Vinyl ether compounds having the formula:

The present invention relates to useful halogenated compounds. More specifically, this invention relates to a family of halogenated vinyl ether compounds, their uses, and the products resulting from their use.
Vinyl ethers containing fluorine and also chlorine are of particular interest in coatings applications because they form polymers and copolymers that exhibit beneficial properties, including high chemical and thermal resistance, high electrical resistivity, low surface energy and low refractive index. These properties can be imparted to a coating surface and, consequently, halogenated vinyl ethers are particularly useful in making protective coatings, release coatings, as well as, surfactants, anticorrosion agents, antioxidizing agents and the like.
Some fluorinated chemical compounds are known in the art which contain oxyvinyl groups such as are described in U.S. Pat. No. 2,732,370 under the generic formula CnF2n+1CH2xe2x80x94Oxe2x80x94CHxe2x95x90CH2. The fluorinated structures near the oxyvinyl group are believed either not to be radiation curable or not to have radiation curable reactivities to the extent desired.
JP 2,000,721 discloses aliphatic fluorinated vinyl ether compounds having the structure Rxe2x80x2Rxe2x80x3CHxe2x80x94Oxe2x80x94CH2CH2xe2x80x94Oxe2x80x94CHxe2x95x90CH2 wherein Rxe2x80x2 is a hydrogen, a lower alkyl group or a polyfluoroalkyl group and Rxe2x80x3 is a polyfluoroalkyl group. U.S. Pat. No. 5,012,011 discloses the synthesis of fluorinated vinyl ethers such as CF3(CF2)xR1OCH2CH(OH)R2OCHxe2x95x90CH2(R1=C1-C20 alkylene, alkoxyethylene, arylene, aryloxyalkylene; R2=C1-C100 divalent organic radicals; and x=1-22). Fluorinated vinyl compounds containing a hydroxyl or alkoxy group are described by U.S. Pat. No. 4,559,179. The preparation of H(CF2CF2)nCH2OCHxe2x95x90CH2 (n=2-4) is reported by Sukhinin et al., Zh. Vses. khim. O-va., 26(3), 344-5 (1981). Because of the heavily fluorinated structure, adherence to substrates and compatibility with solvents and cosolutes may not be as good as desired.
Moreover, vinyl ether monomers or copolymers that can be cured via ultraviolet (UV) radiation offer even more advantages in coatings and other applications. Photocuring technology has grown rapidly within the last decade. The photocuring process involves the radiation induced polymerization or cross linking of monomers into a three dimensional network and has a number of advantages including the environmentally safe, solvent-free 100% conversion to a desired product, as well as short cycle times and limited space and capital equipment requirements.
In the telecommunications industry, for example, there is a need to develop photocurable compositions for optical wave guide and interconnect applications. In order to be useful in these applications, the photocurable compositions must polymerize to form polymers that are highly transparent at the working wavelength and possess low intrinsic absorption and scattering loss.
U.S. Pat. No. 5,274,174 discloses a new class of photocurable compositions comprised of certain fluorinated monomers, such as diacrylates with perfluoro or perfluoropolyether chains, which possess low intrinsic absorption loss. It is, therefore, possible to make low loss optical interconnects from a photocurable system including these materials.
Fluorine substitution in the polymer structure, however, also induces some other less desirable changes in the polymer""s physical properties. One such change is the decrease in refractive index. For a highly fluorinated acrylate photopolymer, the refractive index decreases to the 1.32 region when the H/F mole ratio reaches 0.25. For optical interconnect applications, to avoid loss of light, it is important that the refractive index of the core of a planar waveguide approximate and preferably match that of the optical fiber (generally 1.45).
It is also important to be able to precisely control and fine tune the refractive index of the photopolymer at the working wavelength in optical waveguide and interconnect applications. A desired index of refraction can be produced by mixing photocurable monomers with different refractive indices. Most photopolymers made from conventional photocurable monomers have refractive indices in the region of 1.45-1.55. Depending on the application, it is often desirable to lower a photopolymer""s refractive index. One way to do this is to mix low refractive index fluorinated monomers with conventional hydrocarbon-based monomers. Unfortunately, this is difficult to accomplish because of the incompatibility or insolubility of the different monomer systems. Thus, there is a need for photocurable compositions which: (i) possess low intrinsic absorption loss in the near-infrared region; (ii) possess a refractive index approaching traditional optical fibers; and (iii) are compatible with both conventional hydrocarbon-based and highly fluorinated monomers.
The present invention provides a family of halogenated vinyl ether compounds which are useful for making other compounds, including polymeric compounds, having a wide variety of uses. The vinyl ether compounds of the present invention exhibit the beneficial properties of fluorinated monomers and can be utilized to realize the benefits of photocuring processes.
These novel compounds are readily radiation curable and curable by other means. These compounds are soluble with other components (cosolutes) and in numerous recoverable and re-useable solvents, and can be formulated to be of low viscosity when applied.
