).
SYLOID(copyright) 74X6000 is a synthetic amorphous silica that is available from Grace-Davison (Columbia, Md.).
VITEL(copyright) PE-2700B LMW is a polyester resin available from Bostik, Inc. (Middleton, Mass.).
Backcoat Dye BC-1 is cyclobutenediylium, 1,3-bis[2,3-dihydro-2,2-bis[[1-oxohexyl)oxy]methyl]-1H-perimidin-4-yl]-2,4-dihydroxy-, bis(inner salt). It is believed to have the structure shown below.
Ethyl-2-cyano-3-oxobutanoate has the structure shown below.
Vinyl Sulfone-1 (VS-1) is described in U.S. Pat. No. 6,143,487 and has the following structure:
Resistivity Measurements:
Resistivity of antistatic coatings was measured using three different methods, the xe2x80x9cdecay timexe2x80x9d test, the xe2x80x9csurface resistivityxe2x80x9d test, and the xe2x80x9cwet electrode resistivityxe2x80x9d test.
In the decay xe2x80x9ctime test,xe2x80x9d an ETS Model 406D Static Decay Meter (Electro-Tech Systems Inc., Glenside, Pa.) was used to determine the rate of static charge decay on a sample. The sample is subjected to a fixed voltage to induce an electrostatic charge on its surface. The charge is then dissipated (bled off) by providing a path for current flow to ground. The time for the charge to dissipate to certain pre-selected levels (10% in our test) is recorded.
Decay times were measured in a room maintained at 70xc2x0 F. (21.1xc2x0 C.) and 20% relative humidity (RH) unless otherwise specified. All testing was done in this room after samples had been acclimated for 18 to 24 hours. A +5 kV charge was applied and the time to reach 10% of the charge (90% decay) was recorded. Samples that demonstrate poor antistatic properties do not dissipate charge and their decay times are reported as xe2x80x9cnot conductive.xe2x80x9dIn order to function as an antistatic material, a compound should provide a coating having a decay time of less than 25 seconds and preferably less than 5 seconds at a temperature of 70xc2x0 F. (21.1xc2x0 C.) and a relative humidity of 20%. Decay times less than 1 second are preferred.
In the xe2x80x9csurface resistivityxe2x80x9d (SER) test, three Keithley instruments, a Model 247 High Voltage Supply, a Model 480 Digital Picometer, and a Model 6105 Resistivity Adapter (Keithley Instruments Inc., Cleveland Ohio) were used.
Surface resistivity was again measured in a room maintained at 70xc2x0 F. (21.1xc2x0 C.)/20% relative humidity (RH) and all testing was done in this room. A potential of 500 volts was applied to the sample and the current going through the sample was measured. The conversion from amperes (current) to ohm/sq (resistivity) was calculated using the following equation (provided by Kiethley):
Ohm/sq=26,700/amperes
The Kiethley Device cannot measure current below 1xc3x9710xe2x88x9212 amperes. Thus resistivity greater than 2.67xc3x971016 ohm/sq cannot be calculated. Films having a resistivity calculated greater than 2.67xc3x971016 ohm/sq are reported below as greater than 2.67xc3x971016 ohm/sq. In order to function as an antistatic material, a compound should provide a coating having a resistivity of less than 1xc3x971014 ohm/sq, preferably less than 1xc3x971012 ohm/sq, and more preferably less than 1011 ohm/sq at a temperature of 70xc2x0 F. (21.1xc2x0 C.) and a relative humidity of 20%.
In the xe2x80x9cwet electrode resistivityxe2x80x9d (WER) test, antistatic performance was evaluated by measuring the internal resistivity of the overcoated electrically-conductive antistatic layer using a salt bridge wet electrode resistivity measurement technique. This technique is described in R. A. Elder xe2x80x9cResistivity Measurements on Buried Conductive Layers,xe2x80x9d EOS/ESD Symposium Proceedings, Lake Buena Vista, Fla., 1990, pp. 251-254, incorporated herein by reference. [EOS/ESD stands for Electrical Overstress/Electrostatic Discharge]. Typically, antistatic layers with WER values greater than about 1xc3x971012 ohm/square are considered to be ineffective at providing static protection for photographic imaging elements. We have also found WER measurements to be more predictive of how an antistatic material will perform when used in a commercial product.
Sensitometry Measurements:
Densitometry measurements were made on a custom built computer-scanned densitometer and meeting ISO Standards 5-2 and 5-3 and are believed to be comparable to measurements from commercially available densitometers. Dmin is the density of the non-exposed areas after development and it is the average of the eight lowest density values. | {
"pile_set_name": "USPTO Backgrounds"
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Data storage systems interact with media libraries in data storage and retrieval operations. Media libraries house and control physical media (magnetic tapes, optical disks, and so on) that is used during storage operations, such as data storage operations. Libraries are limited in the number of media components they are able to hold, in many cases due to the physical size of the library. Therefore, a data storage system may need to transfer media components out of the library that are no longer needed or useful for data storage (e.g., media components at their storage capacity, or media components scheduled for offsite archiving), and bring in new media components for future storage operations.
Data storage systems may employ management systems to track the movement of media components to and from media libraries. Periodically, the systems transfer media components to offsite storage locations, such as media components no longer needed or useful for the system at certain times. Management systems may track the movement or location of media components used by a data storage system.
The management systems typically rely on policies that instruct the management systems as to the location of media components and the time at which to transfer media components to a determined location. However, the policies may be somewhat inflexible and lack insight into the needs of a data storage system or its policies, and therefore may instruct the library to perform undesirable media component transfers.
Additionally, libraries may look to similarly rigid policies when ordering new media components to be used in the system. Again, typical data storage systems, using rigid media component ordering and buying policies, generally do not achieve a desirable balance between the needs of a system and the number of media components coming into the system to meet those needs. Some media components are expensive, and thus ordering too many can be costly. Alternatively, it can be detrimental to the system if too few media components are available for a given data store job.
Furthermore, media management systems are not able to control all aspects of media component transfers. Media components are likely to be transferred to offsite storage locations operated by other entities than an entity operating the data storage systems and media libraries. Additionally, new media components enter the system after being purchased from outside vendors. Because outside entities provide, and at time store, media components to the data storage systems, the management of media components may stop or be severely limited when the media components are not physically within or controlled by the system (e.g., when media components are stored offsite).
The foregoing examples of some existing limitations are intended to be illustrative and not exclusive. Other limitations will become apparent to those of skill in the art upon a reading of the Detailed Description below.
These and other problems exist with respect to media management systems.
In the drawings, the same reference numbers and acronyms identify elements or acts with the same or similar functionality for ease of understanding and convenience. To easily identify the discussion of any particular element or act, the most significant digit or digits in a reference number refer to the Figure number in which that element is first introduced (e.g., element 1104 is first introduced and discussed with respect to FIG. 11). | {
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In a cordless telephone system, it is necessary to provide a way of carrying the signal for the contents of communication, normally speech, in both directions between parts of the system which are not connected by a cord or wire. Additionally, it will normally be necessary to pass other signals between the parts, which are used to control the operation of the parts or carry other control messages separate from the content of the communication In some known radio telephone systems, the requirement for two way communication is achieved by providing two radio channels between the parts, each channel being used for communication in one respective direction. In an embodiment of the present invention, multiplexed signal structures are provided enabling a plurality of logical channels to be carried with communication in both directions, over a single signal communications channel. In the embodiment, the use of different multiplex structures at different times permits differences in the logical channel structure of the cordless communication at different stages of the creation and use of the cordless communications link.
In a conventional radio telephone system, an arrangement must be provided enabling a link to be set up so that parts can communicate with each other. When one of the parts is operating in a manner synchronised to some routine, it may be difficult for another part to establish a link with the first part if the second part is not itself synchronised to the same routine.
In an embodiment of the present invention, an arrangement is provided allowing for asynchronous initiation of a link between two parts, even when one of the parts is operating in a synchronous manner.
In a radio telecommunication system, the ability of a radio link to carry useful signals will tend to vary in accordance with external factors, such as interference and transmission past obstructions. Accordingly, it is advantageous to encode transmitted signals for error detection and correction and/or monitor the link quality to enable remedial steps such as breaking and re-establishing the link, possibly on a different radio channel, if the link quality becomes unacceptably low. In an embodiment of the present invention, an arrangement is provided in which two logical channels are multiplexed together, with signals of one logical channel being encoded to enable error detection, and detected errors in this logical channel being monitored and used as a measure of the extent to which the other channel is exposed to errors.
In a system for radio telecommunications, there will typically be a large number of communication devices capable of communicating in the system, some of which may be more sophisticated and have greater communication abilities than others. In order for two devices to communicate with each other, they must communicate in a manner which is within the capabilities of both devices. Thus, when a relatively sophisticated device communicates with an unsophisticated device, they must communicate in a manner within the capabilities of the unsophisticated device. However, it is inefficient to force the sophisticated device also to communicate in this particular manner when it is communicating with another sophisticated device capable of communicating in a different manner. In an embodiment of the present invention, devices conduct an operation (sometimes referred to as a "negotiation" operation) during the creation of a cordless telecommunications link, so as to adopt a way of communicating which is within the capabilities of both devices.
When two devices are communicating over a cordless telecommunications link, it may be necessary for the operations of the devices to be synchronised with each other and this may be done by one device recognising a particular part of a signal transmitted by the other device, the signal part having a predetermined timing. In this case, incorrect synchronisation can arise if the receiving part incorrectly identifies a different part of the transmitted signal as the part to be recognised for synchronisation. In an embodiment of the present invention, a signal is transmitted having a data structure such that a portion used for synchronisation has a low correlation with other portions of the signal not containing the synchronisation part. Additionally, in the embodiment the synchronisation part has a low correlation with time-shifted versions of itself. Preferably, signal parts used for synchronisation are transmitted in both directions between the devices, and a signal part used for synchronisation and transmitted in one direction is arranged to have a low correlation with a signal part used for synchronisation and transmitted in the other direction.
When a plurality of devices capable of communicating over a cordless communications link are present in the same area, and several are scanning communication channels to detect another device seeking to set up a communications link, there is a possibility that two devices may detect the same request for a communications link on a channel and both respond to the request simultaneously. The resulting interference on the channel may result in neither device establishing the communications link. If the subsequent behaviour of the two devices in scanning the channels for requests for a communications link is identical, such a simultaneous response and interference is likely to occur with every subsequent detection of a communication request. In an embodiment of the present invention, some devices are arranged so as to have a behaviour following such a simultaneous response and interference which is different from each other, so as to reduce the likelihood of subsequent repetitions of the simultaneous response and interference.
Devices communicating with each other over a cordless telecommunications link may exchange "handshake" signals to confirm that communication between them over the link is still taking place successfully. If one of the devices fails to receive a handshake signal within a certain period, it may conclude that the link has been broken. However, the device which has ceased to receive handshake signals will typically still be transmitting them until the end of the period at which it concludes that the link has been broken. If these handshake signals are successfully received by the other device, then the other device will not become aware of the failure of the link until a further period after the first device ceases to transmit handshake signals. Thus, when a transmission link fails in one direction only, the reaction of the devices may be delayed and will typically not be synchronised with each other. In an embodiment of the present invention, if a device fails to receive a handshake signal within a first period of its most recent receipt of a handshake signal, it concludes that the link has been lost. In the meantime, it continues to transmit handshake signals, but if it has not received a handshake signal within a second, shorter, period since the most recent handshake signal, it transmits a signal indicating that it is failing to receive handshake signals. Thus, if a link breaks down in one direction only, the device which is continuing to receive transmissions is rapidly notified that the other device has ceased to receive transmissions, and the link re-establishment actions of the devices can be better co-ordinated.
Where two devices communicate with each other in a synchronised manner, it is possible for the transmission of information to become corrupted by a loss of synchronisation, even though the transmission quality of the communication link may be unimpaired. In an embodiment of the present invention, some of the transmitted information is coded to enable error detection, and the detection of errors in this data can be used as an indication that synchronisation between the devices has been lost.
When two devices are communicating with each other over a communications link, in a synchronised manner, one of them may be designated a synchronisation master, and the other a synchronisation slave, such that the slave is required to synchronise itself to the operations of the master. If the link fails, or for any other reason the devices are required to break and re-establish the link, re-establishment may be difficult if the slave device ceases to be synchronised to the master and therefore fails to detect link re-establishment signals from the master. In an embodiment of the present invention, when link re-establishment is required the initial signalling to carry out the re-establishment is always transmitted by the slave device.
If one of the devices in a link is portable or mobile, the link may be broken by the movement of that device. It may then be impossible to re-establish the link between the same two devices. If one of the devices is also an endpoint of a communications path, e.g. a handset, and the other is only a relay station, e.g. a base station linked to a communications network, it is preferable to re-establish the link using the same endpoint device, but possibly a different relay device, for the convenience of the user. However, it may be difficult for the communications network to monitor which relay device an endpoint device is near at any given time. In an embodiment of the present invention the endpoint device transmits the initial signals in link re-establishment, and the link can be re-established using any relay device which receives the transmissions. The endpoint device is typically the mobile device, e.g. a portable telephone handset.
When devices are communicating over a communications link using an alternating transmission burst arrangement, there may be a failure of communication if the timings of the transmissions of the two devices are not properly co-ordinated and their transmissions partially overlap instead of alternating correctly. In an embodiment of the present invention one device derives the timing for the transmission of a burst from the time at which it receives a burst from the other device.
When devices communicate over a telecommunications link, it may be necessary to transmit signals belonging to a logical channel for the purposes of link maintenance, even though there is no information to be transmitted in that channel at that time. If a random signal is sent in that logical channel under the circumstances, it may by chance resemble some meaningful signal transmitted over the communications link, resulting in incorrect operation of the device receiving the signal. In an embodiment of the present invention, a specified signal structure is provided for a logical channel which structure conveys no useful information in that channel, but which is chosen not to resemble a signal the reception of which could cause incorrect operation of the receiving device. | {
"pile_set_name": "USPTO Backgrounds"
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Technical Field
The present application discloses a game mat which is placed on floor for infant crawling and playing. Specifically, it is a multi-mode controlled acousto-optic interaction infant game mat with logic and sensory integration training function.
Related Art
The existing infant crawling mat in the market is a protection soft mat for 0-3 year-old infant to crawl and play indoors. It is made of plastic, foam plastic, cotton, polyester and other materials. The size is equal to or bigger than 1 square meter. The mat is decorated with vivid and colorful patterns. When infants sit or crawl or lie down on the soft mat, the parents may guide the infant from one side while playing or walking to different directions with toys, sound, songs, etc. The infant crawling mat is big in size and made of soft material. It can protect infants from injuries when falling down during indoor activities. The common infant crawling mat cannot guide or positively entertain the infant. For example, a Chinese patent with application number 200920187856.9 discloses a toy mat. It is composed of one cloth mat, and there is a pillow mat sewed on the top part of the cloth mat. The pillow mat is in the shape of a human face and has concave in middle, which is surrounded by U-shaped pillow bumps. The column shaped soft pillows are sewed to both sides underneath the pillow mat. The mat of the patent features a simple structure, attractive appearance, and function of protection, but it doesn't have the function to initiatively guide the infant to crawl and play. Another example is a Chinese patent with application number 201320366228.3. It discloses an infant game mat with piano music, including a first cross slab and a second cross slab. The first cross slab is provided with a first lug at the left side and a second lug at the right side. The second cross slab is provided with a third lug at the left side and a fourth lug at the right side. A piano is installed between the first lug and the third lug. A curved pipe is installed between the second lug and the fourth lug. The piano has a lot many piano keys. Several toys are hung on the curved pipe. The mat of the patent can exercise the infant's hands-on ability, but it is only suitable for older children (at least 2 years old) and it doesn't have the function to initiatively guide the babies. Another example is a Chinese patent with application number 201320509377.0. It discloses a toy mat. It is a mat with at least one light-emitting module, which comes with a light guide plate, which is equipped with at least one switch and at least one illuminator. The mat also has a controller at one side. The controller is connected electrically with the switch and the illuminator. The switch can be triggered by pressing down the light guide plate, so the controller can generate corresponding control actions. When the mat is folded, it overcomes the disadvantage that the carbon black is easily cracked and electricity is disconnected. The mat disclosed in the patent is provided with an illuminator and can solve the problem of electricity conduction, but this mat is not suitable for infant to play, and has no function to guide the infant while crawling or playing. In comparison to the presented application, the existing patents and existing products can't generate both sound and light at same time, or match different kinds of sound with changing light colors according to certain logical rules, therefore they cannot exercise nor strengthen the infant's vision and auditory nerve interaction and help them establish logical induction, logical reasoning concepts through light and sound matching and changing. The game mat disclosed in the present application can also produce vivid light and lovely funny sounds, and control and change the position of light and sound, the game mat can guide the infant to crawl or walk toward the direction of constantly changing lights and sounds. Not only does this strengthen the infant's audible and visual reaction, it also promotes the physical fitness of the infant. More importantly, the present application considers the requirement of all infants in functional structure, materials, safety protection and other aspects. It is even suitable for newborn babies. The existing patents and products do not have those advantages. | {
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A casting system may be, for example, a strand casting system, a billet strand casting system or else a die-operated continuous casting and rolling system. In the case of a strand casting system, a strand, generally a metal strand, in particular a steel strand, is drawn off from a die by means of driven rollers or pairs of rollers. In the case of a billet strand casting system, generally a plurality of extruded billets are cast in a die, generally two to six extruded billets.
Generally, electrical driven rollers or pairs of rollers are provided for guiding a cast material, for example a strand or an extruded billet, when it is being drawn off. For example, a strand is drawn off substantially vertically out of the die and transferred into a substantially horizontal direction by means of a casting bow.
In order to reduce the effort involved in rolling in a rolling mill, in the case of casting systems the rollers or pairs of rollers are advantageously used not only for guiding the strand but also for reducing the thickness of the cast material.
Critical variables in the casting of a cast material are the casting speed and the desired final thickness, if a thickness reduction is envisaged.
The rotational speed of the drives for the rollers or the drives for the pairs of rollers may serve for setting the casting speed of the cast material. For example, the mean value of the speed of all the drives is kept constant for this purpose. As a result, the casting speed drops as the thickness of the strand is increasingly reduced. However, since the driven rollers rotate with the same radial speed, adequate allowance cannot be made for a change in the speed of a portion of the cast material that results from the thickness reduction. Therefore, in the case of such a method, generally no thickness reduction of the cast material is envisaged for this reason.
Alternatively, it may be provided that the rollers or pairs of rollers acting on the cast material are driven by means of drives which all run with the same load. The pairs of rollers together with the drive and means for producing rolling force are referred to as the reduction stand. In the case of a dynamic thickness reduction—dynamic since the rolling forces depend on the time-variable phase response within the strand—of the strand or billet, operation of the drives with the same load has the consequence that, with low vertical force or rolling force on the strand, the frictional forces are so low that the roller loses adherence and does not transfer any forward motion, or transfers reduced forward motion, to the strand. Moreover, increased friction occurs in the case of rollers with increased vertical force or increased rolling force on account of the evenly distributed load on the drives, and increased friction leads to a slowing of the circumferential speed of the roller concerned. This leads to a slowing of the speed of the strand or to the cast material coming to a standstill in the casting system.
On account of a dynamic distribution of forces in the case of roller drives operated with the same load—the thickness reduction of the strand over the various pairs of rollers is highly process-dependent and dynamic during casting—instabilities in the casting speed occur. In particular, the dynamics of the thickness reduction are determined in part by the calculated liquid core component within a strand, which is determined by appropriate models that are not the subject of this application.
Patent specification EP 0 463 203 B1 discloses a guiding method for electrical drives of rollers of a strand casting system in which the strand is drawn off out of the die of the strand casting system by the driven rollers, the drives of which are individually controlled by means of controllers, and can be reduced in its thickness. A disadvantage of this teaching is that the drives consequently cannot be controlled adequately flexibly with regard to use within casting systems with reduction stands. | {
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The invention is based on an apparatus for damping courses of motion as set forth hereinafter. Such an apparatus is known from U.S. Pat. No. 5,024,302.
In this known model, an intervention into the positive volumetric displacement of the damping cylinder is made by open-loop control, thus making this apparatus a so-called active or semi-active damping system. However, this kind of model does not work specifically in the natural frequency range of the wheel. | {
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Nowadays, existing photograph technologies for capturing three-dimensional (3D) pictures require high photographic skill level. Only professional photographers may be capable of shooting 3D pictures. Further, the captured pictures require a lot of post-production editing and processing. Ordinary consumers may find it very difficult to capture 3D pictures or 3D videos that are ready to view directly. In addition, stunning 3D effects usually require large parallax between the stereoscopic images. However, when watching 3D images or 3D videos with large parallax, the viewers may experience dizziness, eye fatigue and other symptoms.
Some technologies correlate parameters in a shooting scene and parameters of camera(s) to conveniently achieve a desirable stereoscopic effect of the shooting scene recorded by the camera(s). Further, setting different parameters of the shooting scene may bring diversified effects to the stereoscopic images. However, when capturing images using these technologies, users need to configure parallax settings which may require a highly skilled professional photographer or a stereographer. Moreover, the captured images are still likely to cause the viewers to experience dizziness, eye fatigue and other symptoms. In addition, these technologies may require complicated calculation and slow down camera responses, causing heavy load to the processor and high power consumption.
Therefore, according to disclosed embodiments, it is desirable to provide a method and apparatus that not only captures stereoscopic images with large parallax, but also ensures a comfortable viewing experience at the same time. The disclosed method and system are directed to solve one or more problems set forth above and other problems. | {
"pile_set_name": "USPTO Backgrounds"
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Intraoperative embolic stroke is one of the most dreadful complications of cardiac, aortic and vascular procedures, diagnosed in 1-22% of patients undergoing cardiovascular surgery. Even more frequently, in up to 70% of cases, patients undergoing heart, valve, coronary artery bypass and aortic surgery experience subclinical embolic events as recorded by transcranial Doppler and MRI. These embolic events lead to cognitive impairment and disability and have a significant impact on patients' recovery.
The main sources of cerebral emboli and stroke in this setting reside in the heart, heart valves, thoracic aorta, and great vessels when these structures are intervened thereon. Even simple cardiac catheterization with an endovascular catheter can induce microtrauma of the atherosclerotic thoracic aorta leading to formation of embolic particles with subsequent embolic brain injury ranging from latent ischemic foci to a massive or even fatal stroke.
Multiple devices are known that attempt to prevent embolization of the carotid arteries during endovascular and cardiac interventions. These anti-embolic devices, however, have not received wide acceptance in surgery of the heart, heart valves and thoracic aorta due to their complexity and invasive character with the risk of additional trauma to the inner vessel wall resulting in a high risk to benefit ratio. Known devices require insertion of additional hardware into the arterial system or aorta, a procedure that is known by itself to be associated with all classical risks of endovascular intervention, including aortic dissection, bleeding, thrombosis, and carotid cerebral embolization and stroke. One known intra-aortic filter device that is inserted into the ascending portion of the thoracic aorta via an aortic cannula to capture potential embolic material released from the heart and aortic wall during heart surgery was found to be quite difficult to implement and was reported to be associated with major trauma to aortic wall and acute aortic dissection.
Another such device for preventing emboli into the cerebral circulation includes a porous deflector/intra-aortic shield that captures or diverts potential emboli into the distal vasculature. A yet additional device has also been proposed for use during aortic valve surgery and is an intra-aortic filter catheter that captures emboli during this procedure. It has been established that intravascular filters are not able to capture emboli smaller than the pore size of the available devices (currently 60-140 μm) resulting in cerebral microembolization. Embolization may also occur due to poor apposition of the filter to the aortic or carotid arterial wall.
Furthermore, the placement of the filter by itself may produce cerebral emboli. For example, the mere passing of a guide wire into a carotid artery generates approximately 40,000 microemboli, with a significant percentage of small, less than 60 μm, particles that are not retained by standard filters. Therefore, in spite of multiple innovations in the field of anti-embolic devices, the problem of cerebral emboli and stroke during cardiovascular surgery is far from being resolved.
It is known to use balloon occlusion catheters for the prevention of embolic stroke. In this regard, the balloon occlusion catheter is placed inside of one of the carotid arteries when a procedure, for example carotid angioplasty and stenting, is conducted on the carotid artery in question. Although capable of preventing stroke when a single carotid artery is operated upon, this device cannot work to prevent stroke during procedures on the heart and aorta, endovascular or open, and cannot provide for bilateral occlusion. This device cannot simultaneously occlude both the left and right carotid arteries to prevent flow simultaneously through both of these arteries, and thus cannot prevent stroke should emboli flow into the non-blocked carotid artery.
Also, the design of known endovascular devices did not address the issue of specific orientation of balloons in carotid arteries. By failing to address this issue, the methods cause an increase in the amount of time and effort needed to make the placement and likewise cause a safety concern.
Further, known endovascular carotid occluding devices require a guide wire to be inserted into the carotid arterial system. This procedure by itself is known to induce carotid trauma and cause the formation of cerebral emboli and resultant stroke. Still additionally, prior endovascular carotid occluding devices are not capable of reducing arterial flow through both right and left vertebral arteries, either at the same time or individually. This deficiency may allow emboli to enter vertebral circulation and cause stroke.
Still further, known systems are not capable of interrupting the flow, if needed, to both vertebral arteries for the period of time when emboli can enter cerebral circulation. Known systems also risk trauma to the carotid artery wall and allow for subsequent cerebral emboli. As such, there remains room for variation and improvement within the art.
Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the invention. | {
"pile_set_name": "USPTO Backgrounds"
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In the world of virtual computing, a guest can be migrated to a different, compatible virtual environment (e.g., an environment comprising one or more guests, a physical or virtual host, and a virtualization component such as a hypervisor). However, when a guest is copied from one virtual environment to another, the target virtual environment might not be compliant with the policies/requirements of the guest. For example, the guest might require a specific amount of memory or disk space that the target virtual environment does not have available, or the guest might have specific network communication requirements that are not met by the target virtual environment. While the guest can verify its own configuration, it lacks the ability to ensure that a virtual environment in which it runs is complaint with its own policy requirements. It would be desirable to address this shortcoming. | {
"pile_set_name": "USPTO Backgrounds"
} |
In printing, treatment fluids may be applied for treating an ink on a substrate or for treating a substrate prior to receiving ink. Ink treatment may be, for example, to improve print quality by enhancing fixation of ink on the substrate or to protect ink on the substrate. Such a treatment may include, for example, a pre-treatment component (e.g., a fixer) or a post-treatment component (e.g., a coating).
For example, a pre-treatment may be applied on a portion of a substrate to enhance fixation (e.g., bonding and/or hardening) of an ink to be subsequently applied on that portion of the substrate. If the ink is deposited on the substrate via an ink fluid, fixation may be desired to address coalescence, bleed, feathering, or similar effects characterized by ink migration across a printed surface. In other examples, a post-treatment may be applied to ink already applied on the substrate. Such a post-treatment may be to provide a coating over ink deposited on the substrate.
Common methods for applying treatments on a substrate include roll coating, spray coating, manual application or treatment ejection, for example, through a jetting device. In an example of treatment application by a jetting device, a printing system may include a printhead including a treatment printhead unit for jetting a treatment fluid on a treatment substrate location. | {
"pile_set_name": "USPTO Backgrounds"
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In recent years, tungsten carbide (WC) has attracted considerable attention for catalytic and electro-catalytic applications since the discovery of its Pt-like characteristics as reported by Levy and Boudart.1 It is well known that WC has high catalytic activity for hydrogenolysis and isomerization reactions.2-7 Tungsten carbide is also reported to exhibit certain activity for many electrochemical reactions of interest, including hydrogen oxidation,8, 9 oxygen reduction,10, 11 hydrogen evolution reaction (HER),12 and oxidation of various organic molecules.9 Although its electro-catalytic activity was usually not sufficient, the low cost and insensitivity to catalyst poisons such as CO make it an interesting alternative to noble metal catalyst. Other than direct use as a catalyst, tungsten carbide has also been intensively studied as a catalyst support for various reactions.10, 13-15 Particularly, its high corrosion resistance and superior electronic conductivity renders WC suitable as an electro-catalyst support for various electrochemical applications, such as fuel cells.16-18 For example, higher catalytic activity has been reported for Pt/WC compared to Pt/C due to the synergistic effect between Pt and WC.19, 20
Also, sustainable hydrogen production through splitting of water has attracted great scientific interest in the past decades.34, 35 By far, extensive research efforts have been made in developing advanced electrocatalysts with reduced overpotential for hydrogen evolution reaction (HER).36-42 Typically, electrocatalytic system for hydrogen evolution incorporates noble metals such as platinum (Pt) because of their high electroactivity. However, the high cost and scarcity of noble metals are serious barriers for their wide use in the water electrolysis.43
Conventionally, several routes have been adopted to synthesize WC powder, including direct carburization of tungsten or W-containing compounds at high temperature (typically, higher than 1400° C.), solid state metathesis and mechanical milling. However, these approaches often lead to low specific surface area, large particle size and poor morphology control. Commercial WC and WC synthesized by reported methods are normally lower than 10 m2 g−1 and the maximum value reported is ˜100 m2 g−1.11, 21-29 To synthesize nanostructured WC with high surface area and controlled morphology still remains a challenge.30, 31 Furthermore, the ability to control specific nanostructure is critical for the tuning of its physical and chemical property, especially when WC is to be used as catalyst support. | {
"pile_set_name": "USPTO Backgrounds"
} |
1. Field of the Invention
The present invention relates to garden tools and more particularly pertains to a manually operable weed remover which utilizes pivotal spikes to capture a weed and its attendant root structure.