The novel fluorine containing compounds provide enhanced surface properties, and are fast curing but have indefinite pot life before exposure to radiation or other curing processes. The compounds, when cured, have a low refractive index. The compounds have good substrate adhesion, and can be chemically bonded into other resins, eliminating migratory problems associated with materials which are not bonded into a formulation. In addition, the compounds can be made from commercially available materials by both known and novel processes. The compounds of the invention include oxyvinyl monoethers, oxyvinyl diethers, oxyvinyl monoesters and oxyvinyl diesters of fluorine containing structures.
In general the compounds of the invention have the general formula:
Rxe2x80x94Oxe2x80x94Xxe2x80x94Oxe2x80x94CHxe2x95x90CH2xe2x80x83xe2x80x83(I)
wherein R is radical having a formula selected from: R1xe2x80x94CnHmxe2x80x94, R1xe2x80x94CnHmxe2x80x94C(xe2x95x90O)xe2x80x94, R1xe2x80x94CnHmCH[xe2x80x94Oxe2x80x94Xxe2x80x94Oxe2x80x94CHxe2x95x90CH2]xe2x80x94, R1xe2x80x94CnHmCH[xe2x80x94Oxe2x80x94Xxe2x80x94Oxe2x80x94CHxe2x95x90CH2]xe2x80x94C(xe2x95x90O)xe2x80x94, R1xe2x80x94CnHmCH[xe2x80x94C(xe2x95x90O)xe2x80x94Oxe2x80x94Xxe2x80x94Oxe2x80x94CHxe2x95x90CH2]xe2x80x94, R1xe2x80x94CnHmCH[xe2x80x94C(xe2x95x90O)xe2x80x94Oxe2x80x94Xxe2x80x94Oxe2x80x94CHxe2x95x90CH2]xe2x80x94C(xe2x95x90O)xe2x80x94, R1xe2x80x94[CFClxe2x80x94CF2xe2x80x94]pCH2xe2x80x94 and HCFClxe2x80x94CF2xe2x80x94, wherein R1 is hydrogen, an unsubstituted or substituted fluorinated aliphatic radical, an unsubstituted or substituted fluorinated cyclic aliphatic radical, an unsubstituted or substituted fluorinated aromatic radical, an unsubstituted or substituted fluorinated araliphatic radical, or an unsubstituted or substituted fluorinated heterocyclic radical; X is an unsubstituted or substituted aliphatic radical, an unsubstituted or substituted cyclic aliphatic radical, an un-substituted or substituted aromatic radical, an unsubstituted or substituted araliphatic radical, or a unsubstituted or substituted heterocyclic radical; n is between 1 and 6, inclusive; nxe2x89xa6mxe2x89xa62n; and p is from 1 to 20, inclusive; provided that when R1 of R1xe2x80x94CnHmxe2x80x94 is a fluorinated aliphatic radical, X is not an ethylene or propylene radical.
Fluorinated oxyvinyl diethers of the invention may be represented by the formula:
R1CnHm[OXOCHxe2x95x90CH2]2
Fluorinated oxyvinyl monoesters of the invention may be represented by the formula:
R1CnHmCOOXOCHxe2x95x90CH2
Fluorinated oxyvinyl diesters of the invention may be represented by the formula:
R1CnHmCH[COOXOCHxe2x95x90CH2]2
Another aspect of the present invention provides curable compositions that contain a curable component that includes at least one compound having the structure of Formula I, in which R and X are as described above for Formula I. Preferred curable compositions include photocurable compositions combining at least one compound having the structure of Formula I and a photo initiator compound.
The curable compositions will contain between about 0.01% to about 99% by weight of at least one compound having the structure of Formula I. For waveguide coatings for example, the curable composition should contain at least 35% by weight of at least one compound having the structure of Formula I.
It has been unexpectedly discovered that the compounds having the structure of Formula I, when added at levels less than about 10% by weight to other curable systems, are cross-linked into the cured polymer, yet are oriented toward the surface of a polymer coating, providing useful modifications to the surface properties. A level between about 0.1% and about 2.0% by weight is preferred. This aspect of the present invention may also be employed with compounds having the structure of Formula I wherein R is a radical having the formula R1xe2x80x94CFHxe2x80x94CF2xe2x80x94 or R1xe2x80x94CFxe2x95x90CFxe2x80x94, wherein R1 and X are the same as described above with respect to Formula I.
The photocurable compositions of the present invention are useful in the manufacture of optical devices having light transmissive regions. Therefore, another aspect of the present invention provides a process for producing an optical device employing the steps of: (a) applying a layer of the photocurable composition of the invention onto a substrate; (b) imagewise exposing the photocurable composition of the invention to actinic radiation to form exposed and non-exposed areas on the substrate; and (c) removing the imagewise non-exposed areas while leaving the imagewise exposed areas on the substrate.
The invention further includes uses of the halogenated vinyl ether compounds of the present invention in coatings, inks, adhesives, structural polymers and optical devices, including fiber optics and waveguides, and to make photocured products using photocuring processes. A preferred aspect of this embodiment of the invention comprises the use of the compounds of the present invention in the preparation of the light transmissive component of an optical device, particularly a waveguide.
The present invention also includes polymers produced by curing the fluorinated vinyl ether compounds of the present invention. Therefore, a further aspect of the invention provides a polymer with one or more vinyl ether repeating units having the structure of Formula II:
wherein R and X are as described above with respect to Formula I.
In Formulae I and II, X is preferably an unsubstituted or substituted C1-C20 aliphatic radical, an unsubstituted or substituted C3-C20 cyclic aliphatic radical, an unsubstituted or substituted C6-C15 aromatic radical, an unsubstituted or substituted C7-C13 araliphatic radical, or an unsubstituted or substituted 3-10 member heterocyclic radical. More preferably, X is an unsubstituted or substituted C1-C20 alkyl radical, an unsubstituted or substituted C3-C10 cycloalkyl radical, an unsubstituted or substituted 3-6 member heterocyclic radical, an unsubstituted or substituted C6-C15 aryl radical, or an unsubstituted or substituted C7-C13 aralkyl radical. The radicals may be substituted with essentially any conventional organic moiety. Examples of substitution groups include C1-C6 aliphatics such as alkyls, halogenated alkyls, alkoxys, and alkenyls, C6-C15 aryls, halogens, particularly fluorine, C3-C8 cyclic aliphatics, nitros, aminos (primary and secondary), amidos, cyanos and hydroxyls.
X as a C1-C20 alkyl radical may be straight chain or branched, for example, a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, or 2-ethylhexyl radical. Any of these groups may be substituted with typical organic moieties, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, methanesulphonyl, cyano, bromine, chlorine or fluorine to form, for example, methoxymethyl, 2-methoxyethyl, 2-ethoxymethyl, 2-n-butoxyethyl, 3-methoxypropyl, 1-methoxybutyl, 2-methoxybutyl, methanesulphonylmethyl, 2-methanesulphonylethyl, 2-cyanoethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, trichloromethyl, 2-chloroethyl, 2-(chloromethyl)ethyl, 2,2,2-trichloroethyl, 2-chloro-n-propyl or 3-chloro-n-butyl. In a preferred class of alkyl radicals, X is a straight chain C2-C6 alkyl radical, especially an ethyl or butyl radical.
X as a C3-C10 cycloalkyl radical may be, for example, a cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl dimethylcyclohexyl, cycloheptyl, or cyclooctyl radical. Any of these groups may be substituted with essentially any conventional organic radical, including, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, cyano, chlorine or fluorine. In a preferred class of cycloalkyl radical, X is a C6-C10 cycloalkyl radical. In a preferred class of cycloalkyl radical, X is a C6-C8 cycloalkyl radical, even more preferably, a cyclohexyldimethyl radical.
X as a 3-6 ring member heterocyclic radical may include known heterocyclic atoms such as N, O and S. Suitable heterocycles include, for example, pyran, thiophene, pyrrole, furan, pyridine, or derivatives thereof.
X as a C6-C15 aryl may be, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, o-xylyl, m-xylyl, p-xylyl, alpha-naphthyl or beta naphthyl. Any of these groups may be substituted with essentially any conventional organic radical, for example, halogens, particularly fluorine, C1-C4 alkoxyl or nitro. In a preferred class of compounds, X is C6-C12 aryl, especially phenyl or naphthyl.
X as a C7-C20 aralkyl radical may be, for example, benzyl, 4-methylbenzyl, o-methylbenzyl, p-methylbenzyl, diphenyl-methyl, 2-phenylethyl, 2-phenylpropyl or 3-phenylpropyl, preferably C7-C9 aralkyl, especially benzyl.
In a still more preferred embodiment, X is an alkyl or aralkyl radical, especially a ethyl, butyl, or cyclohexyldimethyl radical.
For R of Formulae I and II, R1 is preferably hydrogen, an unsubstituted or substituted fluorinated C1-C12 aliphatic radical, an unsubstituted or substituted fluorinated C3-C20 cyclic aliphatic radical, an unsubstituted or substituted fluorinated C6-C15 aromatic radical, an unsubstituted or substituted fluorinated C7-C13 araliphatic radical, or an unsubstituted or substituted 3-10 member fluorinated heterocyclic radical. More preferably, R1 is an unsubstituted or substituted fluorinated C1-C12 alkyl radical, an unsubstituted or substituted fluorinated C3-C11 cycloalkyl radical, an unsubstituted or substituted 3-6 member fluorinated heterocyclic radical, an unsubstituted or substituted fluorinated C6-C15 aryl radical, or an unsubstituted or substituted fluorinated C7-C20 aralkyl radical. Examples of substitution groups include C1-C6 aliphatics such as alkyls, alkyl ethers, alkyl esters, alkoxys and alkenyls, C6-C15 aryls, halogens, C3-C8 cyclic aliphatics, nitro, aminos (primary and secondary), amidos, cyanos, and hydroxyl, thio, mercapto, sulfo, heterocyclo. The substitution groups are preferably attached to non-fluorinated carbon atoms of R1.