2. Description of the Prior Art
There many types of garden tools which can be utilized to remove stubborn weeds from the lawn and garden. Most of these tools rely upon sharpened blades of one type of another whereof such blades are fixedly secured to a handle, and usaully substantial manual effort is required to remove weeds. Further, these types of prior art garden tools are not particularly suited for removing weed root structures. As such, there is a continuing need for new and improved manually operable garden tools which require less physical effort to remove weeds and which at the same time are more efficient at removing weed root structures. In this respect, the present invention substantially fulfills this need. | {
"pile_set_name": "USPTO Backgrounds"
} |
Starter drives as used heretofore have a pinion which engages the ring gear on the engine flywheel when the starting motor is energized. Starters of this kind are noisy because the pinion on the starting mechanism must first mesh with the ring gear before cranking the engine. Also, one or more teeth on the pinion or ring gear may break while the pinion is meshing with the ring gear and disable the starter drive. | {
"pile_set_name": "USPTO Backgrounds"
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Containers for mailing a package or a small parcel are known for example from patent application DE 10 2013 005 231.9. The typical usage area of such containers results from the fact that persons often expect the receipt of packages or small parcels, which do not fit into the usual mailbox arranged at a house or at an apartment or generally at a property.
With a container of the abovementioned type, the person has the possibility to arrange a container at the property temporarily and occasionally, namely concretely in the region of the door, if the person for example expects such a large mailing. A mailman or a parcel carrier has hereby the possibility to insert a mailing which does not fit into the mailbox into this container after opening the lid element and to close the container again hereafter.
As the container itself is fastened irremovably to the property for third parties, there is, apart from forcible action, no possibility to steal the expected mailing in an unauthorized manner.
For fastening such a container, the abovementioned patent application teaches for example the use of a flap, e. g. a flexible textile flap which extends away from the container and which has a thickened region, in particular a thickened end, so that this flap can be guided through a gap region, for example between the door and the frame or between the door and the floor, the thickened region of the flap hereby comes to rest in the interior of the apartment and thus the flap cannot be pulled out from the door region after closing the door. The owner of the apartment or of the house can however release the flap by opening the door and hereby remove the entire container again.
As described here at the outset regarding the possible receipt of a package or of a small parcel mailing, there exists of course also the possibility to insert packages or small parcels or other mailings into the container and to temporarily provide them in front of the house or the apartment door for the collection by a messenger.
The abovementioned patent application already teaches for example to design the side walls of such a container extending between the base element and the lid element in a foldable manner, thus creating the possibility to move the container back and forth between a folded and an unfolded state and thus to provide a large inner volume by e.g. unfolding, into which the package or the small parcel are inserted, whereas the folded state is more space-saving, as the volume is significantly reduced in this state. | {
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The present invention is directed to a system for delivering high energy laser light by means of an optical waveguide, and in one particular application is concerned with laser angioplasty and a means for guiding such a system.
The use of laser energy to ablate atherosclerotic plaque that forms an obstruction in a blood vessel is presently being investigated as a viable alternative to coronary bypass surgery. This procedure, known as angioplasty, essentially involves insertion of a fiberoptic waveguide into the vessel, and conduction of laser energy through the waveguide to direct it at the plaque once the distal end of the waveguide is positioned adjacent the obstruction. In certain embodiments, to enable the physician to ascertain the location of the waveguide as it is being moved through the vessel, additional waveguides for providing a source of illuminating light and for conducting the image from inside the vessel to the physician are fed together with the laser waveguide.
Most of the experimentation and testing that has been done in this area has utilized continuous wave laser energy, such as that produced by Argon Ion, Nd:YAG or Carbon Dioxide lasers. The light produced by this type of laser is at a relatively low energy level. Ablation of the obstruction is achieved with these types of lasers by heating the plaque with constant laser power over a period of time until the temperature is great enough to destroy it.
While the use of continuous wave laser energy has been found to be sufficient to ablate an obstruction, it is not without its drawbacks. Most significantly, the destruction of the lesion is uncontrolled and is accompanied by thermal injury to the vessel walls immediately adjacent the obstruction. In an effort to avoid such thermal injury and to provide better control of the tissue removal, the use of a different, higher level form of laser energy having a wavelength in the ultra-violet range (40-400 nanometers) has been suggested. See, for example, International Patent Application PCT/US84/02000, published Jun. 20, 1985. One example of a laser for producing this higher level energy is known as the Excimer laser, which employs a laser medium such as argon-chloride having a wavelength of 193 nanometers, krypton-chloride (222 nm), krypton-fluoride (248 nm), xenon-chloride (308 nm) or xenon-fluorine (351 nm). The light produced by this type of laser appears in short bursts or pulses that typically last in the range of ten to hundreds of nanoseconds and have a high peak energy level, for example as much as 200 mJ. Although the destruction mechanism involving this form of energy is not completely understood, it has been observed that each single pulse of the Excimer laser produces an incision which destroys the target tissue without accompanying thermal injury to the surrounding area. This result has been theorized to be due to either or both of two phenomena. The delivery of the short duration, high energy pulses may vaporize the material so rapidly that heat transfer to the non-irradiated adjacent tissue is minimal. Alternatively, or in addition, ultraviolet photons absorbed in the organic material might disrupt molecular bonds to remove tissue by photochemical rather than thermal mechanisms.
While the high peak energy provided by Excimer and other pulsed lasers has been shown to provide improved results with regard to the ablation of atherosclerotic plaque, this characteristic of the energy also presents a serious practical problem. Typically, to couple a large-diameter laser beam into a smaller diameter fiber., the fiber input end is ground and polished to an optical grade flat surface. Residual impurities from the polishing compound and small scratches on the surface absorb the laser energy. These small imperfections result in localized expansion at the surface of the fiber when the laser energy is absorbed. The high-energy Excimer laser pulses contribute to high shear stresses which destroy the integrity of the fiber surface. Continued application of the laser energy causes a deep crater to be formed inside the fiber. Thus, it is not possible to deliver a laser pulse having sufficient energy to ablate tissue in vivo using a conventional system designed for continuous wave laser energy.
This problem associated with the delivery of high energy laser pulses is particularly exacerbated in the field of coronary angioplasty because of the small diameter optical fibers that must be used. For example, a coronary artery typically has an internal diameter of two millimeters or less. Accordingly, the total external diameter of the angioplasty system must be below two millimeters. If this system is composed of three separate optical fibers arranged adjacent one another, it will be appreciated that each individual fiber must be quite small in cross-sectional area.
A critical parameter with regard to the destruction of an optical fiber is the density of the energy that is presented to the end of the fiber. In order to successfully deliver the laser energy, the energy density must be maintained below the destruction threshold of the fiber. Thus, it will be appreciated that fibers having a small cross-sectional area, such as those used in angioplasty, can conduct only a limited amount of energy if the density level is maintained below the threshold value. This limited amount of energy may not be sufficient to efficiently ablate the obstructing tissue or plaque without thermal damage.
Even if the energy density is quite high, the small beam that results from the small diameter fiber may not have a sufficiently large target area that effective ablation of the lesion results. Only a small fragment of the lesion might be ablated, and thus not provide adequate relief from the blockage.
A further problem with the use of a fiberoptic wavequide to direct laser energy for purposes of ablating atherosclerotic plaque is that of perforation of the blood vessel. Such perforations can be caused by the waveguide itself contacting and perforating the vessel. Such perforations can also be caused by the laser beam, particularly if the waveguide is not aligned properly within the blood vessel. The perforation problems are related to the intrinsic stiffness of the glass fibers of the waveguide and poor control of laser energy, regardless of laser source or wavelength.
Also related to the stiffness of the glass fibers is the ability to control the position of the fibers radially within the blood vessels. The conventional systems employing fiberoptic waveguides within a blood vessel do not provide means for controlling radial movement within the blood vessel.
One known attempt at developing an angioplasty catheter is disclosed in U.S. Pat. No. 4,747,405. The known catheter includes a center guidewire lumen, a guidewire therein, and a single optical fiber disposed at a side of the catheter for emitting laser energy. The catheter also has a blunt leading end that does not facilitate progress through a blood vessel. A particular problem that potentially results from the disclosed arrangement of the single optical fiber and guidewire is that large segments of the lesion may become loose in the blood stream and could possibly cause an emboli. As a result, the known catheter includes a dedicated channel to remove the loosened debris. | {
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1. Field of the Invention
The present invention relates to an outboard motor including a transmission device arranged to change a speed of rotation of an engine and to transmit the rotation to a propeller.
2. Description of the Related Art
Because an outboard motor that is installed in a small watercraft is subject to large water resistance, there are times when a planetary gear type transmission device that can make a smooth speed change operation during acceleration or deceleration is applied. For example, JP-B-2785200 suggests a planetary gear type transmission device capable of making shifts to a low speed position during low speed traveling or trolling and to a high speed position during normal traveling.
In the planetary gear type transmission device, a sun gear is fixed so as to be unable to rotate when a shift lever is shifted to the high speed position. A planetary gear revolves on the sun gear in response to rotation of an internal gear when rotation of an engine is transmitted from an input shaft to the internal gear. The revolution of the planetary gear is transmitted from a drive shaft to a propeller via a carrier.
However, in many cases the outboard motor is normally operated in forward and high speed positions. Therefore, the outboard motor requires enhanced durability of each gear of the transmission device for the forward and high speed positions that are normally used. However, in the conventional outboard motor, the planetary gear revolves on the sun gear in the normally used high speed position. Therefore, the outboard motor is normally in a state that a load due to engagement between both the gears is large. This results in a problem that it is difficult to obtain sufficient durability in both of the gears. | {
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The present invention relates to a power amplifier, especially protection for a power amplifier against fault conditions.
In a power amplifier system, it is desirable to avoid operation in fault modes, which could result in permanent damage of the system, especially power transistors. With designed protection circuits, the system may recover from fault conditions and resume normal operation without suffering any damage. In a conventional design, the protection circuits protect the power amplifier against any of the following fault conditions: a short at an output terminal to ground, a power supply, or another output terminal; an overload on the power output; an over-, or under-voltage of the power supply; overheating of the package. An example of such protection circuits is disclosed in U.S. Pat. No. 4,053,996.
FIG. 9 is a block diagram showing the protection for a conventional audio power amplifier. The power amplifier comprises an output block 2, an output terminal 3, a bias block 4, a standby pin 5, and a protection block 70.
The output block 2 includes two power transistors in series between a power supply (with a voltage VCC) and a ground. The output terminal 3 is connected between the two power transistors. The bias block 4 provides bias currents for other blocks, thereby biasing the other blocks in activated states, especially the two power transistors conductive. Then, a large amount of current flows through the power transistors and the output terminal 3, and thus power is provided for an outside load, such as a loudspeaker (not shown).
The protection block 70 includes a protection switch block 71, an ASO (Area-of-Safe-Operation) monitoring block 72, and a short-to-ground detection block 73. The protection switch block 71 controls the ON/OFF states of protection switches 7A, which are interposed between the output block 2 and the bias block 4, and allow (or prohibit) bias currents to flow (or from flowing, respectively). The ASO monitoring block 72 is designed to detect the operations of the power transistors outside their ASO. Here, the operations outside the ASO indicate an occurrence of the above-listed fault conditions of the power transistors, such as “a short to ground, power supply, or another output terminal” and “an overload”. The ASO monitoring block 72 monitors the operation of the output block 2 through the currents, voltages, and temperatures of the power transistors. When the currents or voltages exceed the limits of the ASO, which depends on the temperature, the ASO monitoring block 72 sends a signal to the protection switch block 71 (usually after a predetermined delay TD in order to avoid misoperations). Then, the protection switch block 71 turns off the protection switches 7A, and thus cuts off the bias currents for the output block 2. Accordingly, the power transistors are both confined in the OFF states regardless of the fault types. At the same time, the protection switch block 71 connects the short-to-ground detection block 73 to the bias block 4. Then, the short-to-ground detection block 73 is activated and monitors the potential of the output terminal 3 with respect to a ground. In the event of a short to ground at the output terminal 3, the short-to-ground detection block 73 continuously sends a signal to the protection switch block 71. Thereby, the protection switch block 71 maintains the protection switches 7A in the OFF states. Thus, the protection block 70 prevents permanent damage to the power transistors due to an overcurrent. When the short to ground is not detected or removed, the short-to-ground detection block 73 terminates the sending of the signal. Then, the protection switch block 71 turns on the protection switches 7A, thereby allowing the bias currents to flow to the output block 2. Thus, the power transistors are released and the power amplifier recovers the normal operation.
The above-described protection for the power transistors is effective during the normal operation of the power amplifier, since the currents and voltages of the output block 2 is so large that the ASO monitoring block 72 can easily and promptly detect the operation of the power transistors outside the ASO. However, a problem arises when a fault condition, for example, a short to ground at the output terminal 3 occurs during power-up as follows.
FIG. 10 is a timing chart showing the operations of the protection switches 7A, the protection switch block 71, the ASO monitoring block 72, and the short-to-ground detection block 73 during power-up, together with the level of the voltage VSTB at the standby pin 5 (see FIG. 9). In FIG. 10, high (or low) levels represent activated (or non-activated) states of the respective blocks. Here, the voltage VSTB at the standby pin 5 is supplied by an external device, such as a microcontroller, and its level rises at a predetermined rate during power-up. The bias block 4 monitors the level of the voltage VSTB during power-up, and does not provide the bias currents for the protection block 70 until the standby pin 5 is enough activated, that is, the level of the voltage VSTB reaches a predetermined level VON. Thereby, the protection block 70 avoids misoperations due to inrush currents and abrupt voltage rises. In particular, an audio power amplifier prevents a loudspeaker from reproducing an undesired noise (which is known as “popping noise”) at power-up. The arrangement of the standby pin 5 is an ordinary component of prior-art power amplifiers, especially audio power amplifiers.
The protection block 70 is maintained in a non-activated state after the time T0 when power-up starts, until the time TON when the voltage level VSTB of the standby pin 5 reaches the predetermined level VON. Accordingly, the ASO monitoring block 72 cannot detect the operations of the power transistors outside the ASO during the period from the time T0 to the time TON. Therefore, the protection switches 7A are maintained in the ON states during a period PON from the time T0 to the time when the delay TD has elapsed from the time TON. As such, in the event of a short to ground at the output terminal 3 at power-up, excessive currents may flow through the power transistors in the period PON, and a large amount of power may be dissipated in the power transistors. Unless removed within a very short period of time, this dissipation may cause permanent damages to the power transistors, and hence the power amplifier. Since the protection block 70 cannot promptly react to fault occurrences during power-up, it is difficult to reduce the risk of permanent damages to the power transistors.
In order to activate the protection block 70, especially the ASO monitoring block 72, at an earlier stage during power-up, the ASO monitoring block 72 is required to enlarge its detection range and enhance its detection accuracy, thereby ensuring its reliability during power-up. However, the ASO of the power transistor is tightly confined since the output block 2 is usually designed to have a size large enough to deliver sufficient power, while minimizing its chip area. Accordingly, the detection accuracy required of the ASO monitoring block 72 is very high for the normal operation of the power amplifier. In addition, when the power amplifier is designed as a monolithic IC, an area available for implementation of the ASO monitoring block 72 in itself is tightly confined. On the other hand, there is a limit to the accuracy of the design of the ASO monitoring block 72 due to parameter tolerances of wafer process. In a conventional design, the detection range of the ASO monitoring block 72 is confined to cover the operation ranges of the power transistors during the normal operation, thereby ensuring high accuracy of detection. Therefore, it is difficult for the ASO monitoring block 72 to achieve a larger detection range with higher detection accuracy suitable for a reliable protection for the output block 2 during power-up. | {
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1. Field of the Invention
This invention pertains to the generation of maps to be displayed on a CRT by digital processing of digitally encoded geodetic and cultural data that defines the environment to be mapped.
2. Description of the Prior Art
A special problem exists in providing a night-flying aviator with information on the terrain over which he is flying. Scheduled flights to large airports may be adequately served by elaborate instrumentation and flight control instructions, although knowledge of the surrounding terrain is desirable. But low flying military aircraft, or those performing emergency services in sparsely settled areas, rely very much on visual contact; illumination sufficient for seeing conventional maps may impair dark adaption and many maps may be needed to cover the possible range of modern aircraft. A self-luminous display like the face of a cathode ray tube does not require illumination of the background, and may be biased down to the very lower limit of visibility so that it impairs dark adaptation negligibly. Television-type techniques can obviously be employed to present an image of a printed map; a flying-spot scanner has been employed to scan holograms in a similar application. Such a display is clearly limited by an available number of maps and has limited flexibility in the choice of data to be displayed. Generation of maps from stored digital environmental data is known in the art; simulation of radar presentations from similar data is also known and described as "radar mapping" (somewhat loosely since the radar presentation itself may well not be a true map). The applicant's U.S. Pat. Nos. 3,769,442 and 3,883,861 and 4,017,985, and 3,892,051 of Bunker (all assigned to the assignee of this application) variously describe the preparation of digital bases for terrain simulation and the generation of simulated images for pilot training. None of these inventions is subject to size, weight and power constraints of airborne equipment.
Another important constraint to be met is time. A general purpose digital computer can perform all the functions required to generate a map display but, because of the large amounts of data to be processed, it would take many minutes and in some cases over an hour, to generate a single display. This, in airborne applications, is unacceptable. Thus special, dedicated, processing loops to maximize data throughput are required and are a unique feature of this invention.
Effective functioning of a map is subjective; that is, the map is good if it transfers required information accurately and easily to the viewer. A line map gives no sense of altitude, unless it includes elevation contours, which require time for their interpretation. Visual image simulation gives an indication of elevation; but it requires somewhat complicated (and hence equipment-costly) computation and it conceals what lies beyond the next hill, which information may be the reason why a map is needed at all. | {
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1. Field of the Invention
The present invention relates to a constant voltage circuit which is applied to a power supply device, such as a power adapter, and more particularly to a constant voltage circuit for a power adapter which is capable of varying an output voltage with loads so as to reduce the charging time of a system battery.
2. Description of the Related Art
In general, a power adapter, which is adapted to supply a constant voltage for charging of a battery, supplies the constant voltage irrespective of loads, as will hereinafter be described with reference to FIG. 1.
FIG. 1 is a block diagram of a conventional constant voltage circuit.
Referring to FIG. 1, the conventional constant voltage circuit comprises a transformer 10 having a primary coil and secondary coil and acting to transform a commercial alternating current (AC) voltage according to a turn ratio of the primary and secondary coils, a rectifier 20 for rectifying an output voltage from the transformer 10, a voltage detector 30 for detecting the output voltage rectified by the rectifier 20 to output a detected voltage Vd, a comparator 40 for comparing the detected voltage Vd from the voltage detector 30 with a reference voltage Vref to output a difference voltage therebetween, a signal coupler 50 for performing a coupling operation for a signal corresponding to the difference voltage from the comparator 40, and a controller 60 for controlling a primary voltage of the transformer 10 in a pulse width modulation (PWM) manner in response to an output signal from the signal coupler 50.
In this conventional constant voltage circuit, the output voltage from the transformer 10 is detected and the comparison is made between the detected voltage Vd and the internal reference voltage Vref (about 2.5V) to generate a difference voltage therebetween. The controller 60 controls a turn-on duty of a switch, for example, a field effect transistor (FET), connected to the primary coil of the transformer 10 on the basis of the difference voltage, so as to maintain the output voltage constant.
However, the above-mentioned conventional constant voltage circuit has a disadvantage in that the output voltage is controlled to be outputted constantly irrespective of loads, and more particularly even when a battery is in an uncharged state, thereby making it impossible to rapidly charge the battery. | {
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The present invention relates to a pump assembly with an L- or U-shaped separating container with a pump unit mounted thereupon.
A pump assembly of this kind is disclosed in German Patent Application No. 24 60 268. In this assembly, the separating container is in the shape of a U lying down, on which the pump unit is mounted. The gas-liquid mixture expelled by the liquid ring pump is conducted at the free end of one leg of the U into the separating container through an inlet opening provided in said leg, and the gas escapes from the separating container at the free end of the other leg of the U through a corresponding outlet opening. In this separating container, there is a continuous path between the inlet opening and the outlet opening, above the gas chamber of the separating container, through which path the atmospheric noise generated by the pump can propagate undamped.
As a result of the separating container being located beneath the liquid ring pump, the latter drains completely when stopped, so that restarting is possible only with appropriate auxiliary measures. | {
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Additive manufacturing, also known as 3D Printing, is used for the production of complex structural and functional parts via a layer-by-layer process, directly from computer generated CAD (computer aided drafting) models. Additive manufacturing processes are considered additive because conductive materials are selectively deposited on a substrate to construct the product. Additive manufacturing processes are also considered layered meaning that each surface of the product to be produced is fabricated sequentially.
Together, these two properties mean that additive manufacturing processes are subject to very different constraints than traditional material removal-based manufacturing. Multiple materials can be combined, allowing functionally graded material properties. Complicated product geometries are achievable, and mating parts and fully assembled mechanisms can be fabricated in a single step. New features, parts, and even assembled components can be “grown” directly on already completed objects, suggesting the possibility of using additive manufacturing processes for the repair and physical adaptation of existing products. Structural and functional parts created by additive manufacturing processes have numerous applications in several fields including the biomedical and aerospace industries. Traditional milling and welding techniques do not have the spatial resolution to create complex structural parts that can be achieved through additive manufacturing
However, electrochemical additive manufacturing (ECAM) techniques in general have several limitations such as choice of material, porosity, strength, scalability, part errors, and internal stresses. A deposition process must be developed and tuned for each material, and multiple material and process interactions must be understood. Resulting products may be limited by the ability of the deposited material to support itself and by the (often poor) resolution and accuracy of the process, Widespread use of additive manufacturing techniques may be limited due to the high cost associated with selective laser melting (SLM) and electron beam melting (EBM) systems. Further, most additive manufacturing devices currently in the industry use powdered metals which are thermally fused together to produce a part, but due to most metals' high thermal conductivity this approach leaves a rough surface finish because unmelted metal powder is often sintered to the outer edges of the finished product.
Challenges associated with the use of the ECAM processes in commercial systems also include the slow speed of deposition with a single anode, and small (micrometer) size of parts producible by a conventional ECAM method. Microstructures such as metal pillars have been produced using localized electrochemical deposition (LECD) process with a single anode, which is similar to ECAM, but is limited in scope to the fabrication of simple continuous features.
The stereo-electrochemical deposition (SED) process, an extension of the ECAM process, combines two technologies: stereo-lithography and electroplating. By inducing an electric field between the anode and the cathode, and passing metal salts between the electrodes, it is possible to produce metal parts at the cathode rapidly at room temperature. Since the path of the electric field is dependent on the geometry of the part being built, printing of extreme overhang angles approaching 90 degrees without the need for a support structure, is possible.
The SED process is capable of depositing most conductive materials including metals, metal alloys, conducting polymers, semiconductors, as well as metal matrix composites and nanoparticle-impregnated materials. Electroplating and electroforming techniques have established the capability of electrochemical processes to deposit metals over large areas, but localizing the deposition to a controlled area has presented a challenge.
The SED process has the potential to cheaply and quickly produce both metals and composite metal/polymer systems because it is a non-thermal process requiring relatively few moving parts and no expensive optical or high vacuum components. Additionally, the material is deposited atom by atom resulting in good micro-structural properties (such as porosity, grain size, and surface finish) which can be controlled electronically. These characteristics allow the SED process to create certain three dimensional geometries much faster, and with higher quality than conventional methods. | {
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With large-scale application of Internet Protocol (IP) technology and IP networks in telecommunication field, telecommunication services are packetized gradually, such that more value-added services, especially multimedia services, may be provided over packet-based IP networks. At present, IP networks mainly bear Internet services which are best-effort services without strict demand on the Quality of Service (QoS).
The emergence of Next Generation Network (NGN) services puts forward a great challenge to the conventional best-effort Internet networks and technologies. Nowadays, NGN is a focus concerned and discussed by communication enterprises. People wish to provide solutions for issues in various networks such as network convergence, forward/backward-compatible smooth evolution, establishment of profitable business modes for adding Average Revenue Per User (ARPU), Average Profit Per User (APPU) and efficient multi-service added values by means of NGN. Conventional Internet networks and technologies may not provide telecom-level NGN services. More and more telecom organizations and operators believe that NGN should absorb the technologies of Internet, discard the idea of Internet, and refer more to the idea of Public Switched Telephone Network (PSTN) instead. The problems existing in NGN at present are mainly focused on QoS, security, protection, and signaling system, etc. The Service control plane of NGN is most frequently and maturely researched in NGN, and the practice of NGN has shown that the transport service of NGN has become one of the largest technological barriers to the development of NGN.
At present, International Telecommunications Union (ITU-T) divides NGN into a service layer and a transport layer, and each layer may be divided into a user plane, a control plane and a management plane. From the view of the practical network construction of NGN, the service layer of NGN includes various Application Layer devices, and the transport layer is generally composed of IP Routers and Ethernet Switchers, Asynchronous Transfer Mode (ATM), private-line direct interconnection and physical transport layer network; From the view of protocol hierarchy, the transport layer of NGN includes a physical transport sub-layer (L1) and a packet transport sub-layer (L2, L3-L7). This method shifts the processing and switching functions of IP Layer and the protocol layers above IP Layer (including L3-L7 of ISO network protocols) implemented by routers to the transport layer. With appearance of multi-service routers, more and more complicated features of NGN service layer will be implemented in routers, which will cause a confusion of the service layer and the transport layer when the NGN is physically implemented; for example, the multi-service routers in NGN implement not only many functions of the service layer but also functions of the transport layer, which is harmful to a simple, secure and low-cost construction of transport network of NGN, an finally harmful to the building of telecom-level NGN. Therefore, from the view of development, it is more reasonable to logically allocate the functions of IP Layer and the layers above IP layer (L3-L7) to the service layer of NGN, and the physical implementation of the service layer and the transport layer in NGN should be clearly separated.
The network technologies of the Physical Layer in NGN mainly include SDH technology and Optical Transport Network (OTN) technology, in which SDH technology has been very mature after many-year development. At present, the SDH technology is developed toward Multiple Service Provisioning Platform (MSPP); MSPP is a convergence of packet technology and SDH technology; besides Ethernet interface and the layer 2 (L2) switching, ATM interface and ATM switching, MSPP also begins to support Resilient Packet Ring over SDH (RPR over SDH), Multi-Protocol Label Switching over SDH (MPLS over SDH); the enhancement of data characteristics in MSPP and the standardization of technologies such as Generic Framing Protocol (GFP), Link Capacity Adjustment Scheme (LCAS) and Virtual Concatenation make SDH networks possess stronger and stronger transport capability for NGN services. OTN is a development of Wavelength-Division Multiplexing (WDM) technology, which enables a wavelength-division network to have an ability of constructing telecom-level optical transport networks; at present ITU-T has substantially completed the standardization of the main contents of OTN; OTN implements large-granularity transport with bandwidth larger than 2.5G suitable for NGN broadband services, therefore it is one of the key network technologies for Physical Layer transport of NGN in the future.
As for the control plane of the transport layer, the control plane protocols of respective sub-layers of the transport layer are isolated from each other, and there is no strict separation between the control plane and the user plane; wherein the control protocol of MPLS of the packet transport sub-layer has been relatively mature. As for the control protocol of the physical transport sub-layer, the appearance of Automatically Switched Optical Network (ASON) technology makes it possible for the physical layer network to be controlled though signaling; nowadays ASON has been applied in a broader and broader range, which adopts a signaling protocol similar to the signaling protocol of MPLS; therefore from a long-term point of view, it is possible for the control protocol of MPLS sub-layer and the control protocol of ASON to be unified.
In the prior methods for implementing NGN, several methods may be used for implementing the user plane of the transport layer in NGN as follows:
(1) separating the packet transport sub-layer and the physical transport sub-layer: implementing the service layer and the MPLS Packet transport sublayer with routers, bearing them on the physical transport sublayer devices such as Synchronous Digital Hierarchy/Wavelength-Division Multiplexer/Optical Transport Network (SDH/WDM/OTN).
(2) adopting MSPP: MSPP is a convergence of packet technology and SDH technology. At present, the MSPPs of a part of manufacturers possess MPLS function, and their implementation of MPLS may be concluded as two modes:
One mode is to implement MPLS on the User Network Interface (UNI) Board of MSPP, as shown in FIG. 1; the MPLS data flows are directly mapped into SDH Virtual Containers (SDH VCs) through the UNI Interface Board, and then transferred to the SDH High Order/Low Order (SDH HO/LO) crossing.