R1 as a C1-C12 fluorinated alkyl radical may be straight chained or branched, for example, a fluorinated methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl or 2-ethylhexyl. Any of these groups may be substituted with essentially any conventional organic moiety, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, methanesulphonyl, cyano, bromine or chlorine.
C1-C6 fluorinated alkyl radicals are even more preferred. Examples include fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoroethyl, trifluoroethyl, pentafluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, or perfluorohexyl. In the most preferred form, R1 is a trifluoromethyl radical.
R1 as a fluorinated C3-C10 cycloalkyl radical may be, for example, a fluorinated cyclopropyl, cyclobutyl, cyclopentyl, methylcylcopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl or cyclooctyl. Any of these groups may be substituted by essentially any conventional organic moiety, for example, methoxy, ethoxy, n-propoxy, n-butoxy, methanesulphonyl, cyano, bromine or chlorine.
R1 as a 3-10 ring member fluorinated heterocyclic radical may include known heterocyclic atoms such as N, O and S. Suitable fluorinated heterocycles include, for example, fluorinated pyran, thiophene, pyrrole, furan, pyridine or derivatives thereof.
R1 as a C6-C15 fluorinated aryl may be, for example, a fluorinated phenyl, o-tolyl, m-tolyl, p-tolyl, o-xylyl, m-xylyl, p-xylyl, alpha-napthyl, or beta-napthyl. Any of these groups can be substituted with, essentially any conventional organic radical, for example, halogen, C1-C4 alkoxyl or nitro.
R1 as a C7-C20 fluorinated aralkyl radical may be, for example, a fluorinated benzyl, 4-methylbenzyl, o-methylbenzyl, p-methylbenzyl, diphenyl-methyl, 2-phenylethyl, 2-phenylpropyl, or 3-phenylpropyl, and preferably a fluorinated C7-C9 aralkyl, especially fluorinated benzyl. Any of these groups may also be substituted with essentially any conventional organic moiety, for example, halogen, C1-C4 alkoxyl or nitro. The halogen, alkoxyl or nitro may be substituted in the aryl portion of the group, or in the alkyl portion of the group. The fluorine may be substituted in either the aryl group or the aryl portion of the aralkyl group to form, for example, a mono-, di-, tetra-, tert- or penta-fluorophenyl group. Alternatively, the fluorine may be substituted in the alkyl portion of the aralkyl group to form, for example, mono-, di- or tetrafluorobenzyl.
The compounds of Formula I may exist in isomeric form. For example, when R1 is CF3xe2x80x94CFHxe2x80x94CF2xe2x80x94, the compounds of Formula I have an asymmetric carbon at the xe2x80x94CFHxe2x80x94 position, and consequently, they can exist in the form of different combinations of R- and S-isomeric forms as enantiomers or racemates. In addition, cis and trans geometric isomers may also be present in the subject compounds. All racemic and isomeric forms of the compounds of Formula I, including pure enantiomeric, racemic and geometric isomers and mixtures thereof, are within the scope of the invention.
The compounds of the invention may be made by a number of methods. For example, the fluorinated oxyvinyl ethers of the invention may be made the process are disclosed in the above-referenced U.S. patent application Ser. No. 09/009,110.
Specific examples of fluorinated oxyvinyl ethers of the invention are: HCF2(CF2)3CH2O(CH2)4OCHxe2x95x90CH2; CF3CH2O(CH2)4OCHxe2x95x90CH2; HCF2(CF2)5CH2O(CH2)4OCHxe2x95x90CH2; CCl3CH2O(CH2)2OCHxe2x95x90CH2;
HOCH2(CF2)6CH2O(CH2)4OCHxe2x95x90CH2; CH3OCH2(CF2)6CH2O(CH2)4OCHxe2x95x90CH2; HSCH2(CF2)CH2O(CH2)4OCHxe2x95x90CH2; and
The oxyvinyl ethers of the invention are prepared by the process disclosed in the above-referenced U.S. patent application Ser. No. 09/009,110. Likewise, the fluorinated vinyl ether esters of this invention are prepared by the transesterification reaction disclosed in the above-referenced U.S. patent application Ser. No. 09/009,110.
Examples of the oxyvinyl esters of the present invention are: CF3(CF2)5CH2CH2CH[CO2(CH2)4OCHxe2x95x90CH2]2; CCl3(CF2)5CH2CH2CH[CO2(CH2)4OCHxe2x95x90CH2]2; CF3(CF2)9CH2CH2CH[CO2(CH2)4OCHxe2x95x90CH2]2; CF3(CF2)7CH2CH2CH[CO2(CH2)4OCHxe2x95x90CH2]2; CF3(CF2)eCH2CH2CH[CO2(CH2)4OCHxe2x95x90CH2]2;
CF3(CF2)5CH2CH2CH[CO2CH3][CO2(CH2)4OCHxe2x95x90CH2]; CF3(CF2)7CH2CH2CH[CO2CH3][CO2(CH2)4OCHxe2x95x90CH2]; and CF3(CF2)9CH2CH2CH[CO2CH3][CO2(CH2)4OCHxe2x95x90CH2].
The compounds of Formula I in which R is HCFClxe2x80x94CF2xe2x80x94 are prepared by the following reaction scheme:
The compounds of Formula I in which R is R1xe2x80x94CFHxe2x80x94CF2xe2x80x94 or R1xe2x80x94CFxe2x95x90CFxe2x80x94 are prepared by a similar process in which R1xe2x80x94CFxe2x95x90CF2 is substituted for CFClxe2x95x90CF2, which is disclosed in parent U.S. patent application Ser. No. 09/218,201. Depending upon process conditions, an additional product may be formed having the formula R1xe2x80x94CHFxe2x80x94CF2xe2x80x94Oxe2x80x94Xxe2x80x94CHxe2x95x90CH2.
A variety of vinyloxyalcohols are commercially available having the structure of Compound A, including, for example, compounds wherein X is an ethyl or butylene radical (available from Aldrich Chemical Co.); or a cyclohexyldimethyl radical (available from BASF Corp.). Furthermore, many compounds having the structure of Compound A are known in the literature and are obtainable by art-recognized procedures, see, for example, Sukhinin, et al., Zh. Vses. Khim. O-va., 26(3), 344-5 (1981). Compound B is also commercially available from Aldrich Chemical Co.
A number of methods for the preparation of vinyl ethers are known, see Fischer, P. Enol Ethers-Structure, Synthesis and Reactions, p. 761-920, in Patai, S., Editor xe2x80x9cChemistry of Ethers, Crown Ethers, Hydroxyl Groups and Their Sulfur Analoguesxe2x80x9d (Wiley, Chichester, UK (1980). The conversion of Compound A to compounds of Formula I may be accomplished by slight modification of the procedures reported in Bayliff, et al., J. Chem. Soc. Perkin Trans. 1, 4, 763-767, (1987) and Kanunyants, et al., Izv. Akad. Nauk SSSR Otdel. Khim. Nauk, 282 (1953). The disclosures of these publications are incorporated herein by reference.
In a typical procedure, a mixture of Compound A, an aprotic solvent, and a base is stirred, with slow addition, preferably dropwise, of Compound B. Preferably about 2.0 to 2.5 parts by weight of solvent per part by weight of Compound A is employed. However, those of ordinary skill in the art will understand how to successfully employ higher or lower quantities of solvent. Although the reaction is not inhibited by oxygen, it is preferred to conduct the reaction under a blanket of an inert gas such as, for example, nitrogen.
Suitable aprotic solvents include, for example, acetonitrile, dimethylformamide, and tetrahydrofuran. In a preferred embodiment, the aprotic solvent is acetonitrile.
The amount of base used in the synthesis of compounds of Formula I can range from a catalytic to a stoichiometric amount. Catalytic amounts typically range between about 0.1 to about 20 mole percent relative to the hydroxyvinyl alcohol (Compound A) of Reaction Scheme I. In light of this disclosure, one skilled in the art can readily optimize the amount of base used in the reaction without undue experimentation.
The compounds of Formula I obtained from the aforementioned reaction may be purified by conventional methods known to those skilled in the art. For example, aqueous washes, drying, concentrating under reduced pressure, distillation, and the like may be used.
The compounds of Formula I in which R is R1xe2x80x94[CFClxe2x80x94CF2xe2x80x94]pCH2xe2x80x94 were prepared by the reaction scheme shown below, in which p is an integer between 1 and 20, inclusive:
Step 1
The compounds of Formula (C) were prepared by minor modification of the procedure reported by Fikar et al., Collect. Czech. Chem. Commun., 1996, 61, 1215 from methanol and chlorotrifluoroethylene. To a stirred solution of alcohol in a solvent such as THF was added the sulfonyl chloride to afford the intermediate RSO3CH2[CF2CFCl]pR1 (D) which not isolated but used without further purification for the Step 2 of the reaction. A number of sulfonyl chlorides can be utilized for this reaction, for example, benzenesulfonyl chloride, p-toluenesulfonyl chloride, and the like. In the formula RSO2Cl, R=alkyl or aryl; the preferred R is an aryl, such as phenyl or p-toluyl group.