The other mode is to design a centralized MPLS switching module, as shown in FIG. 2; the MPLS data flows accessing through the UNI are mapped into SDH VCs, and transferred into the centralized MPLS switching module through the SDH HO/LO crossing for switching; or the MPLS data flows from the SDH UNI (borne on SDH VCs) are crossed through the SDH HO/LO, and then transferred to the centralized MPLS switching module for switching.
The above-mentioned two modes mainly aim to transport private line services; both of them may not meet the demand of large-scale and large-capacity NGN service transport.
In summary, in the prior network architectures and implementation methods of NGN, the service layer and the transport layer of NGN are confused; for example, the service routers may implement not only many functions of the service layer but also the functions of the transport layer. The lack of independence of the transport layer control plane in NGN makes it difficult to establish a secure signaling plane. The separated implementation of the transport layer functions is unfavorable to the construction of telecom-level transport network with high-efficiency and high-availability, or the reduction of the cost of transport network. | {
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This invention relates to switching and, more particularly to the switching of lights and individual appliances.
Switches are commonly employed to control energy applied to devices. The typical switch has an actuator, such as a manual toggle, with distinctive "on" and "off" positions. Once the switch is turned "on", it typically remains in that condition until someone turns it off.
Unfortunately, switches are often left on long after there is any need for the devices they control. This is particularly true for lights and small appliances. This is frequently due to the fact that the user has moved from the location of the switch and is no longer convenient for him to turn it off. The result is a waste of energy and unnecessary use of the controlled device.
Accordingly, it is an object of the invention to provide for the automatic de-energization of switches that have been left on inadvertently. A related object is to provide for the de-energization of switches with conventional toggle actuators, as well as other forms of actuators.
Another object of the invention is to provide for the automatic de-energization of household switches. A related object is to achieve automatic de-energization in switch boxes used for household switching.
Still another object is to provide automatic or manual de-energization at the option of the user. A companion object is to permit the reactivation of an automatically de-energized switch at any time during the operating cycle of the switch.
A further object of the invention is to provide an indication that the switch is about to be de-energized. | {
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European patent application No. 137,426 (Bayer AG) discloses compositions containing 2-thiazolylthio-alkanoic acid derivatives which have thromboxane antagonizing and platelet aggregation inhibiting activity and may be used in treating migraine headaches.
European patent application No. 201,349 (ICI) discloses hydroxyphenyldioxanyl-alkenyl-tetrazole compounds which are useful as thromboxane A.sub.2 antagonists in the treatment of ischemic heart disease and cerebrovascular disorders such as migraine headaches.
European patent application No. 201,350 (ICI) discloses hydroxyphenyloxa-thienyl-alkenoic acid derivatives useful as thromboxane-A.sub.2 antagonists in treating heart diseases and cerebrovascular disorders such as migraine headaches.
European patent application No. 223,518 (ICI) discloses N-o-hydroxyphenyl-dioxan-cis-yl-hexenoylsulfonamide derivatives useful as antagonists of thromboxane A.sub.2 for treating ischemic heart disease and cerebrovascular disease such as migraine headaches. | {
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1. Field of the Invention
The present disclosure relates to the field of liquid crystal displays (LCD), and more particularly to a cell test method and a cell test device for an LCD panel or an organic light emitting display (OLED) panel.
2. Description of the Prior Art
In manufacturing a liquid crystal display (LCD), product quality needs to be continually monitored, and unqualified products are timely removed, which improves a qualification rate of the products. Issues and existing risk may appear in the manufacturing according to the monitoring. At present, a cell test is performed on a panel before a display driver integrated circuit (IC) and a touch controller IC are bonded. As long as display of the panel is normal, the display driver integrated circuit (DDIC) and a digital diagnosis IC are bonded next. Furthermore, the entire display and other criteria need to be tested until product quality meets client requirements.
At present, cutting a step location of an LCD panel involves making a right-angle cut, therefore, step zone of a thin film transistor (TFT) cannot only put wires of a fanout zone but also put the panel for a cell test. As shown in FIG. 1, the panel includes a test pad 10 and the display driver integrated circuit 11. A relative signal is sent, and the panel can display some patterns without the display driver integrated circuit, which avoids unqualified products from entering a next step. As technology continues to improve, customers are placing more emphasis on size, light, and thickness of the products, which makes panel companies try to improve technology, such as further decreasing thickness of glasses; however, this causes strength of the glasses to be correspondingly decreased. In addition, a traditional backlight basic is a plastic element, and edge of the traditional backlight and an edge of the panel are substantially in alignment, which causes the glasses without cushion protection. As requirement of processing for bonding IC and a flexible printed circuit board, a polaroid cannot be attached to the panel, a step location for attaching the panel and a chip on film panel is weakness, namely wires for bonding the IC, the flexible printed circuit board, a wire on array and the fanout zone are weakness. With improvement of touch technology, more and more panel companies are constantly researching new technology that puts touch integration into their own products, which improves integration and customer experience, which further saves manufacturing cost, and package and transportation cost. Based on the above reason, some panel companies use oblique cut method at the step location of the TFT. In addition, even if the touch integration of the panel is used, quality of the products still needs to be tested. Therefore, wires of the fanout zone of the step location of the panel is dense to cause that the cell test pad cannot be put in a certain place, and the above problem needs to be solved. | {
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The present disclosure generally relates to systems and methods for performing confocal thermoreflectance measurements, and more particularly, to confocal thermoreflectance imaging systems and methods that enable measurement of temperature distributions.
Improved thermal engineering can improve the operating characteristics and lifetimes of optoelectronic devices. For example, heating in semiconductor lasers can limit the maximum output power, shift the lasing wavelength, cause mode hopping, reduce lifetime, reduce the differential efficiency, increase the threshold current density, and limit the small signal modulation response. In addition, thermal stabilization of optoelectronic components is increasingly important to improving the performance of many photonic applications, such as wavelength division multiplexing and high-speed communications networks.
Furthermore, experimental exploration of the remarkably complex heat generation and transport processes in micro- or nano-structured optoelectronic devices such as diode lasers and semiconductor optical amplifiers is also challenging, in large part because the primary heat sources are often buried deep within these devices. Because of these difficulties, the thermal properties of optoelectronic devices are often thought of as bulk characteristics. For example, characterizations of semiconductor lasers such as optical spectra or power vs. current (LI) curves are often quoted at particular operating temperatures for the device as a whole, without detailed attention to the spatial heat distribution in the laser. These techniques are clearly insufficient when investigating nanostructured optoelectronic devices, since thermal variations occur on the submicrometer scale.
Thermoreflectance is a well-established non-contact method for measuring temperature distributions on a variety of different sample types. In the past decade, thermal imaging (as opposed to single point measurements) has become increasingly popular to measure surface temperature changes. As a result, different ways to achieve this goal have been published. Two-dimensional (“2-D”) stochastic-resonance enhanced thermoreflectance imaging has been previously demonstrated with 250 nanometer (“nm”) lateral spatial resolution and 10 milliKelvin (“mK”) thermal resolution.
Thermoreflectance microscopy exploits the change in reflectance R of a material with temperature T:
Δ R R = 1 R · ∂ R ∂ T Δ T ≡ κ · Δ T by measuring small changes in the reflectivity ΔR, of a sample in response to temperature modulation ΔT. Typical values of the thermoreflectance calibration coefficient range from 10−6 Kelvin−1 (“K−1”) to 10−4 K−1, so lock-in techniques are required to extract the temperature signal. The prior single-point measurements and scanning techniques can be replaced by 2-D imaging onto diode-arrays connected to multiple lock-in amplifiers or charge-coupled devices (“CCDs”) with signal processing. However, until recently, it has been thought that the thermal resolution of imaging using a CCD is limited to 1 Kelvin (“K”) by the quantization limit of the camera. This high-resolution 2-D thermal imaging technique can investigate both the thermal behavior of a range of optoelectronic devices and also, in combination with a total energy balance model, characterize the optical power distribution within working photonic integrated circuits and other active devices. However, because current sub-micrometer-resolution thermal imaging techniques offer little depth resolution, they are limited to surface imaging, and therefore cannot be used to investigate heat flow deep within a device.
Heat transport in optoelectronic devices is known to be severely degraded by large numbers of epitaxial interfaces and by the use of alloyed materials. Early work on thin films and superlattices demonstrated strong anisotropy in in-plane versus cross-plane thermal conductivity. Molecular dynamics simulations of heat flow in heterostructures suggest that even a single interface can decrease cross-plane thermal conductivity κz by a factor of two; the presence of tensile strain further reduces κz. Furthermore, thermal conductivity can vary strongly with even small changes in material composition.
Thermal conductivity in superlattices is highly anisotropic and depends on a wide variety of factors, including interface quality, number of layers, layer thickness, lattice strain, and the ratio of the material composition. The cross-plane thermal conductivity κz can be reduced by up to a factor of 10 by phonon reflections at interfaces. Small reductions in the in-plane thermal conductivity κx also occur due to diffuse interface scattering. Results for GaAs/AlAs have shown that while the cross-plane thermal conductivity can be less even than the corresponding alloy value, the in-plane thermal conductivity of a GaAs/AlAs superlattice is usually less than that of the bulk materials but greater than that of the corresponding alloy.
In general, poor heat transport across heterojunctions results in relatively low thermal conductivities for complex optoelectronic devices. In particular, vertical cavity surface-emitting lasers (“VCSELs”) have a high thermal resistance due to their small size and the poor thermal conductivity of the mirrors (e.g., DBR mirror), so remarkably large variations (up to 200° C.) in the internal temperature distribution are predicted, both radially across the active region and vertically along the optical axis. In addition, prior work has shown radial surface temperature variations of up to 5 K between the center and edge of an operating VCSEL. Thermal models of edge-emitting lasers predict large variation in thermal impedance across the plane of the active region, resulting in temperature variations of up to 40%. Other work on quaternary blue-green lasers predicts temperature differences between surface and active region of 0.1-0.5 K for p-side up lasers and 1.5 K for p-side down devices.
A wide range of alternative methods for 2-D surface temperature measurements have been developed. A comparison of several temperature measurement techniques is found in FIG. 1, several of which are discussed below. Liquid crystal (“LC”) thermography provides good spatial and temperature resolution (1 micrometer (“μm”) and 0.05 to 0.5 K), but temperatures can only be measured relative to the clearing point temperature at which the crystals undergo a phase transition. Fluorescent microthermography is a similar thermal imaging technique with better temporal resolution; both of these methods require thin film deposition on the surface of the test device. Optical interferometry based on thermal expansion provides micrometer scale measurements with extremely good thermal resolution (10−6 K), but calibration of temperature based on surface displacement is very difficult for materials without a high thermal expansion coefficient. Scanning thermal microscopy can achieve a spatial resolution of 50 nm; this technique typically uses an atomic force microscope as a measurement platform.
The ability to measure temperature inside a three dimensional structure is currently very limited. Because Si and InP are transparent in infrared (“IR”) measurements (λ>2 μm), it is possible to use near-IR thermography to image flip-chip bonded ICs through the substrate; however, the lateral resolution is limited to 5 μm.
CCD thermoreflectance has been performed using the imaging optics of a widefield microscope, for which there is little depth discrimination and the Rayleigh criterion puts a lower limit on lateral spatial resolution of dx=0.6λ/NA where λ is the illuminating wavelength and NA is the numerical aperture of the microscope objective. Widefield microscopy has proven adequate for imaging the temperature distribution across the surface of a number of active optoelectronic devices, including semiconductor optical amplifiers, edge-emitting and surface-emitting diode lasers. However, accurate investigation of heat transport above and below dielectric layers (e.g., oxide passivation layers), across semiconductor interfaces (e.g., multi-quantum well active regions), or for devices with features less than 250 nm or alternatively offering poor image contrast demands further improvement in lateral and vertical spatial resolutions.
Therefore, there is a need for methods and systems for performing confocal thermoreflectance measurements that can measure temperature from reflective layers, objects, or defects, or for devices with features less than 250 nm or alternatively offering poor image contrast (e.g., devices such as transistors, nanocircuits, etc).
There is also a need for profiling thermal distribution both within an operating device, including LEDs, edge-emitting lasers, and VCSELs signal, and at the surface, heat sink, and sides, so that both the internal distribution and boundary conditions are understood. | {
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Since the dawn of professional sports, it has been common among sports fans, athletes, and others to display sports memorabilia, such as autographed baseballs. While it is of course possible to have players autograph baseballs at sports memorabilia stores, or other locations, a significant number of autograph signings occur at the baseball field prior to a game's start, when players practice and interact with the fans. Nevertheless, this informal and impromptu signing procedure presents a number of problems to both the signing player and the fan.
First, as the player usually does not return to the field from practice but is likely to sign the balls before leaving, he will likely still have on equipment like batting gloves or mitts, which become dirty through game play and which are themselves cumbersome to have to hold on to while also signing a baseball. Additionally, the sweat from a player's hands after a vigorous practice can itself damage the baseball, either by dirtying the surface of an unsigned ball or smearing other signatures on a baseball signed by more than one player. Such scuffing and dirtying of the baseball is of course highly deleterious to its aesthetic and monetary or collectible value. It would therefore be desirable for a fan or baseball collector desiring to have a signed baseball clean from dirt and other field debris to provide the player with a ball which is at least partly clean of such dirt or debris.
Next, as stated previously, the signing player is signing a baseball standing on the field of play while carrying his mitt. Oftentimes the player will be straining for any type of leverage against which he can more easily grip or sign the ball. Many players who would be agreeable to signing a baseball might nevertheless choose not to do so because of these practical obstacles in physically signing the ball. It would therefore be desirable for both a fan or baseball collector and a signing player to provide that player with some form of leverage to assist the player in physically signing the ball while standing.
Finally, many times a player who would be willing to sign a baseball is stymied in his attempt because he does not have a pen. Given the short amount of time a player has between the end of practice and having to depart the field, waiting for a fan to produce a pen is not something a player wishes to do. Also, many times a casual fan does not possess a pen but would still like to have a genuine autographed baseball. It would therefore be desirable for both a fan or baseball collector and a signing player to provide that player with simultaneously with both a baseball to be signed and a pen for the player to use in one convenient package.
A survey of the prior art reveals many devices useful for storing and displaying signed sports memorabilia, which are advantageous to the fan or collector by preventing a viewer from directly handling the memorabilia and thereby damaging the piece, and by protecting the piece from environmental degradation. Thus, U.S. Pat. No. 6,016,910 to Rodearmel describes and claims a device for displaying sports memorabilia having a base member and a memorabilia holder extending outwardly from a display surface of the base member. A music box may also be mounted to the base member, and at least one of the base member, holder or music box comprises indicia such as shapes, decorations, and sounds related to the sport of the memorabilia to provide an enhanced sensory experience for the viewer. Additionally, U.S. Pat. No. 5,379,892 to Reams, et al., describes and claims a protective display case for collectible items such as baseballs and other collectible items, comprising a rigid transparent tube which contains the baseballs and through which they can be viewed; one end cap at each end of the transparent tube to retain the balls; and a rigid backboard to which the end caps are attached for the purpose of holding the end caps in their fixed rigid position. However, while each of these devices indeed helps protect and display the signed baseballs, none of these in any manner facilitates the initial signing of the baseball. | {
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1. Field of the Invention
The field of invention relates to vehicular anti-theft structure, and more particularly pertains to a new and improved vehicular anti-theft lift apparatus wherein the same is arranged for lifting of a vehicle during non-use of said vehicle.
2. Description of the Prior Art
Vehicle anti-theft structure and apparatus related thereto is exemplified in the prior art by the U.S. Pat. Nos. 4,928,506; 4,037,684; 4,934,479; 4,360,074; and 5,040,826.
The instant invention attempts to address a manner of preventing vehicular theft and unauthorized use associated therewith, wherein an elevator structure is arranged in a mounted relationship relative to the drive housing of the vehicle such that upon discontinuance of operation of the vehicle, the elevator structure is actuated to lift the drive housing relative to an underlying support surface and in this respect, the present invention substantially fulfills this need. | {
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Prior art development environments used scripting languages to control the flow of an application. The languages contained individual code constructs called subroutines. Usually, a caller would call a subroutine to perform a certain task, and then receive a return code from the subroutine indicating its result. The caller would then execute a conditional branch instruction conditioned on the return code.
Accordingly, a developer who used subroutines needed to be familiar with all possible return codes that were output by the subroutines. Moreover, the developer needed to design a lengthy branch statement that accounted for all possible returns. Thus, the developer needed to be intimately familiar with the parameters and possible results of the subroutines.
In order to reduce the burden on the developer, prior art development environments had reusable subroutines that performed certain frequently-needed tasks. However, to increase reuse, these subroutines needed to allow for the different conditions that occurred in different calling situations. Therefore, the reusable subroutines had to be parameterized. That is, parameters had to be passed to the subroutine to tell it how to react to different situations. As reusable subroutines grew in complexity, more and more parameters became required. Since the developer had to be familiar with each possible parameter, even reusable subroutines created a heavy burden. In addition, if the application program interface (API) of a reusable subroutine changed, the developer had the burden of locating and changing all of the existing calls to that subroutine.
More recent prior art development environments were graphical in nature. Such graphical development environments used icons to represent various language components. Developers would draw lines or arrows connecting these icons. These lines defined a program flow (call flow). In the prior art, the burden of icon line connection was placed on the developer. Thus, the mechanics of line drawings as well as familiarity with each icon's functionality were burdens to developing successful program flow. For example, icons that behaved as a loop would have different line behaviors than icons that behaved as a branch.
Furthermore, prior art graphical development environments represented a subroutine as an icon in a call flow having a single input line and a single output line, even if the subroutine had multiple return codes. Therefore, the developer still had to be familiar with each possible return code and had to provide a mechanism for dealing with each one.
Prior art non-graphical development environments provided a way to create complex user-defined subroutines without too many parameters: overwritable subroutines. A subroutine can be thought of as containing its various functionalities. Some of these functionalities are always present, others are modified by parameters, and still others can be overwritten by the caller. Prior art non-graphical development environments allowed these overwritable functionalities to be represented as additional subroutines with default functionality defined and invoked by the containing subroutines. The caller of the containing subroutines could replace the default functionality of an overwritable subroutine by providing a corresponding overwriting subroutine. Obviously, the overwritable and overwriting subroutines each shared the same parameters and return codes.
However, the usefulness of overwritable subroutines in prior art was hampered by several limitations. In particular: (1) a lack of graphical representation of overwritable and overwriting subroutines; (2) an overwriting subroutine could only use data that was passed through the pre-defined parameter list--an extreme barrier to extending the default behavior; and (3) overwriting subroutines could only be defined once, not once for each call to the containing subroutine.
Accordingly, there is a need in the art for a graphical development environment that automatically connects icons in accordance with the call flow functionality of the underlying language component.
There is also a need in the art for a graphical development environment that graphically displays subroutines having multiple returns in a manner that eases the burden on the developer.
There is also a need in the art for a graphical development environment which tracks changes in subroutine APIs, so that those changes can automatically be reflected in all calls already made to that subroutine.
There is a further need in the art for a graphical development environment that graphically represents overwritable subroutines and improves their usefulness by enhancing their capabilities. | {
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The invention relates to food, cosmetic, pharmaceutical and textile industry and it may be used in production of alcoholic and soft drinks, confectionery, products made of sour milk, for coloring of tablet capsules, dying of children""s underwear, toys, etc.
Anthocyanic colorants are known to be made of mulberries, grapes, black-currant, black ash-berries, hollyhock, cellular tissues of carrots (UK Patent Application No. 8612587, filed in 1986; RF Patent No. 2057153, 1996; Food Ingredients, Primary Materials and Food Additives No. 1, 2000). Besides, there are processes of producing anthocyanic colorants from various plants, for example red grapes, cake of black ash-berry, hollyhock petals, etc. Such colorants suffer from the following drawbacks: low content of coloring matter, low thermo- and photostability, limited spectrum of colors. At the same time, as it may be seen from the above said, the anthocyanic colorants are made of berries and their cake, i.e. seasonal and perishable materials, and it makes the colorants production a multi-step and complicated process technologically and expensive financially. So, the drawback of the above mentioned processes is that the colorant production is a multi-step process due to low pigment content in the primary material, and besides the process is not efficient for other types of primary materials (RF Patent No. 2099376 to V. M. Bolotov et al, 1995).
Natural edible colorant made of hollyhock petals is the closest prototype of the proposed one (international Application PCT/SU88/00009, grade C 09 B 61/00, dated Jan. 12, 1988, International Publication WO 89/06671 dated Jul. 27, 1989). This colorant is an extract from anthocyanic primary material that includes the following components: glycosides of cyanidin, peonidin, delphinidin, petunidin and/or malvidin. The closest method to the proposed one is colorant production from vegetable materials that includes extraction of anthocyanic materials by aqueous solution of acid and/or alcohol in ultrasonic vibration field, extract separation and concentration to get the final product (RF Patent No. 2077543 grade C09B61/00, 1994).
The drawback of this colorant is that it has low stability while being stored both in pure form and in products where it is used, besides, the mentioned colorant has limited spectrum of colors, which constricts the sphere of its application. Drawbacks of the above method include impossibility to obtain concentrated colorant, high consumption of extracting agent and low output from primary materials containing anthocyan.
The object of this invention is to obtain natural anthocyanic red colorant that will have a wide spectrum of colors, high thermo- and photo-stability, easy production process, that will be based on use of new primary materials, which provide for production of the colorant in any volume irrespective of season and any other factors.
The invention is based on the object to prepare edible colorant from vegetable primary materials by changing and selection of certain components ratio as well as by changing conditions of extraction process from vegetable primary materials, and to develop a process of production thereof. The colorant shall be of high quality, stability, shall have wide spectrum of colors, wide field of application, including production of non-alcoholic tonic of high quality and stable color.
The specified object is achieved by adding pelargonidin glycosides into natural colorant that contains cyanidin glycosides, peonidin glycosides, organic substance and mineral salts. The percentage of components mass shall be as follows, %:
Due to the fact that the colorant solution contains pelergonidin glycoside further to cyanidin and peonidin glycosides, the proposed colorant has expanded color spectrum as it is known that cyanidin is of crimson color, peonidin is pink and purple and pelargonidin is scarlet. Combination of these three anthocyans in the proposed colorant shall provide for the most rich spectrum of red colors. At the same time the ratio of pelargonidin glycoside:peonidine glycoside:cyanidin glycoside must be 1:1.5:2, respectively, and it will provide for preparation of a colorant with a number of important physical properties. Namely, the colorant remains red when pH of the environment is not more than 7, it is thermostable, photostable and maintains its properties during 2 (two) years, besides, its relative optical density will be the highest when it is subjected to the light with wavelength of 505-515 nm. The colorant prepared with the following components ratio has the form of transparent thick liquid of murrey color, which is completely soluble in water and aqueous solutions of ethyl alcohol, with a smell of the primary material and a sour taste. Percentage of dry substance mass is minimum 20, mass proportion of coloring matter is minimum 40 g/l. The proposed colorant is an extract from vegetable materials containing anthocyan. Diversity of its color spectrum shall be provided by different types of anthocyans, their volume and their ratio. Chromatographic examination confirmed that the colorant contained three basic anthocyanides, namely cyanidin (crimson), peonidin (pink and purple) and pelargonidin (scarlet). Organic substance and mineral salts were also discovered in the colorant solution. The proposed colorant has been tested for toxicity on laboratory animals. Testing results prove that the colorant does not contain toxic matter and makes no changes in condition of laboratory animals. Besides, the proposed colorant is an extract of vegetable materials, it contains bio active compounds extracted from primary material. Availability of bio active matter shall increase the quality of the proposed colorant. | {
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DE 28 16 929 describes a device for mincing food consisting of an elongated baseplate provided with a handle, over whose surface the food product to be minced can be moved back and forth by hand. In the middle section, the device has a replaceable mincing insert. DE 28 16 929 also describes a food remnant holder that, while holding the food product to be minced, can be moved back and forth on the baseplate.
DE 28 57 743 describes a food remnant holder for a device for mincing food. The food remnant holder has a tubular receptacle for the food product to be minced and a pusher with a hood that can be placed over the tubular receptacle.
The known holders have the drawback that the food product to be cut is not adequately guided during the cutting procedure, thus having a negative effect on the cutting results. | {
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.gamma.-Poly(glutamic acid) (hereinafter ".gamma.-PGA") is a polymer which is biodegradable. However, the utility of .gamma.-PGA has been limited. For example, synthetic methods typically result in a .gamma.-PGA polymer, or corresponding side chain ester derivatives, having a molecular weight of less than about 10,000, which significantly limits the utility, such as theological or mechanical utility, of the polymer. See, Kovacs et al., Canad. J. Chem., 47: 3670 (1969); Hardy et al., J. Chem. Soc., 6: 605 (1972); Honda et al., Macromol. Chem., 176: 1643 (1978). Also, .gamma.-PGA is typically water-soluble, which limits the utility of this material in both environmental and medical applications.
One attempt to increase the molecular weight of .gamma.-PGA has been to ferment a bacteria, Bacillus licheniformis, which releases a naturally-produced .gamma.-PGA into the fermentation broth. However, naturally-produced .gamma.-PGA degrades over time, thereby significantly diminishing the molecular weight of naturally-produced .gamma.-PGA which can be recovered.
Therefore, a need exists for a method of forming .gamma.-PGA and derivatives thereof which overcome the aforementioned problems. | {
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This invention relates to sealing means having a resilient coat for providing a close seal between a stationary member and a movable member having an irregular surface.
A prior art sealing arrangement is shown in U.S. Pat. No. 2,865,165; note FIGS. 7-9 thereof where the engaging surfaces have metal to metal contact. A similar sealing arrangement is shown in U.S. Pat. No. 3,403,858. | {
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It is desirable to provide coherent reception of transmitted signals in a communications system, for which it is necessary to estimate parameters (amplitude, phase, frequency offset, and delay) of the communications channel which affect signal synchronization. A wireless CDMA system typically has multiple paths with multi-path fading, so that such parameters continuously change and must be estimated in an ongoing manner. Accordingly, accurate channel estimation in a CDMA system presents a substantial challenge.
In current CDMA systems, it has been proposed to allocate four channels for each user for synchronization and data communication. These channels are referred to as the pilot channel (P), for synchronization purposes; the fundamental channel (F), for voice signals and low-rate data transmission; the supplemental channel (S), for high-rate data communication, and the control channel (C), for very low-rate data communication for control purposes. One or more of the last three channels, i.e. the data channels, need not be used by a particular user at any time. For simplicity the following description refers primarily to the fundamental channel, but it should be understood that the same comments apply for any one or more of the data channels.
For efficient operation of the CDMA system, it is desirable for the transmit signal power allocated to the pilot channel (i.e. the relative gain of the pilot channel) to be small relative to that of the data channels. The pilot channel can be used for channel estimation, but its relatively low power can result in poor phase accuracy and poor amplitude tracking, so that channel estimation accuracy is not sufficient. For example, the much stronger fundamental channel constitutes interference when estimating the channel parameters from the pilot channel. Increasing the power allocated to the power channel to improve channel estimation is undesirable.
Channel estimation can also conceivably be based on the signals of one or more of the higher-power data channels, for example the fundamental channel. The complexity of such an arrangement has made it undesirable or impractical in a CDMA system, and it may provide slow convergence, or no convergence, due to poor estimates of information symbols.
Accordingly, there is a need to provide improved channel estimation in CDMA systems. | {
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Louver assemblies for lights are generally used to direct or limit the distribution of the light emitted. U.S. Pat. Nos. 2,065,814 (Lennon) and 2,906,864 (Boutelle) illustrate two such louvers. The louvers are typically placed over the front of a reflector, such as a parabolic reflector, which is used to direct light from a light source and which partially encloses the source. The louver assemblies generally consist of a series of rigid planar slats secured to form a parallel grid.
Louvers are particularly useful in photographic work such as studio photography where artificial light is used to create desired combinations of shading and illumination on the subject matter. The ability to control the dispersion of light through the use of louvers is most helpful in achieving the desired effects. Further, in connection with frontal projection photography of the type described in Jenkins U.S. Pat. No. 2,727,427 wherein a background is projected on a reflex reflector screen which reflects light back only in the direction from which it came, control of the lateral dispersion of the illumination is particularly important. By limiting the light that is directed onto the subject in the foreground to that coming directly from light sources on the sides, the background which is projected from and reflected to the viewing camera's position does not become obliterated by the side illumination.
Since photographic lighting is often moved not only within the studio but to different locations it is desirable that a louver attachment can be removed from the light and collapsed to a small configuration for transportation and storage. It is also desirable that the louver design lend itself to lightweight, durable, and economical construction. It is further desired that the louver attachment be adaptable to fit a variety of configurations of light and reflector arrangements. Such a louver attachment is provided. | {
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1. Field of the Invention
The present invention relates to visual display units for use in vehicles, such as automobiles and aircraft. More specifically, the present monitor is adapted to be mounted in a headrest of a vehicle seat.
2. Description of the Related Art
Monitors for displaying visual images have been commonplace aboard commercial aircraft and motor coaches for quite some time. For example, U.S. Pat. No. 5,267,775 to Nguyen, and U.S. Pat. No. 5,507,556 to Dixon disclose monitors that are adapted to be mounted in a seat back of an aircraft seat. Neither of these monitors is adapted for use in an automobile.
Disadvantageously, each of these monitors pivots automatically with the seat back. A viewer cannot adjust a viewing angle of either monitor independently of a recline angle of the seat back. This limitation prevents a viewer from adjusting the monitor to minimize glare. In an automobile a position and orientation of the vehicle relative to the sun is constantly changing. The movement creates glare at certain times, and viewers prefer to be able to adjust the screen to eliminate the glare. Thus, any monitor for use in an automobile is preferably adjustable so that viewers can minimize glare.
The Nguyen monitor pivots about a lower edge, and pivots into the seat back when a passenger reclines the seat back. Thus, the Nguyen monitor occupies a relatively large depth of the seat back. This configuration is not suitable for use in an automobile headrest, where space is very limited.
The Dixon monitor pivots about an axis located in the upper half of the housing. The axis is spaced downward and inward from the upper outer edge of the monitor (see FIGS. 3-5). The Dixon monitor pivots away from the seat back when a passenger reclines the seat back. However, because of the location of the pivot axis, an upper rear edge of the Dixon monitor moves toward the seat back when the monitor pivots. Like the Nguyen monitor, this configuration occupies a relatively large depth of the seat back and is not well-adapted for use in an automobile headrest, where space is very limited. Further, when the seat of Dixon is in a reclined position, and the monitor is in a position such that a lower edge thereof protrudes from the seat back, tension in a cable within the seat back holds the monitor in position. Thus, if a passenger strikes the monitor in this position, he or she could be injured because the monitor will not retract into the seat back. This configuration is also not appropriate for use in an automobile headrest, where during emergency braking passengers are frequently thrown forward.
Monitors have recently become more popular in private passenger vehicles where space is more limited than in aircraft and motor coaches. For example, U.S. Pat. No. 5,842,715 to Jones, and U.S. Pat. No. 6,250,976 to Chu disclose monitors that are adapted to be mounted in a head rest of an automobile seat. The Jones and Chu monitors are adapted to be mounted in an automobile headrest. However, neither of these monitors is adjustable independently of the headrest.
Unfortunately, none of these patents teaches a monitor that is adapted to be mounted within an automobile headrest, and is independently adjustable by a viewer to provide an optimum viewing-angle and to reduce glare.
Several monitors for use in private passenger vehicles include a plastic housing that is mounted to the vehicle headrest. The housing is glued into a cavity within the headrest, and the screen structure is securable within the housing using a variety of different attachment methods. For example, the housing may include tabs that snap into slots on the screen structure. Unfortunately, the connections between these screen structures and their respective housings are not very sturdy. Furthermore, the glued connections between the housings and their respective headrests are not very sturdy. Thus, during a vehicle collision, the screen structures tend to detach from their housings, and the housings tend to detach from their headrests. The loose screen structures and housings drifting about the passenger compartment pose a threat to the passenger's safety. | {
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High magnetic field electromagnets have become important in various types of equipment over recent years. One important type of such equipment is medical imaging equipment, such as the type commonly referred to as magnetic resonance imaging (MRI) equipment. MRI equipment utilizes the mechanism of nuclear magnetic resonance (NMR) to produce an image, and accordingly imaging systems operating according to this mechanism are also commonly referred to as NMR imaging systems.
As is well known in the field of MRI, a high DC magnetic field is generated to polarize the gyromagnetic atomic nuclei of interest (i.e., those atomic nuclei that have nonzero angular momentum, or nonzero magnetic moment) contained within the volume to be imaged in the subject. The magnitude of this DC magnetic field currently ranges from on the order of 0.15 Tesla to 2.0 Tesla: it is contemplated that larger fields, ranging as high as 4.0 to 6.0 Tesla, may be useful in the future, particularly to perform spectroscopy as well as tomography. The volume of the subject to be imaged (i.e., the volume of interest, or "VOI") is that volume which receives the high DC magnetic field, and within which the DC field is substantially uniform.
Imaging is accomplished in the VOI utilizing the mechanism of nuclear magnetic resonance in the gyromagnetic atomic nuclei contained therewithin. As such, in addition to the large field DC magnet, the MRI apparatus includes an oscillator coil to generate an oscillating magnetic field oriented at an angle relative to the DC field, and at a frequency matching the resonant frequency of the atoms of interest in the selected volume; frequencies of interest in modern MRI are in the radio frequency (RF) range. As the gyromagnetic nuclei in the defined volume will have a common resonant frequency different from atoms outside of the volume, modulation of a gradient magnetic field (produced by a gradient coil) allows sequential imaging of small volumes. The images from the small volumes are then used to form a composite image of the larger volume, such as the internal organ or region of interest. To produce the series of images, the MRI apparatus also includes a detecting coil in which a current can be induced by the nuclear magnetic dipoles in the volume being imaged.
In operation, as is well known, the magnetic dipole moments of those atoms in the volume which are both gyromagnetic and also resonant at the frequency of the oscillating field are rotated from their polarized orientation by the resonant RF oscillation by a known angle, for example 90.degree.. The RF excitation is then removed, and the induced current in the detecting coil is measured over time to determine a decay rate, which corresponds to the quantity of the atoms of interest in the volume being imaged. Incremental sequencing of the imaging process through the selected volume by modulations in the gradient field can provide a series of images of the subject that correspond to the composition of the subject. Conventional MRI has been successful in the imaging of soft tissues, such as internal organs and the like, which are transparent to X-rays.
It is well known in the art that the spatial resolution of MRI tomography improves as the strength of the available magnetic field increases. Conventional MRI equipment useful in diagnostic medical imaging requires high DC magnetic fields, such as 5 kgauss or greater.
Due to the large number of ampere-turns necessary to produce such high magnetic fields, conventional MRI systems now generally utilize superconducting wire in their DC coils. While the magnitude of the current carried in these coils is extremely high, the superconducting material and accompanying cryogenic systems required in such magnets are quite expensive, and also add significantly to the size and weight of the magnet in the MRI apparatus. In the extreme case, some conventional MRI magnets are sufficiently heavy (e.g., on the order of twenty tons) as to limit the installation of the MRI apparatus to a basement or ground floor laboratory. Addition of the necessary coils or iron required to shield the fringe magnetic field generated by such magnets further increases the size, weight and manufacturing costs of the MRI equipment.
By way of background, U.S. Pat. No. 4,783,628 (issued Nov. 8, 1988) and U.S. Pat. No. 4,822,772 (issued Apr. 18, 1989), both incorporated herein by this reference and commonly assigned with this application, describe superferric shielded superconducting magnets. These magnets described in these patents utilize passive shielding of ferromagnetic material, such as iron. The construction of the magnets described in these patents provide a highly efficient magnet, considering the magnetic field strength as a function of the current conducted in the superconducting loops, and with a highly uniform field in the magnet bore even at very strong magnetic fields such as on the order of 4 Tesla; the shielding is also very good in this magnet, with the 5 gauss line at 50 to 100 cm from the outer wall of the bore. The weight and size of the superferric shielded magnets described in U.S. Pat. Nos. 4,783,628 and 4,822,772 can be quite substantial, however, such as on the order of 35 to 130 tons.
Another example of a conventional superconducting magnet, but which relies substantially on active superconducting shielding loops is described in U.S. Pat. No. 4,595,899. The magnet disclosed in this reference has a set of three driving coils surrounded by three shielding coils, with the current through the shielding coils adjusted to exactly cancel the dipole outside of the magnet. External ferromagnetic shielding is also located around the shielding coils to assist in further shielding. Examples of other prior magnets used in MRI are described in U.S. Pat. No. 4,612,505, in which shielding is accomplished by way of magnetic soft iron rods, conducting coils, or both; U.S. Pat. No. 5,012,217, issued Apr. 30, 1992, describes yet another prior superconducting magnet utilizing a combination of active and passive shielding.
While actively shielded magnets greatly reduce the magnet weight relative to superferric shielded magnets, the weight of these magnets is still quite substantial, for example on the order of 20 tons. As a result, when used in medical equipment such as NMR stations, the "footprint" required for installation of the magnet and the weight-bearing capability of the floor of the room are both significant, whether the magnet is constructed of the superferric type, the actively shielded type, or a combination of the two. As a result, from the cost standpoint, it is desirable to reduce the physical size and weight of NMR equipment, to reduce the cost of the NMR laboratory.
In addition to the undesirably large footprint of conventional NMR magnets for medical MRI, a further disadvantage of conventional magnets is patient-related. It has been observed that many patients are uncomfortable when placed in magnets of such length, as the patient's entire body is generally disposed within the magnet during much of the imaging procedure. Indeed, conventional cylindrical NMR magnets have been referred to as "tunnel" magnets, suggestive of the sensation perceived by the human subject when placed inside for an imaging procedure. As an example of the importance of reducing this sensation, U.S. Pat. No. 4,924,185 discloses, relative to another cylindrical superconducting magnet design, that the sense of oppression on the part of the patient is reduced as the ratio of bore length to bore diameter is below 1.90. In addition, especially for patients who are seriously ill, it is essential that the magnet be able to receive the patient without requiring disconnecting life support or monitoring conduits from the patient, and while allowing medical personnel to access the patient during the procedure; conventional cylindrical magnets greatly limit such access.
Accordingly, it is highly desirable to provide NMR tomography equipment of the minimum size but with adequate field strength and uniformity. Toward this end, copending application Ser. No. 715,552, filed Jun. 14, 1991, entitled "A Compact Shielded Superconducting Electromagnet", incorporated herein by this reference and commonly assigned herewith, describes another cylindrical superconducting magnet which advantageously uses a combination of superferric shielding outside of the shielding coils. The magnet disclosed therein thus can be shorter in length while still providing high DC field in the bore and low fringe field away from the magnet.
Copending application Ser. No. 869,544, filed Apr. 15, 1992 in the name of Sergio Pissanetzky, and entitled "An Ultrashort Cylindrical Shielded Electromagnet For Magnetic Resonance Imaging", commonly assigned herewith, incorporated hereinabove by reference, and being the parent of this continuation-in-part application, discloses a short cylindrical superconducting magnet useful in NMR imaging equipment. This application further discloses an important methodology used to design the coils in the DC field generating magnet in such a manner as to optimize the strength and uniformity of the field in the volume of interest (VOI) while maintaining low fringe fields away from the bore. As will be described in further detail hereinbelow, this methodology also proves useful in the design of magnets of other shapes.
By way of further background, U.S. Pat. No. 4,689,591 discloses a superconducting magnet having a plurality of coaxial coils arranged asymmetrically along the axis, resulting in a volume of interest that is offset from the midplane of the magnet. The volume of interest in this magnet, while offset, remains deeply within a cylindrical bore, however, requiring whole body insertion of the patient for MRI procedures.
Another known type of conventional MRI magnet is of the Helmholtz coil type, including such a magnet which utilizes thermally insulated niobium/tin superconducting material. However, this magnet also requires the patient's whole body to be inserted between the Helmholtz coils.
By way of further background, U.S. Pat. No. 5,049,848, issued Sep. 17, 1991, discloses a magnet configuration suited for MRI in mammography. This magnet configuration is of rectangular shape, and includes permanent magnets (5, 6, 7, 8) for generating magnetic flux in two planes in the gap g within which the imaging is to take place. A shimming electromagnet (14) is disclosed as being placed behind the patient, for reducing front edge fringe field.
By way of further background, notched cylindrical coil systems for providing strong magnetic fields are known, as described in M. W. Garrett, "Thick Cylindrical Coil Systems for Strong Magnetic Fields with Field or Gradient Homogeneities of the 6th to 20th Order", J. Appl. Phys., Vol. 38, No 6 (1967), pp. 2563-86. As described in this reference at pages 2578-2583, expansion of ideal magnet elements to larger cross sections by modifying the geometry in an iterative fashion according to Lyle's Principle can be used to arrive at a magnet having a negative current polarity notch or cavity coil within the otherwise cylindrical positive coil; the notch may be at either the inner or the outer radial surface (see FIG. 2 of the reference), or even wholly within the positive coil.
In the method described in the above-cited Garrett article and also according to other conventional methods for designing cylindrical magnets, the designer relies on the property that the axial component of the magnetic field in the bore is a harmonic function within the volume of interest (VOI), which can be expanded into a series of spherical harmonics. The coefficients of this expansion may be expressed as axial derivatives of the axial magnetic field at the origin (center of the VOI). If one assumes that the current density in the cross-section of each magnet coil is constant, these axial derivatives may be calculated directly from coil geometry, without requiring integration of the Biot-Savart Law, allowing the geometry of the magnet to be adjusted so that the undesirable harmonics of the axial field in the VOI vanish. According to this generalized technique, computer-ready methods have been developed as have tabular design conditions (see the Garrett article cited above), facilitating the design of such magnets. This general method constrains the location of the VOI to a high degree, however, in order for the calculations to be readily performed; as such, this general method is practically applicable for a VOI centered at the midplane of the cylindrical magnet.
It is an object of the present invention to provide a method of fabricating an electromagnet for optimizing the field strength and uniformity in a selected volume of interest.
It is a further object of the present invention to provide such a method of fabricating a magnet which is applicable to magnets of various symmetry, including cylindrical and planar magnets.
It is a further object of the present invention to provide a magnet constructed according to such a method.
It is a further object of the present invention to provide such a magnet which allows for optimization of the design for a volume of interest which is not necessarily centered within the magnet bore.
It is a further object of the present invention to provide such a method which allows the center of the volume of interest to be located outside of the magnet bore.
It is a further object of the present invention to provide a superconducting magnet for use in NMR equipment which does not require insertion of the body of the patient into the magnet bore.
It is a further object of the present invention to provide such a magnet which is of sufficient field strength to enable in vivo NMR tomography of the internal organs of humans.
It is a further object of the present invention to provide such a magnet which is suitable for the image of specific organs, such as the brain, the female breast, and the like.
It is a further object of the present invention to provide such a magnet which makes the NMR tomography equipment substantially portable.
Other objects and advantages of the present invention will be apparent to those of ordinary skill in the art having reference to the following specification together with the drawings. | {
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This application relates generally to powered surgical handpieces such as those employed in endoscopic surgery. More particularly, this invention is directed to a powered surgical handpiece that includes an irrigator for applying fluid to a surgical site, a suction conduit for drawing fluid from the site, a means for clearing the suction conduit and a motor for actuating a complementary cutting accessory.
The powered handpiece has evolved into an important tool for performing surgical procedures. A typical powered handpiece includes a housing that contains an electrically driven motor. A coupling assembly is attached to one end of the handpiece. The coupling assembly is used to releasably secure a cutting accessory to the motor so that the motor, when energized, actuates the cutting attachment. The development of powered surgical handpieces and their complementary cutting accessories has made it possible to cut, shape and remove both hard and soft body tissue at faster rates and with a higher degree of accuracy than was possible with the manually powered tools that preceded them.
When a cutting attachment is actuated, the cutting action causes loose tissue and other debris to develop at the surgical site. This material is removed by applying an irrigation fluid to the site and also drawing a suction from the site. The irrigation fluid serves as a transport media for carrying the debris; the suction draws away the fluid and the entrained debris. In order to perform this irrigation and suction, some cutting attachments are provided with conduits through which fluid is applied to and drawn from the surgical site. For example, cutting attachments designed to perform endoscopic surgery or sinus surgery often include a static outer sleeve in which a rotating tube is fitted. The head of the rotating tube is provided with some type of cutting surface or cutting member. Each of these attachments is further shaped so that irrigation fluid can flow to the surgical site through the annular channel between the rotating tube and the static sleeve. The inner rotating tube is further provided with an opening adjacent the head through which a suction is drawn from the surgical site. Thus, the inner tube serves as the conduit through which the irrigation fluid and debris are removed from the surgical site.
A powered handpiece intended for use with the above cutting attachments is designed with complementary features that facilitate the drawing of the suction away from the surgical site. Specifically, this type of handpiece is provided with a suction bore to which a suction pump is applied. The coupling assembly allows fluid flow from the inside of the rotating tube to the suction bore. Moreover, the handpiece is provided with a valve for regulating fluid flow through the suction valve. Thus, a surgeon using this type of handpiece can, with one hand, both manipulate the cutting accessory and regulate the rate at which fluid is drawn from the surgical site.
While current handpieces have provided useful for both driving cutting attachments and drawing a suction, there are some disadvantages associated with their use. In particular, current handpieces and their complementary cutting attachments are designed so that irrigation fluid is introduced into the annular channel through a supply line that is separate from the handpiece. While this supply line may be attached to a handpiece, it has a free end that is typically located forward of the handpiece coupling assembly. The free end of this line has to be manually fitted to an inlet luer integral with the static sleeve. When, during a surgical procedure, the doctor wants to switch cutting attachments, this line must first be removed from the cutting attachment being separated from the handpiece. Then, after the new cutting attachment is installed, the supply line must be manually fitted to the new attachment. The time it takes to perform these steps adds to the overall time it takes to perform the surgical procedure.
Moreover, in these surgical handpieces, the motor is in close physical proximity to the path through which the suction fluid flows through the handpiece. Accordingly, these handpieces must be constructed to include sufficient seals that prevent liquid flow into the components forming the motor. However, over time, and owing to the presence of the moving parts against which these seals press, these seals can wear out. Consequently, it is not uncommon for fluid to enter the motor and cause the components forming the motor to corrode and/or malfunction. Once the integrity of these seals diminishes, this corrosion and motor component wear can occur at a relatively fast rate because the fluid drawn through the handpiece suction is saline.
Also, occasionally, debris can clog the cutting accessory rotating tube through which the suction is drawn from the surgical site. This clogging is especially prone to occur in cutting accessories designed for performing sinus surgery. This is because the diameter of the bore through which this suction flow travels is relatively narrow. Presently, there are two ways a surgeon can try to remove this type of clog in order to reestablish suction at the surgical site. One method involves introducing a large quantity of irrigation fluid into the surgical site. The surgeon takes this action by momentarily running the irrigation pump used to supply fluid at a high speed/high flow flush setting. The introduction of this large quantity of water causes a large fluid pressure head to develop in the rotating tube upstream of the clog. If the conditions are right, the pressure head of this fluid forces the clog-causing debris to flow downstream out of the rotating tube. One problem with this clog removal technique is that the switches for regulating the irrigation pump are typically located off the handpiece. In order for the surgeon to be able to control the pump, he/she must actuate a separate foot or hand switch or instruct an assistant to perform this operation. In each of these situations, the surgeon may have to significantly divert his/her attention from the actual surgical procedure being performed. Still another problem with this method of clog removal is that, often, it simply does not work. Then, the surgeon is left with a situation in which excess fluid has been introduced into the patient.
The second method of clog removal is more mechanical. This method involves running a rigid wire down the rotating tube in order to force the clog out of the tube. When a surgeon has to take this action, he/she must first withdraw the cutting attachment from the surgical site. Then, once the clog is removed, the cutting attachment must be repositioned so that the surgical procedure can be completed. The need to perform these tasks adds to the overall time it takes to perform the surgical procedure.
This invention relates to an improved powered surgical handpiece and a cutting accessory for use with the handpiece. This invention includes a motor that has a rotor integral with the cutting accessory and complementary windings that are integral with the handpiece. The handpiece has a coupling assembly for holding the cutting attachment to the handpiece that has a conduit through which irrigation fluid is introduced into the attachment for application to the surgical site. The handpiece of this invention also has a valve for regulating fluid flow through the conduit through which a suction is normally drawn. Depending on the setting of this valve, a suction can be drawn through the cutting attachment, the suction shut off or irrigation fluid can be introduced into the suction conduit in order to flush out any debris lodged in the conduit. | {
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The conventional auto exhaust gas purifiers include a manifold reactor, a catalyst converter and so on. For the purpose of preserving the internal heat of these devices, while reducing their exhaust gas emission and preventing the heat in these devices from being transferred to the other auto parts with adverse effect, a heat insulating material which is durable at high temperatures is required. The heat resistance of the foamed sodium silicate ceramics heretofore used as heat insulating materials can be improved by adding aluminum hydroxide, but 500.degree.-600.degree. C is said to be the upper limit to which the ceramics thus improved can resist heat.
At the same time, ceramic fibers are often used for insulation of manifold reactors, but they cause various problems in that the fibers tend to fly out into the exhaust gas through gaps in welded joints which have been broken under repeated application of thermal stresses due to temperature variations, or to clog the bypass valve of the catalyst converter or the valve of the exhaust gas recirculator (EGR). | {
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A force moment sensor allows for the sensing of six degrees of freedom force measurement. Dexterous tasks in close proximate operations where camera views are insufficient need these senses of touch to avoid overloading both the payloads they are handling and themselves. A force moment sensor is an instrument that typically is integrated into a robotic arm. It is particularly useful in space applications as well as underwater applications.
Space robotic operations take place over extended time frames (hours to days), under fluctuating temperature environments, on a flexible robotic arm. The need to capture ‘free flying’ bodies (ie spacecraft which are ‘freely floating’ with respect to the capturing robot) is a further challenge over those of terrestrial environments.
Lack of atmosphere drives temperatures to be either hot in sun or cold in shade. Since robots are typically used for moving things around, so they go into and out of shade repeatedly.
There are a number of challenges when determining the force and moment applied to a robotic arm in an unknown environment. These challenges are even more difficult in a space environment. Typically force is not directly measurable. It can be inferred from strain or deflection. However, such measures are affected by thermal distortion. It is well known that long robot arms and the need to capture ‘free flyers’ generate large rotational forces. In addition, a high stiffness requirement makes measurement of strain or deflection more difficult to isolate from thermal distortion. Further, drift in space operations tend to be slow—often taken over a period of hours. Still further, it is important to distinguish all 6 degrees of force measurement, but the shear and moment loading cases can produce difficult to distinguish effects
Accordingly a force moment sensor designed for use in space or underwater would be desirable. | {
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The present invention relates to a containment enclosure for enclosing a cryogenic unit. The containment enclosure has particular application in off-shore locations.
There are many applications which use a cryogenic unit. Such cryogenic units typically include air separation units, gas liquefaction units, and synthesis units. It is sometimes desirable or necessary for reasons of safety to enclose such units, particularly to contain any cryogenic liquids or vapours leaking from the cryogenic unit. Whilst containment enclosures can be desirable in particular in on-shore applications, they are essential in off-shore applications as human operators often have to work and live within a few metres of the cryogenic unit. In many off-shore applications, such as deep sea oil rigs or other platforms and on sea-going vessels, because of the close proximity of the human operators to the cryogenic unit and also because of the difficulties in evacuating human operators from such off-shore applications, containing leaks from a cryogenic unit is of paramount importance.
When a cryogenic liquid or vapour does leak from a cryogenic unit, it is necessary to dispose of or disperse the leaking liquid and/or vapour. In on-shore applications, this can normally simply be achieved by venting the cryogenic liquid and/or vapour to atmosphere. However, venting a cryogenic liquid or vapour to atmosphere can generate a thick fog in the vicinity of the vent, which seriously reduces the visibility in the region of the vent, and can cause icing of neighbouring structures. Moreover, simply venting liquids and vapours to atmosphere can cause a health hazard to human operators working nearby and can cause damage to neighbouring structures, depending on the liquids or vapours which are being vented. For example, where the liquid or vapour is oxygen-rich, there may be a risk of fire or explosion. There is also a risk of structural damage to the carbon steels which are tonically employed in the construction of off-shore rigs by embrittlement fatigue from contact with cryogenic fluids.
In a paper entitled xe2x80x9cTonnage Nitrogen Generation For Oil And Gas Enhanced Recovery In The North Seaxe2x80x9d presented in the Annual Report, Session 6 of the 9th Continental Meeting of the Gas Processors Association, 14th May 1992, there is disclosed a containment enclosure for an air separation unit. The containment enclosure disclosed in that paper utilises a known type of thermal insulation in which loose insulation contained by a wire mesh (xe2x80x9cchicken wirexe2x80x9d) forms a thermally insulating layer which is resistant to penetration of cryogenic leaks from the air separation unit. However, the efficiency of the thermal insulation provided by a loose fill of insulation has been found to be very variable as it is difficult to ensure an optimum and consistent density and hence provide minimum thermal conductivity of the loosely filled insulation. Furthermore, the loosely filled insulation is only merely resistant to cryogenic leaks and severe leaks can penetrate the insulation thereby destroying the integrity and effectiveness of the thermal insulation.
Moreover, where maintenance of a cryogenic unit is required, it is necessary to provide some access through any thermal insulation to the cryogenic unit. In an off-shore application, it is especially important to be able to have easy access to the cryogenic unit for maintenance purposes because any delays in providing maintenance access to the cryogenic unit may increase the safety risk to operators. The removal and addition of any loose filled insulation around a cryogenic unit can be very time-consuming and should preferably therefore be avoided particularly in off-shore applications.
In the containment enclosure disclosed in the paper mentioned above, the containment enclosure has a sump at its base which can receive and contain a liquid leaking from the cryogenic unit contained in the containment enclosure. The sump has a stainless steel liner forming the sump wall. In this prior art proposal, liquid can be passed from the sump to a vaporiser which then vaporises the liquid prior to dispersal.
An object of the present invention is to overcome one or more of the problems mentioned above.
U.S. Pat. No. 4,513,550 discloses a method of building a large-scale tank or reservoir for storing a liquid at low temperature.
U.S. Pat. No. 4,452,162 discloses a corner structure for a cryogenic insulation system used as a large-scale container for storage of cryogenic liquefied gases.
U.S. Pat. No. 4,041,722 discloses a large-scale tank for storage of cryogenic liquefied gases.
DE-A-4038131 and U.S. Pat. No. 4,625,753 each disclose an example of a small-scale container for storage of cryogenic liquefied gases.
According to a first aspect of the present invention, there is provided in combination, a containment enclosure and a cryogenic unit, the cryogenic unit being at least one of an air separation unit, a gas liquefaction unit, a gas synthesis unit, and a gas purification unit, the containment enclosure being arranged to contain liquid leaking from the cryogenic unit and comprising a chamber in which the cryogenic unit is located; a chamber wall which includes thermal insulation for thermally insulating the cryogenic unit in the chamber; and, a sump for receiving liquid leaking from the cryogenic unit; characterised in that: the chamber wall is impermeable to liquid leaking from the cryogenic unit.
The containment enclosure can completely contain all leaks from the cryogenic unit located within the chamber. The integrity of the thermal insulation is maintained at all times.
The chamber wall preferably includes a plurality of thermally insulating bricks for thermally insulating the chamber. The bricks are preferably free of any binder. The bricks are most preferably pre-compressed mineral fibre.
The use of thermally insulating bricks rather than a loose fill thermal insulation as in the prior art greatly facilitates assembly of the containment enclosure and also facilitates access to a cryogenic unit within the chamber for maintenance purposes. The thermal insulation Properties of the bricks can be well defined and will usually be within a very narrow range, which is in contrast to the very variable thermal insulation properties of loose filled thermal insulation. It will be appreciated that the word xe2x80x9cbrickxe2x80x9d used herein includes other substantially self-supporting structures such as, for example, blocks and slabs. It is preferred that the bricks be free of any binder in case any oxygen-containing liquid or vapour leaking from the cryogenic unit does come into contact with the bricks as such binders may have a potential to combust on contact with liquids or vapours containing oxygen.
The bricks are preferably arranged in layers, each layer comprising a plurality of bricks, the bricks in at least one layer being staggered relative to the bricks in an adjacent layer such that the abutment between adjacent bricks in said at least one layer is discontinuous with the abutment between adjacent bricks in said adjacent layer. Staggering the bricks in one layer relative to the bricks in an adjacent layer improves the thermal insulation properties of the bricks as it limits the convection pathways for warm air to enter the chamber from outside the containment enclosure.
A convection break is preferably positioned between at least some bricks. The or each convection break may comprise a sheet of substantially gas-impermeable foil.
In a preferred embodiment, studs or pins are provided for securing the bricks to the chamber wall. The studs can be used to locate the bricks relative to the chamber wall and to each other. The studs can be used, in association with an impermeable panel, to compress the bricks if desired, which may be desirable in order to obtain optimum thermal insulation from the bricks.
At least one panel is preferably affixed to the chamber wall between the insulation and the chamber, said at least one panel being impermeable to liquid leaking from the cryogenic unit to render the chamber wall impermeable to liquid leaking from the cryogenic unit. In a preferred embodiment, a plurality of panels is affixed to the chamber wall between the insulation and the chamber, wherein, at a horizontal connection between adjacent upper and lower panels, the lowermost edge of the upper panel overlies the uppermost edge of the adjacent lower panel on the chamber side of said adjacent upper and lower panels. Preferably, at a vertical connection between adjacent plural panels, the adjoining edges of said adjacent panels are interlocked.
The or each panel is preferably of a material which is such as to prevent any liquids or vapours escaping into the chamber from the cryogenic unit from reaching the insulation. The panel or panels therefore provide a shield or protective layer for the insulation. In the preferred embodiment, plural panels are effectively tiled in a manner similar to roof tiles such that a liquid striking and running down the panels is shed by the panels and does not penetrate into the insulation.
The or at least some of the panels are preferably affixed to and compress the thermal insulation by means of studs which pass through said panels into said insulation. The studs may be fixed at one end to an enclosure wall of the enclosure so that the thermal insulation is compressible between said panels and said enclosure wall.