Step 2
In step 2 the alkoxide anion [M+Oxe2x80x94Xxe2x80x94OCHxe2x95x90CH2] was generated from the vinyloxy alcohol HOxe2x80x94Xxe2x80x94OCHxe2x95x90CH2 To a stirred solution of the alcohol in a solvent such as THF was added a base, sodium tert-butoxide. The resulting alkoxide anion was added to the in situ generated RSO3CH2[CF2CFCl]pR1 (D) in step 1 to afford Compound (E). The thus obtained Compound E was purified by conventional methods of the art, for example, aqueous washes, drying, concentrating under reduced pressure, distillation and the like.
The vinyl monomers of Formula I contain much less hydrogen than conventional photocurable monomers such that their inherent carbon-hydrogen bond absorption is greatly reduced. In addition, the introduction of chlorine or bromine atoms into the molecule can offset the effect of fluorine on the refractive index of the monomer, producing a material with an index of refraction between about 1.40-1.48. As a result, the monomers of the invention may be particularly useful in optical applications in the 1300-1550 nm wavelength region. The monomers are also compatible with both conventional hydrogen-based and highly fluorinated monomers. Because of this compatibility, it becomes possible to fine tune the refractive index and other physical properties of photocurable compositions by mixing these photocurable monomers with the monomers of Formula I, including compounds in which R is R1xe2x80x94CHFxe2x80x94CF2 and R1xe2x80x94CFxe2x95x90CFxe2x80x94.
Accordingly, the curable compositions of the present invention containing the vinyl monomers of Formula I are especially useful in the polymerization of new polymers for a number of optical applications, especially in such high technology areas as optical fibers, optical instruments and equipment, electronics, coatings, laminates, and extruded or molded shapes and articles, for example, for equipment exposed to a corrosive environment such as integrated circuit fabricating equipment. Polymers for such applications may be polymerized from compositions containing vinyl monomers according to Formula I in which R is R1xe2x80x94CFHxe2x80x94CF2xe2x80x94 or R1xe2x80x94CFxe2x95x90CFxe2x80x94.
Coatings derived from compounds of the present invention may be applied for example, to capacitors, resistors, and integrated circuits, for the purpose of encapsulating them to protect them from harmful environment or to provide a highly dielectric layer; to plastic sheets or metal foils for the purpose of protecting them from damage or for making laminates; to interior walls of reactors, especially those employed in highly corrosive reactions with concentrated acids or with hydrofluoric acid, to protect them from corrosion; to light-transmissive devices such as optical lenses, prisms, and glazing to impart to them improved abrasion resistance or resistance against damage in corrosive environments; to glass or quartz cores for optical fibers to form a cladding; and recording heads, disks, and tapes, and to components of radio and microwave receiving equipment such as antenna dishes, etc. to protect them from mechanical or environmental damage.
The compounds of the present invention are also characterized by the ability to form coatings that, upon curing, possess unique and useful surface properties including excellent surface wetting and low surface tension prior to curing, and low surface energy, low friction and high slip, low flammability, high chemical resistance, and excellent moisture resistance after curing. It is believed that the desirable surface properties are the result of the fluorine-containing moieties migrating to the surface of cured coatings of the monomer compound, which contribute protective properties to the coating, as well. The fluorine-containing moieties also contribute surfactant-like qualities to the monomer compound that provide better flow, leveling and wetting, which is desirable for coating and ink compositions. Therefore, in addition to optical applications, the curable compositions of the invention containing the vinyl monomer of Formula I, including the monomers in which R is R1xe2x80x94CHFxe2x80x94CF2xe2x80x94 or R1xe2x80x94CFxe2x95x90CFxe2x80x94, find utility in numerous other areas, including, but not limited to, coatings, inks, photoresists, films, fibers, adhesives, insulators, laminates, elastomers, foams, molds and release coatings.
The present invention thus also provides for a curable composition comprising at least one compound of Formula I. When only a compound of Formula I is present, the resulting polymer is a homopolymer. When other monomers are present, a copolymer is produced.
The compositions may be curable by application of heat energy or exposure to actinic radiation. Initiator compounds may be employed. Microwave radiation may be used to apply heat to the composition. The compositions may also be catalytically cured with or without application of heat or exposure to actinic radiation by using an effective amount of a Lewis Acid catalyst, such as BF3. For example, the vinyl ether compounds of the present invention may be incorporated into sulfonic acid-cured epoxy maleate systems, which then cure at 300xc2x0 F. within 15 seconds. Compounds of Formula I in which R is R1xe2x80x94CHFxe2x80x94CF2xe2x80x94 or R1xe2x80x94CFxe2x95x90CFxe2x80x94 are included among the compounds that may be cured by using a Lewis Acid catalyst.