The sump is preferably open at its uppermost end to receive liquid leaking from the cryogenic unit, the sump being defined by a sump wall and a sump base, and comprising withdrawing means for withdrawing liquid from the sump through the open uppermost end of the sump. The withdrawing means normally requires the specific application of energy (for example electrical power/steam/motive gas) to provide a lift capability for withdrawing liquid. Release of the contained cryogen cannot be achieved by accident as the withdrawing means is remotely energised and can only by achieved by operation of the withdrawing means. A vaporiser may be connected to the withdrawing means for receiving and vaporising liquid withdrawn from the sump. Heating means for heating vapour produced by the vaporiser prior to dispersal of said vapour may be provided. The sump is preferably large enough to contain the whole inventory of the cryogenic unit.
The chamber may have at least one side wall which includes a plurality of insulating bricks for thermally insulating the chamber.
The chamber may have a top wall which includes a plurality of insulating bricks for thermally insulating the chamber.
According to a second aspect of the present invention, there is provided in combination, a containment enclosure and a cryogenic unit, the containment enclosure comprising a chamber in which the cryogenic unit is located, the chamber having a chamber wall which includes a plurality of thermally insulating bricks for thermally insulating the chamber.
The bricks are preferably arranged in layers, each layer comprising a plurality of bricks, the bricks in at least one layer being staggered relative to the bricks in an adjacent layer such that the abutment between adjacent bricks in said at least one layer is discontinuous with the abutment between adjacent bricks in said adjacent layer.
There may be a convection break between at least some bricks.
Preferably, at least one panel is affixed to the chamber wall between the bricks and the chamber to render the bricks impermeable to liquid leaking from the cryogenic unit. A plurality of panels may be affixed to the chamber wall between the bricks and the chamber, wherein, at a horizontal connection between adjacent upper and lower panels, the lowermost edge of the upper panel overlies the uppermost edge of the adjacent lower panel on the chamber side of said adjacent upper and lower panels. A plurality of panels may be affixed to the chamber wall between the bricks and the chamber, wherein, at a vertical connection between adjacent panels, the adjoining edges of said adjacent panels are interlocked.
A sump may be provided for receiving liquid leaking from the cryogenic unit, the sump being open at its uppermost end to receive liquid leaking from the cryogenic unit, the sump being defined by a sump wall and a sump base, the enclosure comprising withdrawing means for withdrawing liquid from the sump through the open uppermost end of the sump. There may be a vaporiser connected to the withdrawing means for receiving and vaporising liquid withdrawn from the sump. Heating means may be provided for heating vapour produced by the vaporiser prior to dispersal of said vapour.
Where panels are provided, the bottom edge of the panels can project beyond the upper lip of the sump to shed liquid without permitting penetration through the insulation behind.
According to a third aspect of the present invention, there is provided in combination, a containment enclosure and a cryogenic unit, the containment enclosure comprising a chamber in which the cryogenic unit is located; a chamber wall which includes thermal insulation for thermally insulating the cryogenic unit in the chamber; a sump for receiving liquid leaking from the cryogenic unit, the sump being open at its uppermost end to receive liquid leaking from the cryogenic unit, the sump being defined by a sump wall and a sump base; and, withdrawing means for withdrawing liquid from the sump through the open uppermost end of the sump.
A vaporiser may be connected to the withdrawing means for receiving and vaporising liquid withdrawn from the sump. Heating means for heating vapour produced by the vaporiser prior to dispersal of said vapour may be provided.
In a preferred embodiment, the sump comprises a sealed membrane of stainless steel or aluminium supported by a floor and walls of glass foam blocks sandwiched between the membrane and the carbon steel outer surface of the enclosure. The foam glass blocks are preferably multi-layered and staggered to avoid continuous abutments through the wall and are laid without adhesive to allow for thermal movement. The faces of adjoining blocks may have a woven glass fibre blanket layer to prevent abrasion of the blocks.
The combination may be situated in an off-shore location.
The cryogenic unit may be an air separation unit or a gas liquefaction unit or a purification or separation unit for other gases. | {
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1. Field of the Invention
The present invention relates to a semiconductor device, in particular a semiconductor device having a level shift circuit and a voltage output circuit.
2. Description of Related Art
Conventionally, a driver circuit of a display device has been composed of a level shift circuit to convert a low amplitude level signal to a high amplitude level signal, and a voltage output circuit to apply high voltage to the display device based on the output of the level shift circuit. For example, Japanese Unexamined Patent Application Publication No. 11-225054 (Isobe et al.) describes a voltage output circuit in related art.
FIGS. 5 and 6 show a driver circuit described in Isobe et al. In FIG. 5, the voltage output circuit is composed of a CMOS type circuit, which is in turn composed of a P-channel type field effect transistor (called “PMOS transistor” hereinafter) and a N-channel type field effect transistor (called “NMOS transistor” hereinafter). Meanwhile, in FIG. 6, the voltage output circuit is composed of two NMOS transistors. In both cases, a voltage output circuit in the related art has circuit structure in which a single transistor is driven by one level shift circuit.
However, in the circuit shown in FIG. 5, the current load characteristic of the transistor in the voltage output circuit largely depends on the power supply potential. Therefore, the lower the power supply potential, the larger the current load characteristic becomes (see FIG. 8). Meanwhile, in the circuit shown in FIG. 6, owing to a zener diode Di inserted between the gate and source of the transistor of the voltage output circuit, the output potential is lower than the power supply potential VCC by an amount corresponding to the voltage drop VZ of the zener diode Di (see FIG. 7).
As explained above, in the case a PMOS transistor is used in the voltage output circuit of the driving circuit in the related art, the current load characteristic depends on the power supply potential, and therefore the lower the power supply potential, the larger the current load resistance becomes. Furthermore, in the case a NMOS transistor is used in the voltage output circuit, the output potential becomes lower than the power supply potential VCC. | {
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1. Field of the Invention
This invention relates to aerosol drug formulations. This invention also relates to dispersing aids for use in aerosol drug formulations. In another aspect this invention relates to aerosol formulations comprising hydrofluorocarbon propellants.
2. Description of the Related Art
Delivery of drugs to the lung by way of inhalation is an important means of treating a variety of conditions, including such common conditions as bronchial asthma and chronic obstructive pulmonary disease. Steroids, .beta.-2 agonists, and anti-cholinergic agents are among the drugs that are administered to the lung for such purposes. Such drugs are commonly administered to the lung in the form of an aerosol of particles of respirable size (less than about 10 .mu.m in diameter). In order to assure proper particle size in the aerosol, particles can be prepared in respirable size and then incorporated into a suspension formulation containing a propellant. Alternatively, formulations can be prepared in solution form in order to avoid the concern for proper particle size in the formulation. Solution formulations must nevertheless be dispensed in a manner that produces particles or droplets of respirable size.
Once prepared an aerosol formulation is filled into an aerosol canister equipped with a metered dose valve. In the hands of a patient the formulation is dispensed via an actuator adapted to direct the dose from the valve to the patient.
It is important that an aerosol formulation be stable such that the dose discharged from the metered dose valve is reproducible. Rapid creaming, settling, or flocculation after agitation are common sources of dose irreproducibility in suspension formulations. Sticking of the valve also can cause dose irreproducibility. In order to overcome these problems aerosol formulations often contain surfactants, which serve as suspending aids to stabilize the suspension for a time sufficient to allow for reproducible dosing. Certain surfactants also function as lubricants to lubricate the valve to assure smooth actuation. Myriad materials are known and disclosed for use as dispersing aids in aerosol formulations. Suitability of materials, however, is dependent on the particular drug and the propellant or class of propellant used in the formulation.
It is sometimes difficult to dissolve sufficient quantities of conventional surfactants in hydrofluorocarbon (HFC) propellants such as HFC-134a and HFC-227. Cosolvents have been used to overcome this problem. An alternative approach that avoids use of cosolvents involves materials that are soluble in hydrofluorocarbon propellants and are said to be effective surfactants or dispersing aids in an aerosol formulation. Among such materials are certain fluorinated surfactants and certain polyethoxy surfactants.
The materials used in medicinal aerosol formulations are taken into the lungs. It is therefore desirable that they be non-toxic or suitably metabolized or eliminated. | {
"pile_set_name": "USPTO Backgrounds"
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1. Field of the Invention
The present disclosure relates to an information processing system, a client device and a method of control.
2. Description of the Related Art
A system has been proposed that enables use of various services on the Internet from a terminal of an intranet provided in a corporate environment. This system generally includes installation of a firewall on the internet/intranet boundary. The firewall allows connection from the intranet to the Internet, but is configured to refuse connection from the Internet to the intranet. In this manner, access from a terminal on the Internet into the intranet is limited. The above configuration is also premised on the fact that a conventional communication system using the WEB generally includes performance of an information acquisition request from a client to a server by PULL-type communication in which the server responds by transmitting the information.
However, in recent years, technical developments in PUSH-type communication have increased in which information is sent from the server to the client. An example of a PUSH-type communication technology is Comet or WebSocket. If an HTTP request is sent by a client to a server in Comet, the server retains the request without immediately responding. Thereafter, when information is produced to be sent from the server to the client, the information is sent as a response to the retained request.
WebSocket is a technology for bidirectional communication prepared by W3C or IETF which is the standardization body for the Internet. Establishment and maintenance of a TCP connection, rather than an HTTP connection, does not require mapping onto a HTTP protocol such as when using Comet, and thereby enables communication at a free timing from either the client or the server.
In this manner, in the context of a PUSH-type communication technology, information can be sent by use of a server connection even in an environment provided with a firewall by establishing and maintaining a connection from a client in an intranet.
Consequently, in recent years, a printing system has been proposed that uses PUSH-type communication. A PUSH-type printing system establishes a connection of a client device (printer) in an intranet with a server apparatus (print server) and constantly maintains that connection. In this manner, the print server can issue a request (print job execution request) when the print server is the starting point, and communicate that request at an arbitrary timing through a firewall to a printer. Japanese Patent Application Laid-Open No. 2008-140275 discloses a communication system configured so that an external host in an external network can transmit communication path maintenance data to an internal host with which access by the external host is restricted by a firewall for the maintenance of a communication path to the internal host.
For the promotion of continuous system development, a PUSH-type communication system using WebSocket has added a WebSocket connection in response to the addition of an application. That is to say, rather than for each printer, a WebSocket connection is required for each application that is installed on a printer.
When a WebSocket connection is provided for each application, the processing load for management of a constant connection for the number of applications by the print server is increased as the number of applications increases. Consequently, print server operations may become unstable or suitable processing operations may no longer be enabled. Furthermore, in a PUSH-type communication system using WebSocket, when a printer is started up, the printer must extend the WebSocket connections corresponding to the number of preinstalled applications. Therefore, the WebSocket connections that correspond to the applications that are not used for execution of a request issued by the print server are consequently an unnecessary resource. | {
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The present invention generally relates to tail construction for heating elements. More specifically, the present invention relates to ceramic heating elements with tails constructed such that the tails heat to substantially lower temperatures than normal "hot tail" construction.
Ceramic heating elements are, of course, generally known and used in the construction industry. Typically, ceramic heating elements are used for pre-heating and post-weld stress relieving piping welds. The most common form of heating element consists of interlocking ceramic beads for electrical insulators forming a flat pad. Typically, the flat pads are approximately three-eighths (3/8") of an inch thick but may vary depending on the beads or other insulators used. Typically, the beads are strung together using 80/20 nichrome wire to form a continuous circuit. The two ends of the wire extend from the corners of a heating element consisting of strung-together ceramic beads. The ends of the wires extend for a sufficient distance to allow for electrical connection of the wires to a source.
The wire leads are commonly called "tails" in the industry and are designed as either "hot" tails or "cold" tails. Each type of tail, however, has its drawbacks.
Hot tail construction connects the resistant wire producing the heat inside the heating element directly to an electrical connector at the end of the tail. Typical electrical connectors are made from brass, but other connectors, of course, may be implemented. As a voltage is applied to the tails of the heating element, electrical current flows through the wire. Typical voltages of eighty volts are applied resulting in a current of approximately sixty Amperes thereby causing the temperature of the nichrome wire to rise. Since the nichrome wire is connected directly to the terminals, each of the terminals also become hot. This type of construction is beneficial in that a continuous wire is connected to the electrical connector resulting in no weak points in the heating element or the tails.
Alternatively, cold tails are provided having a different form of construction than hot tails. Cold tails are constructed so as to lower the resistance of the wire leads thereby lowering the temperature of the tail itself. Typically, cold tails are constructed by one of two methods.
One method of construction of a cold tail is to place a second nichrome wire adjacent to the existing wire in the tail. A metal tube is then slid over both wires up to the main heating element body and crimped to produce an electrical connection. Both of the wires are then run into the electrical connector, typically constructed from brass. Having two wires, the electrical resistance is only one-half of the original amount producing only one-fourth of the heat generated in a system using hot tail construction. Therefore, the connector is substantially cooler. However, this results in several drawbacks.
One drawback is that the tails are flexible and, therefore, the point at which the metal sleeve is crimped becomes a weak point. The crimped sleeve cuts the small individual strands of the heating wire causing a hot spot which fails earlier than any other point on the wire. A second drawback is that a manufacturer of heating elements must also stock and use a different ceramic bead to insulate the tail since the tail has a larger inside diameter than the outer beads needed for the remainder of the heating element.
Another type of cold tail construction involves butt welding of the nichrome wire at the point at which it exits the main heating element. The nichrome wire is butt welded to a nickel wire of the same size. Nickel wire has a substantially lower resistance than the nichrome wire resulting in a lower temperature at the connector. A butt weld, however, is typically difficult to construct. The two wires must be welded together without changing the diameter of the joint. Further, the weld must appear as one continuous wire. Any reduction in diameter causes a hot spot which fails early after use. Any increase in diameter prevents the ceramic insulators from sliding over the joint. Furthermore, any contamination in the weld causes the joint to heat up. Therefore, a clean environment is required to manufacture this type of cold tail.
A need, therefore, exists for an improved tail for heating elements and a method for heating overcoming the deficiencies of the known tail constructions and combining the advantages of both hot tail construction and cold tail construction. | {
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This invention is generally directed to hydroxy gallium phthalocyanines and photoconductive imaging members thereof, and, more specifically, the present invention is directed to processes for the preparation of hydroxygallium phthalocyanines wherein there is avoided the use of a halo, especially a chloro component, such as chlorogallium phthalocyanine. In embodiments, the process of the present invention comprises the preparation of Type V hydroxygallium phthalocyanine which comprises the formation of a precursor gallium phthalocyanine with, for example, an X-ray powder diffraction trace having peaks at Bragg angles of 7.6, 8.1, 9.7, 16.0, 18.4, 19.2, 19.9, 24.7, 25.7 and 26.2, and the highest peak at 8.1 degrees 2.THETA., prepared by reaction of 1,3-diiminoisoindolene with gallium acetylacetonate in a suitable solvent, such as N-methylpyrrolidone, or halonaphthalene like 1-chloronaphthalene, quinoline, and the like; hydrolyzing the precursor by dissolving in a strong acid and then reprecipitating the resulting dissolved pigment in aqueous ammonia, thereby forming Type I hydroxygallium phthalocyanine; and admixing the Type I formed with a polar aprotic organic solvent, for example N,N-dimethylformamide N-methyl pyrrolidone, pyridine, dimethylsulfoxide, and the like. More specifically, in embodiments the process of the present invention comprises the formation of a precursor prepared by the reaction of 1 part of gallium acetylacetonate with from about 1 part to about 10 parts, and preferably about 4 parts of 1,3-diiminoisoindolene in a solvent, such as quinoline, chloronaphthalene, or N-methylpyrrolidone, in an amount of from about 10 parts to about 100 parts and preferably about 19 parts for each part of gallium acetylacetonate that is used to provide a pigment precursor gallium phthalocyanine, which is subsequently washed with a component such as dimethylformamide to provide the precursor gallium phthalocyanine as determined by X-ray powder diffraction with an X-ray powder diffraction trace having peaks at Bragg angles of 7.6, 8.1, 9.7, 16.0, 18.4, 19.2, 19.9, 24.7, 25.7, and 26.2, and the highest peak at 8.1 degrees 2.THETA.; dissolving 1 weight part of the resulting gallium phthalocyanine in concentrated, about 94 percent, sulfuric acid in an amount of from about 1 weight part to about 100 weight parts and in an embodiment, about 5 weight parts, by stirring the pigment precursor gallium phthalocyanine in the acid for an effective period of time, from about 30 seconds to about 24 hours, and in an embodiment, about 2 hours at a temperature of from about 0.degree. C. to about 75.degree. C., and preferably about 40.degree. C. in air or under an inert atmosphere such as argon or nitrogen; adding the resulting mixture to a stirred organic solvent, in a dropwise manner at a rate of about 0.5 milliliter per minute to about 10 milliliters per minute and in an embodiment, about 1 milliliter per minute to a nonsolvent, which can be a mixture comprised of from about 1 volume part to about 10 volume parts and preferably about 4 volume parts of concentrated aqueous ammonia solution (14.8N) and from about 1 volume part to about 10 volume parts, and preferably about 7 volume parts of water for each volume part of sulfuric acid that was used, which solvent mixture was chilled to a temperature of from about -25.degree. C. to about 10.degree. C. and in an embodiment, about -5.degree. C. while being stirred at a rate sufficient to create a vortex extending to the bottom of the flask containing said solvent mixture; isolating the resulting blue pigment by, for example, filtration; and washing the hydroxygallium phthalocyanine product obtained with deionized water by redispersing and filtering from portions of deionized water, which portions are from about 10 volume parts to about 400 volume parts and in an embodiment, about 200 volume parts for each weight part of precursor pigment gallium phthalocyanine which was used. The product, a dark blue solid, was confirmed to be Type I hydroxygallium phthalocyanine on the basis of its X-ray diffraction pattern having major peaks at 6.9, 13.1, 16.4, 21.0, 26.4, and the highest peak at 6.9 degrees 2.THETA.. The Type I hydroxygallium phthalocyanine product so obtained can then be treated with a solvent, such as N,N,-dimethylformamide, by, for example, ball milling said Type I hydroxygallium phthalocyanine pigment in the presence of spherical glass beads, approximately 1 millimeter to 5 millimeters in diameter, at room temperature, about 25.degree. C., for a period of from about 12 hours to about 1 week, and preferably about 24 hours, such that there is obtained a hydroxygallium phthalocyanine Type V, in a purity of up to about 99.5 percent.
Advantages of the present invention include the use of an air stable reagent, gallium acetylacetonate, used in the reaction in place of the highly reactive component gallium chloride, and the generation of a pigment precursor gallium phthalocyanine with an X-ray powder diffraction trace having peaks at Bragg angles of 7.6, 8.1, 9.7, 16.0, 18.4, 19.2, 19.9, 24.7, 25.7, and 26.2, and the highest peak at 8.1 degrees 2.THETA., which when converted to product hydroxygallium phthalocyanine Type V, by the processes described in Examples VI and VII, is free of chlorine as opposed to the process described in Example V, whereby there is generated a pigment precursor chlorogallium phthalocyanine with an X-ray powder diffraction trace having peaks at Bragg angles of 9.1, 11.0, 18.8, 20.3, and 27.0, and the highest peak at 27.0 degrees 2 .THETA., which, when converted to product hydroxygallium phthalocyanine Type V, by the processes described in Examples VI and VII, has residual chlorine levels of, for example, 0.68 percent. It is believed that impurities, such as chlorine, in the photogenerating Type V hydroxygallium phthalocyanine can cause a reduction in the xerographic performance thereof, and in particular, increased levels of dark decay, and such impurities have a negative adverse impact on the cycling performance of the photoreceptor device.
The Type V obtained can be selected as organic photogenerator pigments in layered photoresponsive imaging members with charge transport layers, especially hole transport layers containing hole transport molecules such as known tertiary aryl amines. The aforementioned photoresponsive, or photoconductive imaging members can be negatively charged when the photogenerating layer is situated between the hole transport layer and the substrate, or positively charged when the hole transport layer is situated between the photogenerating layer and the supporting substrate. The layered photoconductive imaging members can be selected for a number of different known imaging and printing processes including, for example, electrophotographic imaging processes, especially xerographic imaging and printing processes wherein negatively charged or positively charged images are rendered visible using toner compositions of appropriate charge polarity. In general, the imaging members are sensitive in the wavelength region of from about 550 to about 900 nanometers, and in particular, from 700 to about 850 nanometers, thus diode lasers can be selected as the light source.
In Bull. Soc. Chim. Fr., 23 (1962), there is illustrated the preparation of hydroxygallium phthalocyanine via the precursor chlorogallium phthalocyanine. The precursor chlorogallium phthalocyanine is prepared by reaction of o-cyanobenzamide with gallium chloride in the absence of solvent. O-cyanobenzamide is heated to its melting point (172.degree. C.), and to it is added gallium chloride at which time the temperature is increased to 210.degree. C. for 15 minutes, and then cooled. The solid is recrystallized out of boiling chloronaphthalene, to give purple crystals having carbon, hydrogen and chlorine analyses matching theoretical values for chlorogallium phthalocyanine. Dissolution in concentrated sulfuric acid, followed by reprecipitation in diluted aqueous ammonia, affords material having carbon, and hydrogen analyses matching theoretical values for hydroxygallium phthalocyanine.
In JPLO 221459, there are illustrated gallium phthalocyanine compounds which show the following intense diffraction peaks at Bragg angles (2 theta .+-.0.2.degree.) in the X-ray diffraction spectrum,
1. 6.7, 15.2, 20.5, 27.0; PA1 2. 6.7, 13.7, 16.3, 20.9, 26.3 (hydroxygallium phthalocyanine Type I); and PA1 3. 7.5, 9.5, 11.0, 13.5, 19.1, 20.3, 21.8, 25.8, 27.1, 33.0 (chlorogallium phthalocyanine Type I). PA1 1. 6.7, 15.2, 20.5, 27.0; PA1 2. 6.7, 13.7, 16.3, 20.9, 26.3; and PA1 3. 7.5, 9.5, 11.0, 13.5, 19.1, 20.3, 21.8, 25.8, 27.1, 33.0.
Further, there is illustrated in JPLO 221459 a photoreceptor for use in electrophotography comprising a charge generation material and charge transport material on a conductive substrate, and the charge generation material comprising one or a mixture of two or more of gallium phthalocyanine compounds which show the following intense diffraction peaks at Bragg angles (2 theta .+-.0.2.degree.) in the X-ray diffraction spectrum,
In Konica Japanese 64-17066/89, there is disclosed, for example, the use of a new crystal modification of titanyl phthalocyanine (TiOPc) prepared from alpha-type TiOPc (Type II) by milling it in a sand mill with salt and polyethylene glycol. This publication also discloses that this new polymorph differs from alpha-type pigment in its light absorption and shows a maximum absorbance at 817 nanometers while the alpha-type exhibits a maximum at 830 nanometers. The Konica publication also discloses the use of this new form of TiOPc in a layered electrophotographic device having high photosensitivity at exposure radiation of 780 nanometers. Further, this new polymorph of TiOPc is also described in U.S. Pat. No. 4,898,799 and in a paper presented at the Annual Conference of Japan Hardcopy in July 1989. In this paper, this same new polymorph is referred to as Type Y, and reference is also made to Types I, II, and III as A, B, and C, respectively.
Layered photoresponsive imaging members have been described in a number of U.S. patents, such as U.S. Pat. No. 4,265,900, the disclosure of which is totally incorporated herein by reference, wherein there is illustrated an imaging member comprised of a photogenerating layer, and an aryl amine hole transport layer. Examples of photogenerating layer components include trigonal selenium, metal phthalocyanines, vanadyl phthalocyanines, and metal free phthalocyanines. Additionally, there is described in U.S. Pat. No. 3,121,006 a composite xerographic photoconductive member comprised of finely divided particles of a photoconductive inorganic compound dispersed in an electrically insulating organic resin binder. The binder materials disclosed in the '006 patent comprise a material which is incapable of transporting for any significant distance injected charge carriers generated by the photoconductive particles.
The use of certain perylene pigments as photoconductive substances is also known. There is thus described in Hoechst European Patent Publication 0040402, DE3019326, filed May 21, 1980, the use of N,N'-disubstituted perylene-3,4,9,10-tetracarboxyldiimide pigments as photoconductive substances. Specifically, there is, for example, disclosed in this publication N,N'-bis(3-methoxypropyl)perylene-3,4,9, 10-tetracarboxyldiimide dual layered negatively charged photoreceptors with improved spectral response in the wavelength region of 400 to 700 nanometers. A similar disclosure is revealed in Ernst Gunther Schlosser, Journal of Applied Photographic Engineering, Vol. 4, No. 3, page 118 (1978). There are also disclosed in U.S. Pat. No. 3,871,882 photoconductive substances comprised of specific perylene-3,4,9,10-tetracarboxylic acid derivative dyestuffs. In accordance with the teachings of this patent, the photoconductive layer is preferably formed by vapor depositing the dyestuff in a vacuum. Also, there are specifically disclosed in this patent dual layer photoreceptors with perylene-3,4,9,10-tetracarboxylic acid diimide derivatives, which have spectral response in the wavelength region of from 400 to 600 nanometers. Also, in U.S. Pat. No. 4,555,463, the disclosure of which is totally incorporated herein by reference, there is illustrated a layered imaging member with a chloroindium phthalocyanine photogenerating layer. In U.S. Pat. No. 4,587,189, the disclosure of which is totally incorporated herein by reference, there is illustrated a layered imaging member with a perylene pigment photogenerating component. Both of the aforementioned patents disclose an aryl amine component as a hole transport layer.
In copending application U.S. Ser. No. 537,714 (D/90087), the disclosure of which is totally incorporated herein by reference, there are illustrated photoresponsive imaging members with photogenerating titanyl phthalocyanine layers prepared by vacuum deposition. It is indicated in this copending application that the imaging members comprised of the vacuum deposited titanyl phthalocyanines and aryl amine hole transporting compounds exhibit superior xerographic performance with low dark decay characteristics and high photosensitivity, particularly in comparison to several prior art imaging members prepared by solution coating or spray coating, reference for example U.S. Pat. No. 4,429,029 mentioned hereinbefore.
In U.S. Pat. No. 5,153,313 (D/90244), the disclosure of which is totally incorporated herein by reference, there is illustrated a process for the preparation of phthalocyanine composites which comprises adding a metal-free phthalocyanine, a metal phthalocyanine, a metalloxy phthalocyanine or mixtures thereof to a solution of trifluoroacetic acid and a monohaloalkane; adding to the resulting mixture a titanyl phthalocyanine; adding the resulting solution to a mixture that will enable precipitation of said composite; and recovering the phthalocyanine composite precipitated product.
In U.S. Pat. No. 5,166,339 (D/90198), the disclosure of which is totally incorporated herein by reference, there is illustrated a process for the preparation of titanyl phthalocyanine which comprises the reaction of titanium tetrapropoxide with diiminoisoindolene in N-methylpyrrolidone solvent to provide Type I, or .beta.-type titanyl phthalocyanine as determined by X-ray powder diffraction analysis; dissolving the resulting titanyl phthalocyanine in a mixture of trifluoroacetic acid and methylene chloride; adding the resulting mixture to a stirred organic solvent, such as methanol, or to water; separating the resulting precipitate by, for example, vacuum filtration through a glass fiber paper in a Buchner funnel; and washing the titanyl phthalocyanine product. Examples of titanyl phthalocyanine reactants that can be selected in effective amounts of, for example, from about 1 weight percent to about 40 percent by weight of the trifluoroacetic acidic solvent mixture include known available titanyl phthalocyanines; titanyl phthalocyanines synthesized from the reaction of titanium halides such as titanium trichloride, titanium tetrachloride or tetrabromide, titanium tetraalkoxides such as titanium tetra-methoxide, -ethoxide, -propoxide, -butoxide, -isopropoxide and the like; and other titanium salts with compounds such as phthalonitrile and diiminoisoindolene in solvents such as 1-chloronaphthalene, quinoline, N-methylpyrrolidone, and alkylbenzenes such as xylene at temperatures of from about 120 to about 300.degree. C.; specific polymorphs of titanyl phthalocyanine such as Type I, II, III, and IV, the preparation of which, for example, is described in the literature; or any other suitable polymorphic form of TiOPc; substituted titanyl phthalocyanine pigments having from 1 to 16 substituents attached to the outer ring of the compound, said substituent being, for example, halogens such as chloro-, bromo-, iodo- and fluoro-, alkyls with from 1 to about 6 carbon atoms such as methyl-, ethyl-, propyl-, isopropyl-, butyl-, pentyl-, and hexyl-; nitro, amino, alkoxy and alkylthio, such as methoxy-, ethoxy- and propylthio- groups; and mixtures thereof.
Disclosed in U.S. Pat. No. 5,164,493 (D/90524) is a process for the preparation of titanyl phthalocyanine Type I which comprises the addition of titanium tetraalkoxide in a solvent to a mixture of phthalonitrile and a diiminoisoindolene, followed by heating. The disclosure of this application is totally incorporated herein by reference. Disclosed in U.S. Pat. No. 5,189,156 (D/91152) is a process for the preparation of titanyl phthalocyanine Type I which comprises the reaction of titanium tetraalkoxide and diiminoisoindolene in the presence of a halonaphthalene solvent; and U.S. Pat. No. 5,206,359 (D/91151) is a process for the preparation of titanyl phthalocyanine which comprises the treatment of titanyl phthalocyanine Type X with a halobenzene, the disclosures of which are totally incorporated herein by reference.
Illustrated in copending patent application U.S. Ser. No. 105,264 (D/93101), the disclosure of which is totally incorporated herein by reference, are processes for the preparation of Type II dihydroxygermanium phthalocyanine, which comprises the reaction of phthalonitrile or diiminoisoindolene with tetrahalogermanium or tetraalkoxygermanium in a suitable solvent, treatment of the resultant dihalogermanium phthalocyanine or dialkoxygermanium phthalocyanine intermediate with concentrated sulfuric acid, and then water, and filtering and washing of the dihydroxygermanium phthalocyanine precipitate with water using care that the filtrate of the washing does not exceeds a pH of 1.0, removing the absorbed acid on the dihydroxygermanium phthalocyanine product with an organic base, such as amine, and optionally washing the pigment crystals with an aprotic organic solvent, such as an alkylene halide like methylene chloride, tetrahydrofuran, or dimethylformamide; and the preparation of Type II dihydroxygermanium phthalocyanine by polymorphic conversion from other polymorphs, such as Type I polymorph, by simply treating with concentrated sulfuric acid, followed by the same washing processes as described above. The different polymorphic forms of dihydroxygermanium phthalocyanine can be readily identified by various known analytical methods including solid state absorption spectra and X-ray powder diffraction analysis (XRPD).
Also, in U.S. Ser. No. 169,486, the disclosure of which is totally incorporated herein by reference, there is illustrated a process for the preparation of hydroxygallium phthalocyanine Type V, essentially free of chlorine, whereby a pigment precursor Type I chlorogallium phthalocyanine is prepared by reaction of gallium chloride in a solvent such as N-methylpyrrolidone, present in an amount of from about 10 parts to about 100 parts, and preferably about 19 parts, with 1,3-diiminoisoindolene (DI.sup.3) in an amount of from about 1 part to about 10 parts, and preferably about 4 parts DI.sup.3 for each part of gallium chloride that is reacted; hydrolyzing the pigment precursor chlorogallium phthalocyanine Type I by standard methods, for example acid pasting, whereby the pigment precursor is dissolved in concentrated sulfuric acid and then reprecipitated in a solvent, such as water, or a dilute ammonia solution, for example from about 10.to about 15 percent; and subsequently treating the resulting hydrolyzed pigment hydroxygallium phthalocyanine Type I with a solvent, such as N,N-dimethylformamide, present in an amount of from about 1 volume part to about 50 volume parts and preferably about 15 volume parts, for each weight part of pigment hydroxygallium phthalocyanine that is used by, for example, ball milling said Type I hydroxygallium phthalocyanine pigment in the presence of spherical glass beads, approximately 1 millimeters to 5 millimeters in diameter at room temperature, about 25.degree. C., for a period of from about 12 hours to about 1 week, and preferably about 24 hours such that there is obtained a hydroxygallium phthalocyanine Type V, ball milling contains very low levels of residual chlorine of from about 0,001 percent to about 0.1 percent, and in an embodiment about 0.03 percent of the weight of the Type V hydroxygallium pigment, as determined by elemental analysis.
The disclosures of all of the aforementioned publications, laid open applications, copending applications and patents are totally incorporated herein by reference. | {
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Because of their high strength and toughness, various duplex alloys have been used in the field of iron alloys known as “special steels.” A number of special steels with various two-phase structures have been in practical use. A representative special steel is the duplex stainless steel standardized under Japanese Industrial Standard JIS SUS329J1.
In the ceramics field, on the other hand, research and development of single-phase ceramics and putting them to practical use is being promoted. By the use of combustion synthesis under controlled pressure and temperature, we have succeeded in synthesizing a “silicon alloy” from inexpensive silicon, which exists in the Earth's crust in large quantities, and are promoting its practical application as a structural material to replace special steels. Duplex ceramics, however, are yet to be developed.
Relevant prior art can be found in unexamined Japanese Patent Publication No. 91272/2004, unexamined Japanese Patent Publication No.162851/2008, Japanese Patent Publication No. 4339352, Japanese Industrial Standard JIS G4304-1999, and in Toshiyuki Watanabe et al., “FC Report 26,” p. 68, Japan Fine Ceramics Association, Tokyo, 2008.
A major difference between fine ceramics and steels as structural materials lies in their plastic deformability. It has been generally recognized that ceramics are brittle, whereas steels are tenacious, and it has been considered that ceramics are unable to replace steels completely because ceramics exhibit brittle fracture morphology.
Because it is a solid solution, a silicon alloy has a good chance to be composed of two phases by utilizing eutectic reaction after combustion synthesis. Ceramics with a duplex structure, combining advantages of each phase, have a good chance to exhibit ductility similar to that of duplex steels, and are expected to be much stronger than traditional single-phase ceramics.
However, only a single-phase silicon alloy has been obtained by conventional combustion synthesis. The reason appears to be that the conventional combustion synthesis process employs a small combustion synthesis apparatus and a cooling apparatus having a high cooling capacity. Therefore the silicon alloy is cooled too rapidly. The same can be said concerning metals such as steels. That is, slow cooling is necessary in order to obtain eutectic properties. Accordingly, there is a good chance that a silicon alloy having a duplex eutectic structure can be obtained by controlling the cooling rate following combustion synthesis.
Such duplex eutectic silicon alloys can be commercialized easily by applying the manufacturing processes described in Japanese Patent Applications Nos. 158407/2009 and 202440/2009, which processes are already in practical use. The latter Japanese patent application corresponds to U.S. patent application Ser. No. 12/871,009, filed Aug. 30, 2010, the disclosure of which is incorporated by reference.
Thus, it can be expected that development of a duplex eutectic silicon alloy will increase the chance for ceramics to replace special steels as general-purpose industrial materials, and will expand the fields in which a silicon alloy metal-ceramics can be utilized. Therefore it is an object of this invention to obtain a eutectic silicon alloy having a duplex structure. | {
"pile_set_name": "USPTO Backgrounds"
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The invention relates to a method for determining the position of a tool of a rock drill in a known system of coordination relative to rock when using a rock drilling equipment comprising a base, at least one drilling boom mounted pivotally relative to the base and a rock drill connected pivotally relative to the boom to the other end of the boom and provided with a tool, in which method the position of the base of the rock drilling equipment in said system of coordination is determined and the position of the tool in said system of coordination is determined on the basis of the position of the base.
In excavating underground spaces, the accuracy of excavation is highly significant--the space to be excavated, e.g. a traffic tunnel, has been set a nominal measure which must not be reduced. When using the drilling/explosion method, drilling accuracy has a significant effect on the accuracy of excavation. In order to improve the drilling accuracy of holes, the positions of planned holes can be measured in advance with separate measuring devices and marked on the rock surface. Another method is to use instrumented or automatic drilling equipments in which the drilling boom is provided with sensors measuring the position of its joints; on the basis of the sensors the position and direction of the rock drill and thus of its tool relative to the base of the equipment can be determined--when this information is connected to a separately determined position and direction of the base of the equipment, the position and direction of the drill relative to the planned drill pattern can be determined and thus controlled. Regardless of the use of different methods, drilling accuracy has in practice been variable. This is because the methods require either handiwork or skill or that the measuring of the position of the joints of the drilling boom are sensitive to e.g. variation in the mechanical characteristics of the parts of the boom caused by wear and exterior forces acting on the boom. The variation in drilling accuracy leads, for example, to that in practice, more rock has to be excavated as a precaution than was planned. This causes additional costs in drilling, in explosion, in handling the blasted rock and in supporting the space. The variation in drilling accuracy is also harmful when excavating ores in which case the excavation of extra rock only incurs costs. Also, the precise direction and positioning of a tool is difficult in other rock drilling activity, such as when extracting off rock blocks with a percussion hammer by means of a striking tool or when doing any essential work with varying rock drilling equipments.
Finnish Patent Application 884,970 discloses an arrangement in which a feed beam of a rock drilling equipment is directed by using at least three laser beams the direction and position of which relative to the general system of coordination is known and by placing transmitters/receivers at each beam and at the feed beam at a distance from one another so that the direction and position of the feed beam in the general system of coordination of the tunnel can be measured on the basis of the oscilllation waves from the transmitters. This arrangement is suitable for long hole drilling but it is difficult to apply to tunnel drilling because laser beams have to be detached from their positions for the duration of explosion so that they would not be damaged. Further, if drilling equipments comprising more than one feed beam are used, not even three laser beams are necessarily enough so that the direction and position of all feed beams could be measured by means of them.
British Patent Application 2 180 117 discloses a method in which the position of the measuring tip is determined by using three measuring units mounted at fixed positions in the surroundings and two detectors mounted to the shaft of the measuring tip, whereby each measuring unit measures the position and distance of the detector and on the basis of this the position of the measuring tip is calculated. This arrangement requires that the measuring units are fixedly mounted in the surroundings, wherefore this method cannot be applied as such to rock drilling, nor can the arrangement disclosed in said Finnish Patent Application.
The object of this invention is to achieve such a method for measuring the position of a tool of a rock drill of a rock drilling equipment that can be used effectively and easily in all drilling and also when using more rock drilling equipments, if required.
The method of the invention is characterized in that the position of the tool relative to the base is determined by measuring, using at least three measuring devices situated at a known position relative to the base and at a distance from one another, wherein at least two are attached to the base, and at least one measuring device is located at a known position relative to the tool. At least some of the measuring devices comprise a transmitter for transmitting oscilllation energy and correspondingly, at least some of the measuring devices comprise a receiver for receiving oscilllation energy. The distance between the transmitters and receivers is measured on the basis of the oscilllation energy transmitted by each transmitter; the distances between the receivers and transmitters are calculated on the basis of the measured distances; and the position of the tool relative to the base is determined on the basis of the distances calculated.
The essential idea of the invention is that at least two measuring devices, that is, transmitters or receivers, mounted in the base of the rock drilling equipment are used and similarly, receivers or transmitters arranged at a known position relative to each rock drill or, when desired, in both cases transmitter-receivers, whereby the position of the rock drills and their tools can always be determined relative to the base. A further essential idea of the invention is that the position of the base of the rock drilling equipment relative to the rock in the general system of coordination is determined in some manner known per se, such as by means of laser or fixed point navigation, whereby when determining the position of the rock drill relative to the base, they are at the same time determined relative to the general system of coordination. According to one preferred embodiment of the invention, a separate transmitter-receiver unit, for example, can be used to help in determining the position of the rock drills. The transmitter-receiver unit is placed at a suitable position in the vicinity of the rock to be drilled, such as below rock drills or booms after which the position of this separate transmitter-receiver unit is determined by means of measuring devices fixedly mounted in the base after which the separate unit can be used for measuring the position of the rock drills.
A logical and readily useable measurement is achieved with the method according to the invention at the same time as a reliable measurement is obtained in all conditions by using several different measuring devices. | {
"pile_set_name": "USPTO Backgrounds"
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1. Technical Field of the Invention
This invention pertains to IP packet filtering. More specifically, it relates to a use of small, optimized sequences of binary 6-tuples representing filter rules to achieve very fast IP packet filtering.
2. Background Art
Internet protocol (IP) network address translation (NAT) and IP filtering are functions which provide firewall-type capability to an Internet gateway system. In one specific system, this is accomplished by providing means for the system administrator to specify specific NAT and filtering rules via an operational navigator graphical user interface (GUI).
IP packet filtering is the process of checking each Internet protocol (IP) packet that is going to be sent from or has just arrived at a gateway system, or node, in a communications network, and based upon that check of making a decision. The decision is (typically, and insofar as it relates to the preferred embodiment of this invention) whether the packet should be discarded or allowed to continue. These are termed the `deny` and `permit` actions. IP filtering is widely used in Internet firewall systems, by independent service providers (ISPs) and organizations connected to the Internet.
Filter rules are most commonly an ordered list of rules, processed sequentially from top to bottom (order is specified by the system administrator). Each rule permits a certain kind of IP traffic. Processing for an IP packet continues until the packet is permitted, explicitly denied, or there are no more rules, in which case it is denied. Usually a number of filter rules must be written for each protocol to be permitted.
It is important the IP filtering actions be particularly efficient and very fast because of the huge volume of IP packets a typical gateway system will handle each day, and because of the fairly large number of filter rules that might have to be processed for each IP packet. Typically, each IP packet that flows through the system must be processed by all the filter rules. A moderately busy system can easily be expected to process 10**6 packets per day. Hence, any unnecessary overhead might cause throughput problems.
It is an object of the invention to provide an improved IP packet filtering system and method.
It is a further object of the invention to provide a very fast IP packet filtering system and method. | {
"pile_set_name": "USPTO Backgrounds"
} |
1. Field of the Invention
The present invention relates generally to trellis-coded communications systems, and more specifically to Viterbi decoder having a high processing speed.
2. Description of the Related Art
A Viterbi decoder with a code rate 1/2 and a constraint length 3 (four metric states) is disclosed in Japanese Laid-Open Patent Specification Hei-6-303153. The disclosed decoder includes a branch metric calculator and a pair of add/compare/select (ACS) circuits to which the outputs of the branch metric calculator are supplied on a time-shared basis. The outputs of the ACS circuits are stored back into memories as intermediate results of an ACS process to be updated with new branch metrics from the calculator. A maximum likelihood decision circuit compares path metrics from the ACS circuits to select path metrics of the most likely path in the trellis diagram.
In most data communication systems, however, the constraint length is usually 7 which implies that the metric states amount to as large as 64. If a Viterbi decoder with constraint length 7 were implemented using the prior art technique, it would be necessary to provide as many connections for the data path of the path metrics as there are state metrics. Since the access to the path metric memories is a dominant factor on the overall performance of the Viterbi decoder, a long queue would be formed in the ACS circuits if parallel mode of operation is implemented. | {
"pile_set_name": "USPTO Backgrounds"
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1. Field of the Invention
The present invention is concerned with UV ray irradiation equipment used for UV ray irradiation of untreated water for sterilization, oxidative decomposition of organics, decomposition of harmful substances, etc.
2. Description of the Prior Art And Related Information
When the conventional UV irradiation equipment has been used for an extended period of time for the purpose of removing impurities from untreated water such as sewage, iron, hardness components such as calcium and so forth precipitate on the surface of the UV ray transmission tubes which have internal UV ray irradiation lamps therein which surface comes in contact with the untreated water. These precipitates (or scale) obstruct the transmission of UV rays through the UV ray transmission tubes and deteriorate the irradiation efficiency and therefore degrade the purity of the treated water. To cope with the above-mentioned deterioration of UV ray transmission efficiency due to fouling on the surface of the UV ray transmission tubes, scrapers made of rubber, Teflon.RTM. and the like have been used to physically clean the surface of the UV ray transmission tubes. However, this physical method of scraping the surface of the UV ray transmission tubes leaves much to be desired as hardness components and other scales deposited on the surface of the UV ray transmission tubes usually consist of very fine particles which tend to penetrate into and clog concave pits on the surface, thereby making it difficult to wash out such scale by scrapers.
Alternatively, the UV ray transmission tubes are immersed in a tank filled with a cleaning solution such as a solution of weak acids, e.g. phosphoric acid, a solution of scale dispersant or the like, thereby removing scale such as hardness components from the surface of the UV ray transmission tubes.
The foregoing chemical cleaning of the surface of the UV ray transmission tubes has the following drawbacks:
(1) It is cumbersome and time-consuming to disassemble a UV ray transmission tube on the surface of which scale such as hardness components has deposited and to immerse the tube in a cleaning tank. PA1 (2) In order to carry out the above-mentioned cleaning work, ongoing UV irradiation has to be suspended, which in turn results in deterioration of the UV irradiation efficiency. PA1 (3) An excessive quantity of cleaning solution has to be used in the cleaning tank, which entails an expensive cleaning cost. PA1 (4) The cleaning work is not amenable to automation and cannot therefore go with the trend of equipment automation. PA1 (1) To easily clean off in situ scale comprised of hardness components, etc. from a UV ray transmission tube without disassembling the UV ray irradiation unit and taking out the tube(s) fouled with scale; PA1 (2) To keep up the UV irradiation efficiency without interrupting the UV irradiation process for cleaning work to remove scale comprised of hardness components, etc. and deposited on the UV transmission tube; PA1 (3) To minimize the cleaning cost by reducing the consumption of cleaning solution by feeding a small quantity of a cleaning solution to the surface of the UV ray transmission tube and cleaning off scale comprised of hardness components, etc. and deposited on the surface of the UV ray transmission tube by means of a scraper ring; and PA1 (4) To facilitate automation of the cleaning work thereby going with the trend of equipment automation.
Accordingly, a need presently exists for a means of more efficiently and economically cleaning scale from the surfaces of UV ray transmission tubes used in UV ray treatment systems. | {
"pile_set_name": "USPTO Backgrounds"
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Polycrystalline silicon is a vital raw material used to produce many commercial products including, for example, integrated circuits and photovoltaic (i.e., solar) cells. Polycrystalline silicon is often produced by a chemical vapor deposition mechanism in which silicon is deposited from a thermally decomposable silicon compound onto silicon particles in a fluidized bed reactor or onto silicon rods as in a Siemens-type reactor. The seed particles continuously grow in size until they exit the reactor as polycrystalline silicon product (i.e., “granular” polycrystalline silicon). Suitable decomposable silicon compounds include, for example, silane and halosilanes such as trichlorosilane.
Silane may be produced by reacting silicon tetrafluoride with an alkali or alkaline earth metal aluminum hydride such as sodium aluminum tetrahydride as disclosed in U.S. Pat. No. 4,632,816, which is incorporated herein by reference for all relevant and consistent purposes. Silane may alternatively be produced by the so-called “Union Carbide Process” in which metallurgical-grade silicon is reacted with hydrogen and silicon tetrachloride to produce trichlorosilane as described by Müller et al. in “Development and Economic Evaluation of a Reactive Distillation Process for Silane Production,” Distillation and Adsorption: Integrated Processes, 2002, which is incorporated herein by reference for all relevant and consistent purposes. The trichlorosilane is subsequently taken through a series of disproportionation and distillation steps to produce a silane end-product. The starting compounds of silane production are relatively expensive components in silane-based production of polycrystalline silicon.
A continuing need exists for processes for producing polycrystalline silicon that reduce the amount of hydrogen and chlorine used relative to conventional methods and for methods that are capable of producing polycrystalline silicon in a substantially closed-loop process relative to hydrogen or chlorine (e.g., hydrogen chloride). A continuing need also exists for systems for producing polycrystalline silicon that make use of such processes.
This section is intended to introduce the reader to various aspects of art that may be related to various aspects of the disclosure, which are described and/or claimed below. This discussion is believed to be helpful in providing the reader with background information to facilitate a better understanding of the various aspects of the present disclosure. Accordingly, it should be understood that these statements are to be read in this light, and not as admissions of prior art. | {
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This invention relates to an ignition distributor arrangement for internal-combustion engines wherein the ignition distributor is fastened to the internal-combustion engine and is driven by a camshaft. The ignition distributor is aligned in the same direction as the axis of the camshaft and has a rotor which is substantially cylindrical in shape and which interacts with a cylindrical cam arranged at an end of the camshaft.
In a known arrangement of the above mentioned type (Porsche 944 Customer Service Information WKW 450 610, 07/81, Page 6), the rotor of the ignition distributor is arranged above the cam and is secured by a screw extending in a radial direction, i.e., transversely to the central longitudinal axis of the camshaft. A disadvantage of this arrangement is that the vibrations of the internal-combustion engine may cause loosening of the screw.
An object of this invention is to provide an improved ignition distributor arrangement wherein the fastening arrangement for the cam and the rotor securely withstands the vibrations occurring during the operation of the internal-combustion engine.
These and other objects are achieved in an ignition distributor arrangement for internal-combustion engines which comprises a generally cylindrical distributor rotor having a central longitudinal axis of rotation, and means for drivingly attaching the rotor to an end of the engine camshaft such that the central longitudinal axis of the rotor is aligned with a central longitudinal axis of the camshaft. In a preferred embodiment, a generally cylindrical cam is attached to the end of the camshaft by a screw. The cam has a flange which extends transversely to the central longitudinal axis of the camshaft. The rotor is fastened to the flange by means of an extension of the rotor, which is aligned with the flange, and one or more screws. The screws which attach the rotor to the cam are aligned such that their central longitudinal axis extends parallel to the central longitudinal axis of the camshaft. In an especially preferred embodiment, three spaced apart screws are used for fastening the rotor to the flange. In this embodiment, the rotor has an asymmetrical control finger. This control finger, the rotor extension, and the screws are arranged around the central longitudinal axis of the rotor so as to provide an essentially symmetrical distribution of mass around this axis, thus reducing vibrations when the engine is operating.
The outer diameter of the flange of the cam fits into an opening in a housing which surrounds a portion of the ignition distributor arrangement. The diameter of the opening is only slightly larger than the outside diameter of the flange.
The main advantages of the arrangement according to this invention are that a cam and rotor connection that is designed in this way is not loosened by vibrations occurring during operation of the internal-combustion engine. This result is due, at least in part, to the symmetrical distribution of mass at the rotor which avoids the occurrence of an unbalanced rotating mass.
Because the outside diameter of the flange is relatively close to the diameter of the opening, the rotor space is effectively closed with respect to the toothed-belt wheel space, making an additional dust cap unnecessary.
Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of a preferred embodiment of the invention, when considered in conjunction with the accompanying drawings. | {
"pile_set_name": "USPTO Backgrounds"
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The physical control layer contains information necessary to configure physical channel parameters at the receiving end of a wireless communication system. The control information needs to be decoded prior to the processing of the actual data samples composed of payload information provided by the higher layers. The control bits are either transmitted prior to the payload or in parallel. In general, to minimize the synchronization efforts and the size of latency buffers, and to reduce system throughput, the configuration, or reconfiguration of the receiver should be accomplished as fast as possible. Therefore, a latency constraint decoding and configuration problem should be addressed, where only a few bits, or control bits, are to be decoded as fast as possible.
The reliability of the control information should be guaranteed, since the remaining payload processing becomes obsolete in cases of erroneous control signaling. Error robustness can be guaranteed by adding redundancy to the control bits. Upon reception of the encoded control information, the receiver feeds the data into the corresponding decoder to recreate an exact copy of the originally transmitted control bits. The drawback is a considerable increase in processing complexity to implement the sophisticated algorithms. Moreover, the system designers can pick from various forward error correction techniques with different complexity and error correction characteristics. Forward error correction codes comprise linear block codes and convolutional codes.
The limited bandwidth of the air interface, coupled with the large amount of redundancy required to guarantee reliable transmission, limits the number of control bits to be transmitted. To further improve transmission reliability, a modulation scheme with advantageous distance properties among the different signal constellation points should be chosen. Simple modulation schemes such as BPSK (binary phase-shift keying) or QPSK (quaternary phase-shift keying) are ideal candidates for reliable transmission due to high SNR (signal-to-noise ratio) of adjacent symbols. However, with wireless systems becoming more and more complex, the need for smaller, faster and more power-efficient approaches is the key challenge of future system-on-chip designs.
Conventional approaches determine a sequence of bits from a reference sequence space comprising a large number of reference sequences, and that requires a correspondingly large memory size. Such a method is known in the art as maximum-likelihood sequence estimation (MLSE). Despite its exponential complexity, one key property of the MLSE decoding method is its inherent flexibility. That is, each sequence can be decoded in an optimal way no matter what encoding scheme was used. However, the MLSE decoding method requires a one-to-one mapping between the bits before and after encoding. As a result, it is necessary to unambiguously decode the sequence at the receiving side. | {
"pile_set_name": "USPTO Backgrounds"
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The fluid dynamic bearing device supports a shaft member by fluid film formed in a bearing gap so as to be capable of relative rotation. The bearing device of this type is excellent particularly in rotational accuracy at the time of high-speed rotation, silence, and the like, and is suitably used as a bearing device for a motor mounted to various electrical apparatuses such as an information apparatus. Specifically, the bearing device is suitably used as a bearing device for a spindle motor in a magnetic disk drive like an HDD, an optical disk drive for a CD-ROM, CD-R/RW, DVD-ROM/RAM, or the like, or a magneto-optical disk drive for an MD, MO, or the like, or as a bearing device for a motor such as a polygon scanner motor of a laser beam printer (LBP), a color wheel motor of a projector, or a fan motor.
Normally, in a fluid dynamic bearing device, a shaft portion of a shaft member is inserted along an inner periphery of a bearing sleeve or the like, and a radial bearing portion is constituted between the outer peripheral surface of the shaft portion and the inner peripheral surface of the bearing sleeve. Further, in some fluid dynamic bearing devices, a flange portion is provided at one end of the shaft portion, and between the end surface of the flange portion and the surface opposed thereto (for example, the end surface of the bearing sleeve), a thrust bearing portion is constituted (for example, refer to Japanese Patent Application Laid-open No. 2003-239951).
As described above, the outer peripheral surface of the shaft portion constitutes a radial bearing portion, and the end surface of the flange portion constitutes the thrust bearing portion. Thus, it is necessary to finish those surfaces with high accuracy. Simultaneously, in the case where the radial bearing portion and thrust bearing portion are constituted together with each other, it is important to take into consideration not only the surface accuracy of the individual bearing portions, but also the shape accuracy therebetween, that is, perpendicularity between the outer peripheral surface of the shaft portion and the end surface of the flange portion.
Proposed examples of a method of integrating the shaft portion and the flange portion separated from each other with high accuracy include fixation means in which an annular thrust plate is press-fitted to a fixation shaft (for example, refer to Japanese Patent Application Laid-open No. 2000-324753 and Japanese Patent Application Laid-open No. 2001-317545).
Further, as another means for fixing the shaft portion and the flange portion by press-fitting with high accuracy, there has been proposed a press-fitting device in which a guide member is used and press-fit fixation is performed with use of a shaft member (shaft portion) which is provided with an R portion on the outer periphery of the lower end thereof and a ring member (flange portion) which is provided with a chamfered portion on the inner peripheral edge of the upper end of the hole thereof, the guide member having a shaft holding surface and a ring contact surface which are worked so as to achieve perpendicularity of high accuracy therebetween, the R portion and the chamfered portion are brought into contact with each other at the time of starting press-fitting (for example, refer to Japanese Patent Application Laid-open No. 2001-287124). In this case, first, the R portion provided at the lower end of the shaft member is brought into contact with the chamfered portion of the hole of the ring member. With this operation, the ring member is moved in the horizontal direction, whereby press-fitting is performed in the state in which the shaft member and the ring member are coaxial with each other.
Further, in accordance with recent downsizing and enhancement in portability of information devices, there has been demanded enhancement in resistance to falling-off and the like (impact resistance) with respect to fluid dynamic bearing devices mounted to those information devices. Accordingly, when the shaft member is constituted by the shaft portion and the flange portion separated from each other, it is important to increase fastening strength therebetween.
As means for increasing the fastening strength, there has been proposed, for example, means by which a flange portion is pressurized in the axial direction in a seal state in which an expansion of an outer diameter portion of a flange material is regulated, and the inner peripheral surface of the flange portion is reduced in diameter, whereby fastening fixation with respect to the shaft portion is achieved (for example, refer to Japanese Patent Application Laid-open No. 2004-204916). [Patent Document 1] Japanese Patent Application Laid-open No. 2003-239951 [Patent Document 2] Japanese Patent Application Laid-open No. 2000-324753 [Patent Document 3] Japanese Patent Application Laid-open No. [Patent Document 4] Japanese Patent Application Laid-open No. 2001-287124 [Patent Document 5] Japanese Patent Application Laid-open No. 2004-204916 | {
"pile_set_name": "USPTO Backgrounds"
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The spectral subtraction method (herein after referred to as the “SS method”), the Wiener filtering method, the minimum mean-squared error (MMSE) method and the like have been heretofore known as techniques for suppressing noise components in an observed signal based on a speech on which noises are superimposed.
The existence of stationary noise is a prerequisite for the SS method. The SS method is designed to learn an average power of noise components for each frequency in a noise section, which is a non-speech section, and to subtract the average power of the noise signal from the power of the observed signal in a speech section for each frequency (see Non-patent Document 1, for example). When the subtraction is done, the average power of the noise components is normally multiplied by an excessive subtraction weight in a range of 1.0 to 4.0. When an output as a result of the subtraction drops below 0.01 to 0.5 times the power of the original speech signal, processing or “flooring” is performed together where the result of the subtraction is replaced with a value which is obtained by multiplying the original speech signal by a “flooring” coefficient.
If a larger subtraction weight is introduced, a “musical” noise is reduced. However, loss of information and speech distortion in a speech section become conspicuous. For this reason, a larger flooring coefficient is needed for compensating for the loss of information and the speech distortion. Nevertheless, if a lager flooring coefficient is introduced, the power of a noise signal is not reduced sufficiently. If, therefore, there would be a measures to inhibit a musical noise from being produced even in a case that a small subtraction weight in a range of 1.0 to 1.5 is used, the loss of a speech and a speech distortion to be brought about after the subtraction can be suppressed to a minimum, and concurrently a smaller flooring coefficient in a range of 0.01 to 0.1 can be introduced. Accordingly, the power of the noise signal can be reduced sufficiently.