For purposes of the present invention, compositions that are curable by exposure to actinic radiation are defined as being xe2x80x9cphotocurable.xe2x80x9d Suitable sources of actinic radiation include light in the visible, ultraviolet or infrared regions of the spectrum, as well electron beam, ion or neutron beam or X-ray radiation. Actinic radiation may be in the form of incoherent light or coherent light such as light from a laser.
In photocuring processes, the actinic radiation is used to initiate addition polymerization of the vinyl ether compounds. Initiation of addition polymerization by actinic radiation is greatly enhanced by the use of photoinitiators. A unique feature of the present invention is that either free-radical or cationic photoinitiators may be employed. Free-radical photoinitiators propagate addition polymerization of terminal ethylenically unsaturated groups of the curable components in the compositions of the present inventions. Suitable free-radical photoinitiator compounds may be readily selected by those skilled in the art, and include, for example, DAROCUR 1173, DAROCUR 4265, IRGACURE 184, IRGACURE 261, IRGACURE 369, IRGACURE 500, IRGACURE 651, IRGACURE 784, IRGACURE 907, IRGACURE 1700, IRGACURE 2959, IRGACURE 1800, IRGACURE 1850, IRGACURE 819, AND IRGACURE 1300 (each commercially available from Ciba Specialty Chemicals) and GE-PI (commercially available from GE Corporation).
Cationic photoinitiator compounds propagate the addition polymerization of vinyl ether compounds, which include the curable components of the compositions of the present invention. Cationic photoinitiators undergo photolysis under the influence of actinic radiation, resulting in the formation of Lewis acids that, in turn, propagate the addition polymerization. Suitable cationic photoinitiator compounds may also be readily selected by those of skilled in the art, and include, for example, the onium salts conventionally employed as cationic photoinitiators, including triarylsulfonium and triaryliodonium salts.
The free radical or cationic initiator is present in an amount sufficient to effect polymerization of the curable component. The free radical or cationic initiator may comprise from about 0.01 to about 10% by weight, preferably from about 0.1 to about 6% by weight, and more preferably from about 0.5 to about 4% by weight of the total curable composition. Photocurable compositions contain an amount of a free radical or cationic photoinitiator within the foregoing ranges that is sufficient to effect photopolymerization of the photocurable component upon exposure to sufficient actinic radiation. Compounds of Formula I in which R is R1xe2x80x94CHFxe2x80x94CF2xe2x80x94 or R1xe2x80x94CFxe2x95x90CFxe2x80x94are included among the compounds that may be photocured using a cationic photoinitiator.
The amount of curable component in the curable compositions may vary widely. Depending upon the application, the component is present in an amount of from about 0.01 to about 99% by weight of the overall composition. For applications which rely upon physical properties of the curable compound other than surface properties, the curable component is preferably present in the curable composition at a level of at least about 35% by weight. In a preferred embodiment, the curable component is present in an amount of from about 80 to about 99% by weight, and, more preferably, from about 95 to about 99% by weight of the overall composition. Photocurable compositions contain an amount of the curable component within the foregoing ranges that is sufficient to photocure and provide image differentiation upon exposure to sufficient actinic radiation.
For applications which rely upon the ability of the curable component to modify the surface properties of other polymer systems, the curable component is preferably present in the curable composition at a level between about 0.10% and about 2.00% by weight. A level of about 0.50% by weight is preferred. For this aspect of the present invention, R is also R1xe2x80x94CFHxe2x80x94CF2xe2x80x94 and R1xe2x80x94CFxe2x95x90CFxe2x80x94.
In addition to the compound of Formula I, other curable compounds which are known in the art may be incorporated into the curable compositions of the present invention. These compounds include monomers, oligomers and polymers containing at least one terminal ethylenically unsaturated group and being capable of forming a high molecular weight polymer by free radical initiated, chain propagating addition polymerization. Suitable monomers include, but are not limited to, ethers, esters and partial esters of: acrylic and methacrylic acids; aromatic and aliphatic polyols containing from about 2 to about 30 carbon atoms; and cycloaliphatic polyols containing from about 5 to about 6 ring carbon atoms. Specific examples of compounds within these classes are: ethylene glycol diacrylate and dimethacrylate, diethylene glycol diacrylate and dimethacrylate, triethylene glycol diacrylate and dimethacrylate, hexane diacrylate and dimethacrylate, trimethylolpropane triacrylate and trimethacrylate, dipentaerythritol pentaacrylate, pentaerythrytol triacrylate, pentaerythrytol tetraacrylate and trimethacrylate, alkoxylated bisphenol-A diacrylates and dimethacrylates (e.g., ethoxylated bisphenol-A diacrylate and dimethacrylate and propoxylated bisphenol-A diacrylates and dimethacrylates), alkoxylated hexafluorobiphenol-A diacrylates and dimethacrylates and mixtures of the above compounds. Preferred monomers include multifunctional aryl acrylates and methacrylates. Preferred arylacrylate monomers include di-, tri- and tetraacrylates and methacrylates based on the bisphenol-A structure. More preferred arylacrylate monomers are alkoxylated bisphenol-A diacrylates and dimethacrylates such as ethoxylated bisphenol-A diacrylates and dimethacrylates, and ethoxylated hexafluoro-bisphenol-A diacrylates and dimethacrylates.