The following literature is considered: [Non-patent Literature 1] S. Boll, “Suppression of Acoustic Noise in Speech Using Spectral Subtraction,” IEEE Trans. on ASSP, Vol. ASSP-27, pp. 113-120, April 1979 [Non-patent Literature 2] Lockwood, P., Boudy, J., “Experiments with a Nonlinear Spectral Subtractor (NSS), Hidden Markov Models and Projection, For Robust Recognition in Car,” Speech Commun, Vol. 11, pp. 215-228, June 1992 [Non-patent Literature 3] J. A. Nolazco Flores, S. J. Young, “Continuous Speech Recognition in Noise Using Spectral Subtraction and HMM Adaptation,” Proc. of ICASSP, 1994, Vol. I, pp. 409-412 [Non-patent Literature 4] Gary Whipple, “Low Residual Noise Speech Enhancement Utilizing Time-Frequency Filtering,” ICASSP-94 [Non-patent Literature 5] Y. Ephraim, D. Malah, “Speech Enhancement Using a Minimum Mean-Squared Error Short-Time Spectral Amplitude Estimator,” IEEE Trans. on ASSP, Vol. ASSP-32, pp. 1109-1121
The SS method has a plurality of derivative methods. Among them are a non-linear spectral subtraction (NSS) method, which is designed to adjust only a subtraction weight for each frequency in response to a signal-to-noise ratio (SNR)(see Non-patent Literature 2, for example), and a continuous spectral subtraction (CSS) method, which is designed to subtract a local average power in a real-time manner without discriminating between a noise section and a speech section (see Non-patent Literature 3, for example). In these methods, however, a musical noise is produced, even though their levels of the musical noise is lower.
A post-mortem method has been proposed where an output to be obtained after processing by the SS method is observed and a musical noise and its equivalent are reduced if they are found. Specifically, a power of a spectrum is observed in the system of coordinates constituted of a time axis and a frequency axis, thereby erasing a portion which looks like an isolated island (see Non-patent Literature 4, for example), or thereby reducing it with a median filtering. In addition, there is a spectral smoothing method for smoothing powers over several neighboring frames. However, these methods have their own limits, and performance in reducing a musical noise is insufficient.
To begin with, a musical noise results from “subtraction” processing. It is assumed that a musical noise is not produced if a speech signal to be obtained after reducing a noise component is produced by “multiplication” instead of “subtraction.”
The Wiener filtering method is designed to estimate a clean speech with some measures, and to define a transfer function of the Wiener filtering in a way that the transfer function agrees with the estimated clean speech. In this point, since the clean speech is unknown by nature, an estimated value concerning the speech is used. Depending upon measures to estimate the estimated value, therefore, the property of the Wiener function to be implemented varies to a large extent. Generally speaking, even though this method is employed, it is difficult to make reduction in a residual noise and minimization of speech distortion compatible with each other.
The MMSE method is designed to adjust a multiplication coefficient for each frequency by use of a minimum square method on a presumption that independent power distributions are present in a noise and a speech respectively (see Patent Literature 5, for example). Since multiplication is done, a musical noise is not produced. However, a speech processed by the MMSE method has a large amount of speech distortion. This speech distortion is conspicuous, particularly in a case that the speech distortion is measured by a widely-used MEL-cepstral representation. For this reason, the MMSE method is not suitable for its adaptation to speech recognition.
It is desirable to achieve clear speech in a severe noise environment such as an emergency telephone call made in a highway. In addition, a speech enhancement technique for offering higher articulation has been awaited in the field of hearing aids for people with hearing impairment.
An SS method which is designed to subtract an average spectrum of noise components from an observed signal is effective for reducing noise components from an observed signal based on a speech on which a stationary noise is superimposed. However, a conventional SS method can not avoid producing an offensive musical noise as a side effect.
In other words, in the present framework of the SS method, clarity of a speech and performance in speech recognition can not be compatible with each other. For the purpose of suppressing speech distortion to a minimum level, it is desirable to introduce a smaller subtraction weight. When the subtraction weight is set smaller, however, noise components which can not be subtracted are large in number, thus deteriorating performance in speech recognition in a noise environment. For the purpose of lowering the overall noise power including noise power in non-speech sections, it is desirable to introduce a smaller flooring coefficient. When the flooring coefficient is set smaller, however, a musical noise is conspicuous, thus causing errors to crop up with regard to a short word. Consequently, if performance in speech recognition is intended to be enhanced with priority given, clarity of a speech in terms of auditory sense may be sacrificed in some cases.
For the same reason, in a conventional SS method, performance in speech recognition based on an observed signal to be obtained after noises are reduced is susceptible to an influence caused by the two parameters of a subtraction weight and a flooring coefficient. Optimal parameter values vary depending upon the quantities (S/N) and qualities of noises and further on a task of speech recognition. For this reason, the optimal parameter values are somewhat difficult to obtain in an actual environment. To achieve more robust speech recognition, a method for reducing noises which is not sensitive to variation of the parameters has been awaited. | {
"pile_set_name": "USPTO Backgrounds"
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The present invention relates to garment hangers and more particularly to end-clips for garment hangers which can include a retention means or stop member which allows for improved retention of garments such as undergarments, e.g., bras and underpants.
Examples of garment hangers that can be used with the present invention include, but are not limited to, those shown and described in U.S. Pat. Nos. 4,629,102, 4,828,155, 5,632,423 and 6,357,638. The disclosures of these patents are incorporated by reference herein. In these hangers, for example , the strap of a bra is secured in the hanger end-clip between a pressing member and an elongated bar portion of the hanger.
Referring now to FIG. 1 which shows an end-clip 16 of a hanger, a problem of the hangers discussed above is that the strap of a garment can get caught in area A near a pressing member 18. To solve that problem, U.S. Pat. No. 5,632,423, for example, inserted a stop formation 38 to be substantially aligned with pressing member 18 so that when a garment strap is inserted in the hanger in an area 32 between pressing member 18 and an elongated bar portion 14 of the hanger, the stop formation 38 blocked the garment strap from traveling into area A.
Thus, as evidenced by U.S. Pat. No. 5,632,423, it is desirable to have a hanger that can accommodate both thick and thin garments, as well as a variety of materials, and in addition, which can retain these garments in their proper position once arranged on the hanger.
U.S. Pat. No. 6,357,638 claims a stop formation that is not located substantially adjacent to the end of the pressing member. The patent further claims instead, that the stop formation is located above the inner arm, along the trajectory of the outer end of the inner arm, so as to block access along a predetermined path or trajectory described by the end of the inner arm, as it flexes upwardly in response to the presence of a narrow strap. The patent goes on to claim that by moving the stop formation upwardly, they block access to the inner space when the inner arm is flexed upwardly. | {
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Extensible markup language (XML) is increasingly becoming the preferred format for transferring data. XML is a tag-based hierarchical language that is extremely rich in terms of the information that it can be used to represent. For example, XML can be used to represent information spanning the spectrum from semi-structured information (such as one would find in a word processing document) to generally structured information (such as that which is contained in a table). XML is well-suited for many types of communication including business-to-business and client-to-server communication. For more information on XML, XSLT, and XSD (schemas), the reader is referred to the following documents which are the work of, and available from the W3C (World Wide Web consortium): XML Schema Part 2: Datatypes; XML Schema Part 1: Structures, and XSL Transformations (XSLT) Version 1.0; and XML 1.0 second edition specification.
With so much information being described and transferred through XML, it is increasingly important to have ways to view that information. One way to view information in an XML document is to transform it with an XSLT file into an HTML (or XHTML) document. HTML documents can be used to render, or view, information, such as information from an XML file. Using XSLT, rather than other transforming languages, is often preferred because XSLT is a W3C standard.
One purpose for using an XSLT file to transform an XML document is to create electronic forms. Electronic forms can be used not only to view information within an XML document, but also to allow a user of the electronic form to add, remove, or change information within the XML document by editing data in a data-entry field within the electronic form.
Currently, to create an HTML document (e.g., an electronic form) that renders information within an XML document, a programmer writes an XSLT file to transform the XML document into the HTML document. The programmer, however, must have a high degree of skill in programming XSLT to program an XSLT file, especially to create an electronic form.
Also, even with a high degree of programming skill, programming an XSLT file can be very time consuming and difficult. It can be difficult and time-consuming because an XSLT programmer cannot see the HTML document that he is creating as he is creating it. The programmer, rather, must complete an XSLT file and apply it to an XML file before he can see the view created with the resulting HTML document. Even with the view, each mistake made by the programmer, such as the style, layout, and structure of the view, can be very difficult to relate back to the mistake made in the XSLT file, further complicating programming of XSLT files to create HTML documents.
For these reasons, creating electronic forms and other HTML documents by transforming an XML document with an XSLT file is difficult, time consuming, and requires a high degree of skill. | {
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Embodiments of the present invention generally relates to systems and methods for mapping gaze direction of at least one person to the environment around the person, and in particular, to systems and methods using a computer vision approach combined with a wearable device using at least information from a scene camera linked with the wearable device. | {
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Cartilage is an avascular tissue of which chondrocytes are the main cellular component. The chondrocytes in normal articular cartilage occupy approximately 5% of the tissue volume, while the extra-cellular matrix makes up the remaining 95% of the tissue. The chondrocytes secrete the components of the matrix, mainly proteoglycans and collagens, which in turn supply the chondrocytes with an environment suitable for their survival under mechanical stress. In cartilage, collagen type II, together with the protein collagen type IX, is arranged in solid fibril-like structures which provide cartilage with great mechanical strength. The proteoglycans can absorb water and are responsible for the resilient and shock absorbing properties of the cartilage.
One of the functional roles of cartilage in the joint is to allow bones to articulate on each other smoothly. Loss of articular cartilage, therefore, causes the bones to rub against each other leading to pain and loss of mobility. The degradation of cartilage can have various causes. In inflammatory arthritides, as rheumatoid arthritis for example, cartilage degradation is caused by the secretion of proteases (e.g. collagenases) by inflamed tissues (the inflamed synovium for example). Cartilage degradation can also be the result of an injury of the cartilage, due to an accident or surgery, or exaggerated loading or ‘wear and tear’. Cartilage degradation may also be the result of an imbalance in cartilage synthesizing (anabolic) and cartilage degrading (catabolic) processes. The ability of cartilage tissue to regenerate after such insults is limited. Chondrocytes in injured cartilage often display reduced anabolic activity and/or increased catabolic activity. The limited ability of cartilage to self-repair after injury, disease, or surgery is a major limiting factor in rehabilitation of degrading joint surfaces and injury to meniscal cartilage.
The degeneration of cartilage is the hallmark of various diseases, among which rheumatoid arthritis and osteoarthritis are the most prominent.
Osteoarthritis (also referred to as OA, or wear-and-tear arthritis) is the most common form of arthritis and is characterized by loss of articular cartilage, often associated with hypertrophy of the bone and pain. The disease mainly affects hands and weight-bearing joints such as knees, hips and spines. This process thins the cartilage. When the surface area has disappeared due to the thinning, a grade I osteoarthritis is reached; when the tangential surface area has disappeared, grade II osteoarthritis is reached. There are further levels of degeneration and destruction, which affect the deep and the calcified cartilage layers that border with the subchondral bone. For an extensive review on osteoarthritis, we refer to Wieland et al., 2005.
Rheumatoid arthritis (RA) is a chronic joint degenerative disease, characterized by inflammation and destruction of the joint structures. When the disease is unchecked, it leads to substantial disability and pain due to loss of joint functionality and even premature death. The aim of an RA therapy, therefore, is not to slow down the disease but to attain remission in order to stop the joint destruction. Besides the severity of the disease outcome, the high prevalence of RA (˜0.8% of the adults are affected worldwide) means a high socio-economic impact. (For reviews on RA, we refer to Smolen and Steiner (2003); Lee and Weinblatt (2001); Choy and Panayi (2001); O'Dell (2004) and Firestein (2003)).
The clinical manifestations of the development of the osteoarthritis condition are: increased volume of the joint, pain, crepitation and functional disability that lead to pain and reduced mobility of the joints. When disease further develops, pain at rest emerges. If the condition persists without correction and/or therapy, the joint is destroyed leading to disability. Replacement surgery with total prosthesis is then required.
In mature articular cartilage, chondrocytes maintain the cartilage-specific matrix phenotype. Early signs of OA include progressive loss from articular cartilage of the proteoglycan aggrecan, due to damage to type II collagen. This protein represents the major structural collagen found in articular cartilage in healthy individuals. There is ordinarily a strict balance between the production of type II collagen and degradation of this protein by catabolic enzymes during normal remodeling of cartilage. Pathological conditions such as OA are characterized by a loss of this balance with increased proteolysis.
In general, elevated expression of MMPs is associated with the degradation of cartilage and/or extracellular matrix (ECM) but not all proteases are capable of degrading native collagen. Among the matrix metallo proteinases, MMP1, MMP8, MMP13 and MMP14 display the highest capacity for degrading collagen type II. Expression and contents of MMP-1 (collagenase-1) and MMP-13 (Mitchel et al., 1996; Shlopov et al., 1997), expression of MMP-8 (collagenase-2), and collagenase activity (Billinghurst et al., 1997, Dahlberg et al., 2000) are upregulated in human OA cartilage. In particular, MMP-13, also known as collagenase-3, is thought to play an important role in type II collagen degradation in articular cartilage and especially in OA (Billinghurst et al., 1997, Mitchell et al., 1996, Dahlberg et al., 2000, Billinghurst et al., 2000) as indicated by various observations. 1) The expression of MMP13 is increased in the cartilage of OA patients and of animals subjected to arthritogenic surgery like meniscectomy (Appleton et al., 2007) 2) The localization of MMP1 and MMP13 in arthritic cartilage appear to coincide with the location of cartilage destruction, as revealed by antibodies revealing neo-epitopes induced by cartilage cleavage. (Wu et al., 2002) 3) Overexpression of MMP13 in cartilage of transgenic mice lead to an OA-like cartilage destruction phenotype (Neuhold et al., 2001). 4) Type II collagen is the preferred substrate for MMP-13 (Billinghurst et al., 1997; Mitchell et al., 1996). Taken together, MMP13 is well-accepted as a key player in OA-induced cartilage and ECM degeneration.
Therapeutic methods for the correction of the articular cartilage lesions that appear during osteoarthritic disease have been developed, but so far none of them have been able to mediate the regeneration of articular cartilage in situ and in vivo.
Osteoarthritis is difficult to treat. At present, no cure is available and treatment focuses on relieving pain and preventing the affected joint from becoming deformed. Common treatments include the use of non-steroidal anti-inflammatory drugs (NSAIDs). Although dietary supplements such as chondroitin and glucosamine sulphate have been advocated as safe and effective options for the treatment or amelioration of osteoarthritis, a recent clinical trial revealed that both treatments did not reduce pain associated with osteoarthritis (Clegg et al., 2006). Taken together, no disease modifying osteoarthritic drugs are available.
In severe cases, joint replacement may be necessary. This is especially true for hips and knees. If a joint is extremely painful and cannot be replaced, it may be fused. This procedure stops the pain, but results in the permanent loss of joint function, making walking and bending difficult.
Another possible treatment is the transplantation of cultured autologous chondrocytes. Here, chondral cellular material is taken from the patient, sent to a laboratory where it is expanded. The material is then implanted in the damaged tissues to cover the tissue's defects.
Another treatment includes the intra-articular instillation of Hylan G-F 20 (e.g. Synvisc®, Hyalgan®, Artz®), a substance that improves temporarily the rheology of the synovial fluid, producing an almost immediate sensation of free movement and a marked reduction of pain.
Other reported methods include application of tendinous, periosteal, fascial, muscular or perichondral grafts; implantation of fibrin or cultured chondrocytes; implantation of synthetic matrices, such as collagen, carbon fiber; administration of electromagnetic fields. All of these have reported minimal and incomplete effects, resulting in a poor quality tissue that can neither support the weighted load nor allow the restoration of an articular function with normal movement.
Stimulation of the anabolic processes, blocking catabolic processes, or a combination of these two, may result in stabilization of the cartilage, and perhaps even reversion of the damage, and therefore prevent further progression of the disease.
The present invention relates to the relationship between the function of selected proteins identified by the present inventors (hereinafter referred to as “TARGETS”) and inhibition of cartilage and/or extra-cellular matrix (ECM) degradation and inhibition of inflammation. | {
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Computer systems contain large amounts of information. This information includes personal information, such as financial information, customer/client/patient contact information, audio/visual information, and much more. This information also includes information related to the correct operation of the computer system, such as operating system files, application files, user settings, and so on. With the increased reliance on computer systems to store critical information, the importance of protecting information has grown. Traditional storage systems receive an identification of a file to protect, then create one or more secondary copies, such as backup files, containing the contents of the file. These secondary copies can then later be used to restore the original data should anything happen to the original data.
In corporate environments, protecting information is generally part of a routine process that is performed for many computer systems within an organization. For example, a company might back up critical computing systems related to e-commerce such as databases, file servers, web servers, and so on as part of a daily, weekly, or monthly maintenance schedule. The company may also protect computing systems used by each of its employees, such as those used by an accounting department, marketing department, engineering department, and so forth.
Although each computer system contains certain unique information, many systems may contain very similar information. For example, although a computing system used by a marketing employee and a computing system used by an engineering employee will generally contain unique information created by each employee in the course of their work, both computing systems will likely have the same operating system installed, with thousands of identical or similar files used by the operating system. Similarly, both computing systems will likely have at least some similar application programs installed, such as a word processor, spreadsheet, Internet browser, and so on. Both systems may also have similar corporate information. For example, each employee may have an electronic copy of an employee manual distributed by the company. Information other than files may also be identical or similar between systems. For example, user settings and preferences may have similar default values on each system and application programs may contain similar templates on each system that are stored as application-specific information. As another example, several employees may have received a copy of the same email, and the email may be stored in each employee's electronic mailbox.
As a result of the amount of redundant information in an organization, secondary copies of an organization's information are often very large and can require the purchase of expensive storage devices and storage media. The restoration of data in the event of data loss is also slowed by the large size of the secondary copies. As the size of secondary copies increases, locating and restoring information requires more actions to be taken. For example, it may be necessary to search many tapes or other media to find the correct secondary copy. The great quantity of storage media, such as tapes, may mean that some secondary storage media has been moved offsite requiring that it first be retrieved before information can be recovered from it. Each of these factors increases the cost of protecting information and the time required to recover information in the event of data loss. Quick recovery of information is often critical to today's businesses, and any additional delay can affect business operations and customers' satisfaction with the business.
Single instancing in a data management system is the process of attempting to store only a single instance of each file. Some prior systems permit data de-duplication, or single instancing, at a file level or at a block level, but such systems are unable to determine similar blocks of data within a given application. Data objects are often stored in large, monolithic files that are intended to be read only by the application that created them. For example, a Microsoft Exchange email server stores email messages in one or more large data files that typically hold thousands of different users' mailboxes. As another example, a database server often stores tables, forms, reports, and other data objects in one or two large data files that provide persistence for the entire database. Thus, typical data management systems are only able to perform data management operations on the large data file, rather than the data objects themselves. In the case of the email server, a given electronic mail application may generate multiple email messages that all differ, but which all contain the same attachment. Prior systems may not be able to differentiate these messages, and thus each would be stored with the attachment. Further, if two files had different properties or metadata, such prior systems would store both files, even though the data they contain are identical and differ only by their metadata.
Another problem with prior single instancing systems is that they may work fine within a given local environment, but if remote clients or devices provide data to a central single instancing system, each of the various remote clients sends data to the central single instancing system, even if much of that data is duplicative and ultimately ignored by the single instancing system. Thus, bandwidth and resources are wasted.
There is a need for a system that overcomes the above problems, as well as one that provides additional benefits.
In the drawings, the same reference numbers and acronyms identify elements or acts with the same or similar functionality for ease of understanding and convenience. To easily identify the discussion of any particular element or act, the most significant digit or digits in a reference number refer to the Figure number in which that element is first introduced (e.g., element 604 is first introduced and discussed with respect to FIG. 6). | {
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The present invention is directed to a novel article of manufacture made from natural fruits and a process for its manufacture. More particularly, a novel, readily reconstitutable, free flowing flaked product is produced by a novel and synergistic dehydration drying process.
The product of this invention is natural dried fruit flakes which are free from extenders, binders, and other additives heretofore thought to be required in producing same when utilizing a continuous dehydration process.
This invention also has application to the production of other products and processes into which the dried fruit product hereof and the process for making same may be incorporated, such as fruit flavored cereals and the like.
When referring to the flaked product of the present invention, it will be recognized that the term "flakes" encompasses a free flowing solid material having an exceptionally low moisture content which can readily be spooned from a jar or other container, is not prone to lumping in a sealed container, and readily becomes free flowing with agitation or stirring even after the container is initially opened to atmosphere. No specific particle size is implied by the term "flake", however, the process of this invention permits flakes to have a large particle size without sacrificing the foregoing properties. The term "reconstitutable" as used herein relates to mixing the flaked fruit product with a liquid of various temperatures ranging from hot to cold, including various liquids such as, e.g., milk or water, to form a reconstituted product. The term "readily reconstitutable" is meant to include a virtually instantaneously reconstitutable product of varying viscosities, as desired; additionally, one in which the viscosity may be adjusted even after the product has been initially reconstituted.
Fresh fruit products such as applesauce and the like typically contain large percentages of water. This high water content places a heavy burden on the packaging, handling, storing and shipping of such products and has thus stimulated the development of many processes for the dehydration of fruit products. These processes, however, have not as yet satisfied the need for a natural dried fruit product since the present state of the art indicates that natural fruit concentrates and purees cannot be commercially dried in a continuous manner to form a readily reconstitable free flowing flaked fruit product which is free from unwanted additives.
The conventional manner of forming a flaked product is to drum dry a concentrate into a continuous sheet which is then flaked. The present state of the art requires, however, the addition to the concentrate of extenders, binders, gels, gums, and other additives to achieve the formation and removal of a continuous sheet of product from the drum dryer. One of the inherent disadvantages of such processes is that the additives remain in the final product and therefore, the product is undesirable as a natural food. For example, the additives are in most cases either inorganic substances, or carbohydrates or proteinaceous materials, which deleteriously affect the reconstitution properties of the product, or dilute the product's flavor, desired nutritional value, consummer acceptability, or the like. Moreover, many of the prior art processes, while claiming to produce a satisfactory product, generally treat the puree in such a manner which destroys the cellular structure of the natural fruit, either mechanically, thermally or chemically, and thus does not retain the naturally occurring constituents or integrity of the fruit. It will be understood that the term "extenders" as used herein encompasses any additive made to the puree for purposes of forming a sheet on a dryer, releasing the puree from the surface of a dryer, or otherwise permitting the natural fruit puree to be continuously drum dried and may, for example, include binders, gels, gums, polysaccharides, and extenders as may be known and utilized in this art.
The prior art processes therefore do not produce a natural fruit product, which reconstitutes to a fresh fruit food which does not have added starches, saccharides, binders, extenders, or other additives, while at the same time preserving the natural constituents of the fruit and therefore its nutritional value, taste, and the like. | {
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Amorphous and polycrystalline solar cells are limited in their efficiency to convert light into energy. Single crystal high mobility materials are capable of much higher efficiency, but are typically much more expensive. Conventional equipment is designed for semiconductor applications with extreme requirements and with a very high cost involved. However, these systems all have high cost and are not capable of high throughput automation.
To achieve very low cost epitaxial deposition for photovoltaic applications at high throughput, the inventors believe that a radical change is required rather than simply making everything larger. For example, the inventors have observed that batch reactors are limited in throughput with high cost of materials, consumables, and automation challenges. Very high flow rates of hydrogen, nitrogen, water, and precursors are also required. Furthermore, a large amount of hazardous byproducts are generated when growing thick films.
Continuous reactors have been attempted many times for epitaxial processes but have never been production worthy nor achieved good precursor usage. The major issue is poor film quality and excessive maintenance.
On the other hand, single wafer reactors have very inefficient utilization of precursors and power (electrical) and have lower per wafer throughput. Plus single wafer reactors need complex substrate lift/rotation mechanisms. Thus, although single wafer reactors can have very high quality, low metal contamination levels, and good thickness uniformity and resistivity, the cost per wafer is very high to get these results.
Therefore, the inventors have provided embodiments of a substrate processing tool that may provide some or all of high precursor utilization, simple automation, low cost, and a relatively simple reactor design having high throughput and process quality. | {
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This invention relates to methods for separating and isolating pathogens from biological fluid samples such as blood and blood components by means of high density microparticles.
Whole blood includes cellular (erythrocytes or red blood cells, leukocytes or white blood cells, thrombocytes or platelets) along with non-cellular components (plasma). When blood is collected from a donor for use, the whole blood is typically separated by centrifugation into such components, which can then be used therapeutically, rather than administering whole blood, in order to maximize the clinical and economic utility of blood. The leukocytes present in whole blood are often carried during processing into each of the blood components. Leukocytes may transmit infectious agents, such as cell-associated viruses (e.g. cytomegalovirus or human immunodeficiency virus) or they may cause adverse immunological reactions, such as alloimmunization. For those reasons, leukocyte removal is often desirable and several methods have been developed to remove leukocytes without causing appreciable damage to the blood or blood component. See for example, Coulter, et al., U.S. Pat. No. 5,576,185 and Pall, et at., U.S. Pat. No. 5,229,012.
However, other pathogenic substances may still be present in whole blood or its various components, that can be harmful to a patient receiving such blood. This is of particular concern when the patient is immune compromised and more susceptible to pathogens that may be present in the blood. Such pathogens include viruses, protozoa and bacteria. In addition, more recently, concern has arisen over prions, which are protein agents believed to be capable of transmitting spongiform neuropathies such as Creutzfeld Jacob""s Disease. Experimental evidence in animals suggests that these agents may be transmitted by blood transfusions (Houston et al., Lancet 356(9234): 999-1000, 2000), and concern over transmission of these agents has resulted in recall of some human blood-derived products.
Although substantial removal of some pathogens such as cell-associated viruses may occur during leukocyte removal, there is a continuing need to develop more quantitative and broader methods of removing such pathogens from whole human blood and blood components, while maintaining the integrity of the blood.
One method of eliminating pathogens is by inactivation, for example, by directly or indirectly inhibiting the virus""s ability to replicate. Reichl, U.S. Pat. No. 5,633,349 describes the inactivation of prions, viruses and other infectious agents by treatment with a chaotropic agent such as urea or sodium thiocyanate. Use of a chaotropic agent for treatment of blood cells has the undesired consequence of destroying the therapeutic utility of the resulting cellular product. Miekka, et at., U.S. Pat. No. 6,106,773 relates to the use of an iodinated matrix to disinfect biological fluids by inactivating pathogens contained therein. Cook et at., PCT/US98/00532 describes the use of frangible compounds for chemical inactivation of pathogens by targeting nucleic acids. Other inactivation methods use photoactivation, which is a combination of a photochemical agent and light. Such agents include psoralens (Lin, et at., U.S. Pat. No. 5,459,030), methylene blue (Wolf, Jr., et at., U.S. Pat. No. 5,527,704) and phthallocyanines (Horowitz, et at., U.S. Pat. No. 5,637,451).
Inactivation is not uniformly successful in eliminating pathogens since some are not susceptible to inactivation under conditions that preserve the therapeutic or diagnostic usefulness of a biological fluid. The Hepatitis A virus is a small non-enveloped, blood borne virus that resists inactivation by detergents, heat and most small-molecule chemical and photochemical inactivating agents. Prions are another example of a pathogen that resists inactivation by almost all forms of sterilizing treatment, including heat, ionizing radiation, and chemical treatments. In particular, because prions lack nucleic acids and form an extraordinarily stable protein structure, they are generally resistant to practical methods of inactivation. For agents such as these, a removal method that also preserves the therapeutic or diagnostic utility of the biological fluid is clearly desirable.
Methods of removing pathogens also include physical separation techniques such as by filtration or chromatography. Wick, et at., U.S. Pat. No. 6,051,189 relates to the detection and extraction of submicron particles such as viruses and prions, by centrifligation and ultrafiltration. Gawry, et al., U.S. Pat. No. 5,808,011 describes a method of prion removal using an anion exchange chromatographic column under conditions that cause a gradient elution.
Physical separation techniques often use magnetic particles. For example, Giaever, et at., U.S. Pat. No. 3,970,518 describes the use of antibody-coated magnetic particles to separate select cells, bacteria or viruses from multi-cell, bacteria or virus populations. Magnetic particles are available in various sizes and can be either non-uniform (Josephson, U.S. Pat. No. 4,672,040) or very uniform (Homes, et at., U.S. Pat. No. 5,512,439). Magnetic particles are generally less than 4.5 xcexcm in diameter and have a density of less than 1.8 g/cm3. The magnetic microspheres are intended to be maintained in suspension in the sample and consequently are designed not to settle by gravity.
Non-magnetic, physical separation methods have also been used to separate various cell components from samples of whole blood or bone marrow. Coulter, et at., U.S. Pat. No. 5,576,185, describes the use of reactant-coated, high density microparticles that separate under gravity, a mechanism that allows for separation of undesired cells without substantially physically damaging the blood cells. The advantages of high density microparticles over magnetic particles in the area of cell separation are well established. However, until now, no one has attempted to apply this technology for removal of cellular pathogens such as viruses, bacteria and non-cellular pathogens such as prions.
The invention provides a novel method for separating pathogens from a biological fluid sample. A plurality of high density microparticles (xe2x80x9cHDMxe2x80x9d) having a reactant such as an anti-pathogen antibody, bound thereto are mixed with the sample. The HDM, with the pathogen bound thereto, are allowed to differentially settle by gravity and the remaining sample is removed.
One aspect of the invention pertains to a method of removing at least one population of target pathogens from a biological fluid sample, comprising: providing a plurality of high density microparticles having bound thereto a reactant which specifically binds to the target pathogen, and having a density sufficient to provide differential gravity settling of the target pathogen from the sample; mixing a portion of the sample with the microparticles to bind the microparticles to the target pathogen; settling the microparticles with the bound pathogen in the sample to produce a supernatant substantially free from the bound pathogen, where the settling is accomplished primarily by gravity; and separating the microparticles bound to the pathogen from the supernatant.
The term xe2x80x9chigh density microparticlesxe2x80x9d or xe2x80x9cHDMxe2x80x9d is used to mean particles having a density greater than that of the non-target materials present in the sample, so that the HDM are able to settle out of the sample by differential gravity, i.e., the HDM will settle more rapidly than the non-target materials. Typical xe2x80x9cnon-targetxe2x80x9d materials include red blood cells or white blood cells, platelets, plasma proteins and so forth. Clearly, the greater the differences in density between the HDM and the non-target materials present in the sample, the faster the differential settling will occur. Preferably the particles have a density of at least twice, more preferably 2 or 3 times the density of the non-target materials present in the sample. In particular, HDM preferably have a density greater than 2 g/cm3, typically on the order of 7-10 g/cm3. Preferably the HDM are nickel, which has a density of about 9 gm/cm3.
The term xe2x80x9csamplexe2x80x9d is intended to mean the substance to be analyzed or used therapeutically, where the substance is either a fluid itself or is suspended in a fluid medium. The sample is typically a biological fluid, which includes by means of illustration and not limitation, whole blood or a component thereof such as plasma, a platelet-enriched blood fraction, a platelet concentrate or packed red blood cells; cell preparations such as dispersed tissue, bone marrow aspirates or vertebral body bone marrow; cell suspensions; urine, saliva and other body fluids; bone marrow; spinal fluid; and so forth. The sample can also be a lysed preparation, such as cell lysates, which can be formed using known procedures such as the use of lysing buffers, and so forth. The volume of the sample used in the methods of the invention will vary depending upon the particular application. For example, when the method is being used for a diagnostic or research application, the volume of the sample will typically be in the microliter range, and can be 10 xcexcl or greater. When the method is being used for a therapeutic application such as for clinical transplantations, the volume of the sample will typically be in the milliliter to liter range, for example, 100 milliliters to 3 liters. In an industrial application, such as purification of pooled donor plasma, the volume may be tens of thousands of liters.
The term xe2x80x9cpathogenxe2x80x9d is intended to include any biological organism that is harmful to humans and includes, by way of illustration and not limitation, non-cellular pathogens such as prions, including classical CJD and new variant CJD; protozoa such as giardia; viruses such as Human Immunodeficiency Virus, Herpes Simplex Virus, Epstein Barr Virus, cytomegalovirus, T-cell lymphotrophic virus, varicella zoster virus, adenovirus, Hepatitis A virus, Hepatitis B virus, Hepatitis C virus, human B-19 parvovirus, Nipah virus, hantaviruses, yellow fever virus (family Flaviviridae or Flavivirus) the tick-borne hemorrhagic fever viruses, or the tick-borne encephalitis viruses; cellular pathogens such as bacteria, which include, for example, streptococcus, diptheria, mycobacterium, treponema, Yersinia enterocolitica, Klebsiella pneumoniae, Pseudomonas aerugonisa, Staphylococcus, aureus, Bacillus anthracis (causative agent of anthrax), Clostridium botulinum and its toxins (causative agents of botulism), Yersinia pestis (causative agent of plague), Variola major (causative agent of smallpox), Francisella tularensis (causative agent of tularemia), Coxiella burnetti (causative agent of Q fever), bacteria of the genus Brucella (causative agents of brucellosis) Burkholderia mallei (causative agent of glanders), Ricinus communis and its toxins, Clostridium perfringens and its toxins, such as the epsilon toxin, Staphylococcus toxins, such as enterotoxin B, bacteria which cause multidrug resistant tuberculosis such as drug-resistant Mycobacterium tuberculosis strains, or other pathogenic bacteria known to be transmitted by biological fluids; fungi such as such as candida; and parasites such as plasmodium, ascaris, leishmania, and Trypanosoma cruzi. The term xe2x80x9ctarget pathogenxe2x80x9d refers to the pathogen of interest that is to be removed from the sample.
The term xe2x80x9cpathogen removalxe2x80x9d means the substantial reduction of the number of pathogenic particles from a biological fluid as measured by a biological, chemical or physical titration assay. Pathogen removal is usually measured as a logarithmic function, for instance a 1-log removal indicates that starting titer of the pathogen has been reduced by 90%. A 2-log removal indicates a reduction by 99%, and so on. Substantial reduction of a pathogen can include removal of 1- to 3-logs or greater, and preferably results in greater than 4- to 5-logs of removal or a final titer below the limit of detection of the pathogen assay. Pathogen detecting assays include physio-chemical assays, for instance a fluorescence assay, or biochemical assays, for instance an ELISA assay. Pathogen detecting assays may involve the in vitro use of cells such as viral plaque assays or microbial growth assays. For some pathogens, the only appropriate endpoint is an in vivo titration assay since the pathogen only replicates in a particular host animal. These and other methods known to those in the art may be used for measuring pathogen removal.
The present invention is based on the finding that high density microparticles (xe2x80x9cHDMxe2x80x9d) offer advantages over other solid supports, primarily magnetic particles, for the removal of pathogens from biological fluids. While not being limited to a particular mechanism, the density of the HDM is such that during mixing, the HDM contact the target pathogen in the sample at rates greater than by classical diffusion because the particles are moving through the solution under the influence of gravity, thus leading to the need for significantly fewer particles than used in state of the art methods, and more effective and rapid mixing. This results in a more cost-effective reagent and significantly lower non-specific binding due to the lower surface area. xe2x80x9cSurface areaxe2x80x9d refers to the area of the particle surface available for reaction, and fewer particles translates to lower surface area per reaction.
Additional advantages of the instant invention include: rapid reaction kinetics (speed of target pathogen capture), lack of requirement for ancillary devices such as a magnetic separator, simplicity of rinsing and adding of reagents and of particle separation, and economy of reagents because the speed of capture is such that significantly fewer particles are required than with magnetic separation as noted above. Further, the use of gravity settling to separate the particles is far less vigorous and time consuming than traditional separation techniques such as centrifugation which generates shear forces, which can degrade desirable materials present in the biological fluid.
A further advantage of the method of the invention is that the method does not cause substantial cell damage and preserves the function of the sample. This is of particular concern when the sample is a biological fluid such as whole blood or a component thereof which is intended for therapeutic use. Preservation of function can be assessed readily based on the intended use by one skilled in the particular art and accepted medical practice defines a large range of cellular, biochemical and physical properties of blood cells that are therapeutically acceptable. For instance, regulatory standards of product approval recognize that blood cells with far less than 100% activity may be therapeutically useful. For instance, 24-hour post transfusion recovery of red blood cells as low as 70% after processing and storage has been deemed an acceptable value for therapeutic use. After depletion of pathogens in a red blood cell suspension, the function of the red blood cells can be measured using standard in vitro methods, including hemolysis, ATP levels, cellular deformability and pH. The functionality of red blood cells can also be measured in vivo by determining the 24-hour post-transfusion recovery in human subjects. Similarly, platelet recoveries 24-hour post transfusion of 30-50% are considered routine and acceptable in transfusion medicine. Platelet function can be measured by standard in vitro tests including aggregation assays, pH, shape change, osmotic shock and morphology, as well as by in vivo determination of the 24-hour post transfusion recovery. Hematopoietic stem cells can be enumerated via flow cytometry and their viability determined by dye exclusion methods, and their proliferative potential by colony-forming assays.
The present invention relates to methods of using high density microparticles (xe2x80x9cHDMxe2x80x9d) to separate or isolate target pathogens by gravity sedimentation. In one embodiment of the invention, the HDM are first added to the sample in a mixing step. Following the mixing step, the sample is simply stood on end and the HDM bound to the target pathogen, settle out by gravity, typically over a one to four minute time period. A unique feature of the methods of the invention is that the gentle settling of the HDM by gravity is such that the fluid is pushed aside by the falling HDM thus eliminating non-specific trapping of undesired materials and other cellular components by the HDM. This represents a significant improvement over use of magnetic particles where nonspecific trapping occurs as the particles traverse through the fluid toward the magnet.
The HDM can be made of numerous materials, including by way of illustration and not limitation, metals such as iron, nickel, aluminum, copper, zinc, cadmium, titanium, zirconium, tin, lead, chromium, manganese and cobalt; metal oxides and hydrated oxides such as aluminum oxide, chromium oxide, iron oxide, zinc oxide, and cobalt oxide; metal silicates such as of magnesium, aluminum, zinc, lead, chromium, copper, iron, cobalt, and nickel; alloys such as bronze, brass, stainless steel, and so forth. The microparticles can also be made of non-metal or organic materials such as cellulose, ceramics, glass, nylon, polystyrene, rubber, latex, and so forth. The microparticles can also be a combination of a metal and a non-metal or organic compound, for example, methacrylate or styrene coated metals and silicate coated metals. The base material may be doped with an agent to alter its physical or chemical properties, for instance the inclusion of rare earth oxides in aluminosilicate glasses to create a paramagnetic glass materials with high density (White and Day (1994) Rare Elements in Glasses, Key Engineering Materials Vol. 94-95:181-208.)
Suitable commercially available HDM, include for example, nickel (Type 123, VM 63, 18/209A, 10/585A, 347355 and HDNP sold by Novamet Specialty Products, Inc., Wyckoff, N.J.); 08841R sold by Spex, Inc.; 01509BW sold by Aldrich), stainless steel (P316L sold by Ametek), zinc dust (Aldrich), palladium (D13A17 sold by John Matthey Elec.), TiO2, SiO2 or MnO2 (Aldrich).
As noted above, the HDM have a density of at least twice, more preferably 2 or 3 times the density of the non-target materials present in the sample. In this manner, the HDM are designed to settle under gravity and thus be separated them from the non-target materials. For example, the non-target materials commonly include blood cells, which have a density on the order of 1.05 gm/cc. Therefore, for the preferred methods of the invention, the HDM should be substantially more dense than the blood cells, e.g., as stated above, on the order of 2-3 times more dense than the blood cells.
The configuration of the HDM can vary from being irregular in shape to being spherical, from having an uneven or irregular surface to having a smooth surface, and can be finely divided powders or ultrafine particles. The particle size (nominal diameter) is not critical to the invention but will typically range from 1-50 xcexcm, more typically 3-35 xcexcm, and is preferably about 5 xcexcm. The microparticles can be uniform in size or can vary in size with the average particle size preferably being in the aforementioned range.
The shape of the HDM also may be useful in that removal of a specific pathogenic protein in a mixed cellular-plasma fluid characteristic of blood, a spherical component moves through the fluid more efficiently, and minimizes entrapment of cellular components.
Size specificity also can be determined by the target pathogen, where cellular targets may be removed by particles which preferably are 1 to 5 microns in size.
In one embodiment, the HDM have a surface area of at least 0.4 m2/g, preferably from about 0.4 m2/g to about 0.5 m2g.
The preferred HDM are formed from carbonyl nickel, such as the nickel powders made by Novamet, a subsidiary of INCO, USA, as Nickel Powder Type 123. The microparticles are not uniform in size, but have a size range of 3-35 xcexcm, with a nominal diameter of about 5 xcexcm.
The aforementioned particle materials are intended to be illustrative only and are not intended to be limiting in any manner, since any particle material, along with any particle size or configuration, can be used as long as the microparticles settle by differential gravity as required by the invention.
The HDM are linked to a reactant and are preferably coated before being linked to the reactant. Numerous coatings as are well known in the art can be utilized, for example the microparticles can be coated with human serum albumin, tris (3-mercaptopropyl)-N-glycylamino) methane (Siiman, et at., U.S. Pat. No. 6,074,884), gelatin-aminodextrans (Siiman, et at., U.S. Pat. No. 5,466,609) or amino acid homopolymers or random copolymers. A preferred random amino acid copolymer is poly(glutamate, lysine, tyrosine) [6:3:1] obtainable from Sigma Chemical Co. as Product No. P8854. It is a linear random polymer of the amino acids glutamic acid, lysine, and tyrosine in a ratio of 6 parts glutamic acid, 3 parts lysine, and 1 part tyrosine. In another embodiment, the amino acid copolymer is an amino acid copolymer including lysine and tyrosine in a ratio of 4 parts lysine to 1 part tyrosine. In yet another embodiment, the amino acid copolymer is an amino acid copolymer including lysine and alanine in a ratio of 1 part lysine to 1 part alanine. Such coatings will be selected with a view to optimal reactivity and biocompatibility, according to the need of the biological fluid to be treated. Another suitable coating involves first coating the HDM with a synthetic polymer, and then activating the polymer prior to linkage with the reactant. For example, the HDM can have a thin coating of hydrated silica (xe2x80x9csilicatexe2x80x9d) or a silicate derivative, obtained by a process referred to as xe2x80x9csilanolizationxe2x80x9d which uses sodium metasilicate and ammonium acetate. An aqueous solution of sodium/metasilicate is formed, ammonium acetate is added, followed by the addition of the particles to be coated.
It may be desirable to pre-treat the microparticles prior to coating. Such pre-treatment of the nickel microparticles serves to sterilize and depyrogenate and also creates an oxide layer on the particle surface. Typically, such pre-treatment involves heating the nickel microparticles for about 2-6 hours, preferably for about 5 hours, at a temperature within the range of about 200-350xc2x0 C., preferably about 250xc2x0 C. This pretreatment is particularly beneficial when metallic microparticles are used.
The reactant is a molecule capable of binding with the requisite affinity and specificity to the target pathogen. Suitable reactants include monoclonal and polyclonal antibodies (including antibody fragments) that specifically bind to the target pathogen, or synthetic molecules designed or selected to have high affinity for target pathogens. Synthetic molecules can be produced using directed chemical synthesis, combinatorial chemistry or biological methods (e.g. phage display) followed by screening, as is know to those skilled in the art. Depending on the complexity of the library of products generated using a combinatorial method, screening may involve automated, high throughput methods or may utilize a biological selection for identifying the desired ligand. The term xe2x80x9cspecifically bindxe2x80x9d refers to the specific affinity of the reactant for the target pathogen compared to the substantially reduced affinity for other macromolecules, pathogens or cells.
As indicated above, the present invention relates to methods of using HDM to separate or isolate target pathogens by gravity sedimentation, using coated microparticles, coupled to a reactant, preferably an antibody, and used to specifically remove or isolate certain targeted pathogens such as prions, protozoa, viruses, bacteria, fungi, parasites, and so forth.
The reactant can be directly attached to the HDM by adsorption or by direct chemical bonding such as by means of a covalent reaction, for example as described in Hermanson (1996) Bioconjugate Techniques New York: Academic Press. The ligand itself may be directly activated with a variety of chemical functionalities including nucleophilic groups, leaving groups, or electrophilic groups. Activating functional groups include alkyl and acyl halides, amines, sulfhydryls, aldehydes, unsaturated bonds, hydrazides, isocyanates, isothiocyanates, ketones, and other groups known to activate for chemical bonding. Alternatively, the HDM and ligand may be bonded through the use of a small molecule coupling reagent. Non-limiting examples of coupling reagents include carbodiimides, maleimides, N-hydroxysuccinimide esters, bischloroethylamines, bifunctional aldehydes such as glutaraldehyde, anyhydrides and the like. Alternately, the reactant may be coupled to the HDM through affinity binding such as a biotinstreptavidin linkage or coupling, as is well known in the art. Where biotinstreptavidin coupling is preferred, streptavidin can be bound to the microparticles by covalent or non-covalent attachment and the biotinylated reactant can be synthesized using methods that are well known in the art. See for example, Hermanson (1996) Bioconjugate Techniques New York: Academic Press. Once the reactant is attached to the HDM, the HDM can be added directly to the fluid sample without further dilution or washing steps.
For covalent binding, the HDM may be coated with a polymer that contains chemical moieties or functional groups that are available for covalent attachment to a suitable reactant, typically through a linker. For example, the amino acid polymers described above may have groups, such as the xcex5-amino group of lysine, available to couple the reactant covalently via appropriate linkers.
The invention also contemplates placing a second coating on the microparticles to provide for these functional groups. Functional groups by which the reactant can be attached to the microparticles, are well known in the art and include all those functional groups known to be useful for attaching nucleic acids to solid supports. These include, by way of illustration and not limitation, amino, hydroxyl, carboxyl, aldehyde and sulfhydryl groups. The available functional groups may be further modified to create new functionality. For instance, carboxylates may be converted to primary amines using diamines such as ethylene diamine; carbohydrates and other biological moieties containing polysaccharides may be functionalized to contain aldehyde groups by periodate oxidation; amines may be reacted with 2-iminothiolane to form sulfhydryl groups; hydroxyl groups may be converted to carboxylate moieties using chloroacetic acid. These methods are but a small number of the means known to those of skill for creating new functionality on the HDM or coated HDM (Hermanson, supra).
A plurality of dense, relatively heavy microparticles having the appropriate reactant bound thereto are mixed with the biological fluid sample. The HDM capture the target pathogen rapidly and are then allowed to differentially settle by gravity thus separating the target pathogen(s) from the remainder of the reaction mixture. One advantage of the instant invention is that the methods described herein are particularly adaptable to automation since both the mixing and settling steps can be easily automated. Automation is particularly desirable when the methods of the invention are used in diagnostic applications.
One embodiment of the method of the invention is a method of removing at least one target pathogen from a biological fluid sample. This method can be used to remove more than one population of target pathogens, and they can be removed sequentially or all at one time. The method comprises the following steps: (a) providing a plurality of high density microparticles having bound thereto a reactant which specifically binds to at least one population of target pathogens and having a density sufficient to provide differential gravity settling of the target pathogen from the sample; (b) mixing a portion of the sample with the microparticles to bind the microparticles to the target pathogen; (c) settling the microparticles with the bound pathogen in the sample to produce a supematant substantially free from the bound pathogen, where the settling is accomplished primarily by gravity; and (d) separating the microparticles bound to the pathogen from the supernatant.
The method of the invention also contemplates pretreating the sample by lysis, for example by the addition of lysis buffers.
Mixing Step
The mixing can be effected by passing the microparticles at least once through the sample, such as by gravity. In this manner, the mixing and settling are conducted simultaneously such that mixing is effected solely by differential gravity settling. Therefore, in one embodiment, the method can be performed without any additional mixing step, instead relying only on the microparticles movement though the sample by gravity. When the mixing and settling steps are combined, this mixing/settling will typically take about 1-5 minutes.
The mixing can, however, also be enhanced by causing the microparticles to repeatedly pass or settle through a substantial portion of the sample. For small volumes, on the order of microliters (typically less than 0.5 milliliter), the mixing can be rapid such as by vortexing or xe2x80x9cnutationxe2x80x9d such as is described in Coulter, et al., U.S. Pat. No. 5,238,812, which is incorporated herein by reference. For larger volumes, on the order of greater than or equal to 0.5 milliliters (typically 0.5 ml to 3 liters), mixing can also be achieved by gently tumbling the microparticles and the sample in an end over end fashion such as is described in Coulter, et at., U.S. Pat. No. 5,576,185, which is incorporated herein by reference. Such tumbling can be accomplished, for example, by means of a device configured to hold a test tube or other configuration of a reaction vessel, and which slowly rotates the test tube or vessel end over end. When a separate mixing and settling step are utilized, the mixing step will typically take about 15 seconds to 5 minutes, and the settling step is usually carried out for about 1-4 minutes.
Settling Step
As noted above, the settling aspect of the methods of the invention can be performed relying solely on gravity sedimentation. However, for certain applications, it may be desirable to modify the method to accelerate this step. In one such modification, the HDM and sample are briefly spun in a centrifuge to accelerate the settling step.
Separation Step
Separation of the resulting supematant can be done by numerous methods that are well known in the art such as decanting or siphoning the supernatant, thus leaving the HDM at the bottom of the reaction vessel. For separation of HDM from blood components or other biological fluids, a device commonly referred to as a xe2x80x9cplasma extractorxe2x80x9d may be used to separate HDM from the fluid if a flexible plastic container is used. Automated versions of plasma extractors may also be used.
When the supernatant is intended for therapeutic use, such as by being transplanted in a human, or where for other reasons it is desired to prevent carry over of particles, it may be desirable to use HDM that are comprised of a magnetic material such as nickel. In this manner, a magnet or magnetic field can be applied to the bottom of the reaction vessel after the HDM have settled, to ensure that the HDM are not removed with the supernatant in the separation step.
The HDM may also be of a sufficient size that they can be differentially filtered to separate them from the biological fluid. When the fluid is a non-cellular product, for instance blood plasma, the HDM may have a wide range of sizes. When the fluid contains cells that are desired for later use, the HDM must be sufficiently larger than the cells so that the microparticles can be differentially filtered from the cell suspension. Preferably the HDM in this circumstance have a diameter of at least 7 microns, and more preferably they are 10 microns or greater in diameter in order to be filtered away from the desired cells.
In one embodiment of the invention, the method is used to remove pathogens from a cell preparation, the supernatant of which can be used for clinical transfusion or transplantation, research or diagnostic applications. In a preferred embodiment, the resulting supernatant, substantially free of the contaminating pathogens, is used therapeutically, either in clinical transfusion or transplantation.
Devices for Performing the Methods of the Invention
The methods of the invention for removing at least one population of target pathogens from a biological fluid sample, can be accomplished using separation devices and components as are well known in the art. For example, the cell separation apparatus described in Coulter, et al., U.S. Pat. No. 5,576,185, can be readily adapted for use with the methods described herein. In general, the method of the invention can be practiced using a device that comprises: (a) a plurality of HDM which (i) have bound thereto a reactant which specifically binds to the target pathogen, (ii) have a density sufficient to provide differential gravity settling of the target pathogen from the sample, and (iii) are capable of settling with the bound pathogen in the sample to produce a supernatant that is substantially free from the bound pathogen, where the settling is accomplished primarily by gravity; (b) a means for mixing a portion of the sample with the HDM to bind the HDM to the target pathogen; and (c) a means for separating the HDM bound to the pathogen from the supematant.
Suitable devices would include the biological sample containing the target pathogens and a source of the HDM, along with a container in which the sample and HDM can be mixed and subsequently settle. The device may also include a source of the biological sample, for example a blood donor or a container containing a unit of whole blood or a blood component. The sample can be transferred by tubing to a container such as a primary collection container. This primary collection container is sterile and either holds the HDM or is connected to a second container holding the HDM. Accordingly, the HDM can be added to the primary collection container either before, during or after the transfer of the sample into the container.
After the HDM are dispersed through the sample or have been mixed with the sample, the HDM are allowed to settle to the bottom of the container. The device may also include an expressor that allows for removal of the treated sample from the HDM bound to the target pathogen. The expresser can serve to compress the container thereby reducing its volume and forcing the sample, with the pathogens removed, out of the container. Typically the sample is expressed through a tube to another container, while the HDM with bound target pathogen will generally be retained at the bottom of the container due to their greater density.
The containers used in the methods of the invention, as well as in any devices designed for use with these methods, will be determined by the sample size and can be small, such as a 10 microliter container (e.g., a test tube) or large, such as a 100 milliliter to 3 liter container (e.g., a blood bag). In one embodiment, the containers are sterile and formed from flexible plastic sheeting that is biocompatible with the blood or blood components, such as polyvinyl chloride or polyethylene or other materials known to those skilled in the art of making blood storage containers.
The sample container, the HDM as well as other components of the apparatus that contact the sample directly can be sterilized by controlled heat, ethylene oxide gas or by radiation. The preferred method of sterilization will be selected by one skilled in the art to preserve the activity of the HDM, particularly the reactant bound thereto, and will be dependent on the physical characteristics, composition and number of HDM. Preferred sterilization methods will also depend on whether the device is xe2x80x9cdry,xe2x80x9d that is lacking a solution component, or xe2x80x9cwet.xe2x80x9d Alternatively, it is well known to those skilled in the art of making sample (e.g., blood) storage containers that individual incompatible components can be separately sterilized by different means and then joined via a sterile connection process that connects two devices via sterile tubing leads. The preferred method of sterilization will be a terminal sterilization at the 10-6 Sterility Assurance Level in order to enable extended storage of the sample after processing in the apparatus.
The apparatus may optionally include a secondary means for insuring the separation of the sample from the HDM with bound target pathogen. The purpose of the secondary capture step is to further reduce the probability that HDM will be found in the treated sample, which is of particular concern when the final processed sample is a blood component(s). The nature of this secondary capture will take advantage of specific properties of the HDM. When HDM are used that are made of or incorporate a magnetized or paramagnetic substance, the device may include a magnet or a magnetic field, positioned such that it can be applied to the bottom of the container to either accelerate settling or to insure complete that the HDM are not removed during separation step, in particular when the treated sample is to be reinserted into a living organism, such as the human body. The expressor may also be used in combination with the magnet, or if the container is more rigid, the container may be rotated with the magnet held at the bottom, to allow the treated sample to pour or drain. Alternately, the magnet or a magnetic field can be positioned such that the sample can be passed by or through a magnetic field after it is separated from the HDM, but before it is reinserted into the body. This will also serve to insure that no HDM remain in the sample.
The device can also include an optional secondary means of retaining the HDM during the decanting process, which relies on the size or rigidity of the HDM relative to the sample. If the more rigid HDM are large relative to the red blood cell, for example 10 microns in diameter or greater, they may be retained by a sizing filter placed at the outlet of the container. In particular since red blood cells are known to be highly flexible, the size differential to achieve the separation of the more rigid particles may not need to be large, i.e. the HDM and the red blood cells may in fact be of comparable size.
Another optional secondary means of retaining the particles is to compact the HDM by centrifugation after settling. In this manner, the device may include a centrifuge. The device may include a means for briefly spinning the container, if it is desired to accelerate the settling of the HDM. This could be a centrifuge and would operate simultaneous with settling. In this manner, centrifugation would serve to enhance the rate at which the HDM settle and would also lead to enhanced compaction of the HDM with bound pathogen at the bottom of the container The device can be automated such that the sample and HDM are automatically mixed and then moved between the stations or the device can require manual steps that would be carried out by an operator or can be a combination of the two procedures.
For use of the method of the invention in a large scale, such as in an industrial setting, the HDM can be utilized in a large reaction vessel or fluidized bed reactor or as part of a flow process involving column fractionation.
Another embodiment of the invention is a kit containing a plurality of HDM having bound thereto a reactant which specifically binds to a target pathogen of interest, in combination with instructions for using said microparticles in a method of removing a pathogen of interest from a biological fluid sample. The HDM have a density within the range of 7-10 g/cm3 and may optionally be lyophilized to improve stability during storage. HDM could be packaged integral to a sterile disposable for processing the biological fluid. Formulations of HDM include liquid suspensions, or lyophilized or powdered HDM. Liquid formulations may be stored at a temperature between xe2x88x9215 to 15xc2x0 C., preferably at 2-8xc2x0 C., and most preferably can be stored at ambient temperature. Alternatively, the kit could comprise a separate container of HDM, such as a vial, with appropriate means for attaching to commercially available disposable fluid containment sets. Vials may be made of glass or polypropylene. Means of attachment include aseptic spiking and sterile connection using any number of commercially available systems.
As discussed above, it is often desirable to remove or separate the pathogens from a biological fluid sample. Such instructions may indicate that a plurality of HDM, attached to a suitable reactant, are to be mixed with the sample. The HDM, with the target pathogen(s) bound thereto, are then allowed to differentially settle by gravity and the remaining sample is removed. One such application of this kit is for therapeutic uses, where the fluid sample that has been purged of pathogens, is to be reinserted or transplanted into a living organism, such as the human body. In such a case, as well as in all applications described herein, it may be preferable to use HDM that have magnetic properties so that a magnetic field can be used after completion of the gravity settling step, to further insure that all the HDM are removed from the sample.
The general methods of the invention are best understood with reference to the following examples which are intended to enable those skilled in the art to understand more clearly and to practice the present invention. These examples are not intended, nor are they to be construed, as limiting the scope of the invention, but merely are illustrative and representative thereof. | {
"pile_set_name": "USPTO Backgrounds"
} |
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