Suitable oligomers include, but are not limited to, epoxy acrylate oligomers, aliphatic and aromatic urethane acrylate oligomers, polyester acrylate oligomers, and acrylated acrylic oligomers. Epoxy acrylate oligomers (such as Ebecryl 600 by UCB) are preferred.
Suitable polymers include, but are not limited to, acrylated polyvinyl alcohols, polyester acrylates and methacrylates, acrylated and methacrylated styrene-maleic acid copolymers. Acrylated styrene-maleic acid copolymers are preferred.
Other curable compounds known in the art that may be incorporated into the curable compositions of the present invention include monomers, oligomers and polymers containing at least one terminal epoxide ring and being capable of forming a high molecular weight polymer by cationic ring-opening polymerization. Suitable epoxide-functional compounds include aromatic, aliphatic and mixed aromatic and aliphatic epoxy acrylates and polymers and oligomers thereof, epoxy novolaic polymers and oligomers, and cycloaliphatic epoxies, and polymers and oligomers thereof. Epoxy acrylate oligomers are preferred, including acrylated diglycidyl ethers of bisphenol-A, such as Ebecryl 600. Oligomers of diglycidyl ethers of bisphenol-A are also preferred.
Significantly, the vinyl ether compounds of the present invention polymerize with the ethylenically unsaturated and epoxide-functional compounds, either by free radical initiated chain propagation addition polymerization with the ethylenically unsaturated compounds, or, with cationic photoinitiators, by a combination of ring-opening polymerization of epoxide group and addition polymerization of vinyl ethers.
When other ethylenically unsaturated or epoxide-functional monomers, oligomers or polymers are employed, the weight ratio of the monomer compound of Formula I to the ethylenically unsaturated or epoxide-functional compounds may vary from about 0.1:99.9 to about 99:1, preferably from about 1:9 to about 9:1, and more preferably from about 25:75 to about 75:25.
Various optional additives may also be added to the curable compositions of the invention depending upon the application in which they are to be used. Examples of these optional additives include antioxidants, photostabilizers, volume expanders, fillers (e.g., silica and glass spheres), dyes, free radical scavengers, contrast enhancers and UV absorbers.
Antioxidants include such compounds as phenols and particularly hindered phenols including Irganox 1010 from Ciba Specialty Chemicals; sulfides; organoboron compounds; organophosphorus compounds; and N, Nxe2x80x2-hexamethylene-bis(3,5-di-tert-(butyl-4-hydroxy-hydrocinnamamide)) available from Ciba Specialty Chemicals under the trade name Irganox 1098. Photostabilizers and more particularly hindered amine light stabilizers include, but are not limited to, poly[(6-hexamethylene)2,2,6,6-tetramethyl-4-piperidinyl)imino)] available from Cytech Industries under the trade name Cyasorb UV3346. Volume expanding compounds include such materials as the spiral monomers known Bailey""s monomer. Suitable dyes include methylene green and methylene blue. Suitable free radical scavengers include oxygen, hindered amine light stabilizers, hindered phenols, and 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO). Suitable contrast enhancers include other free radical scavengers. UV absorbers include benzotriazoles and hydroxybenzophenone.
The additives may be used in amounts, based on the total composition weight, of from about 0 to about 6%, and preferably from about 0.1% to about 1%. Preferably all components of the curable composition are in admixture with one another, and, preferably, in a substantially uniform admixture.
The photocurable compositions of the invention can be used in the formation of the light transmissive element of an optical device. Examples of such devices are planar optical slab waveguides, channel optical waveguides, ribbed wave-guides, optical couplers, routers, combiners and splitters. The photocurable composition of the invention can also be used in the formation of negative working photoresists and other lithographic elements such as printing plates. In a preferred embodiment, the photocurable composition is used for producing a waveguide comprising a substrate containing a light transmissive element. Such waveguides are formed by applying a film of the photocurable composition of the invention to the surface of a suitable substrate. The film may be formed by any method known in the art, such as spin coating, dip coating, slot coating, roller coating and evaporation.
The substrate may be any material on which it is desired to establish a waveguide including semiconductor materials such as silicon, silicon oxide, gallium arsenide, polymers and compound materials. In the event the light transmissive region on the substrate is to be made from a photocurable material which has an index of refraction which is lower than that of the substrate, an intermediate buffer layer possessing an index of refraction which is lower than the substrate must be applied to the substrate before the photocurable composition is added. Otherwise, the light loss in the waveguide will be unacceptable. Suitable buffers are made from semiconductor oxides, lower refractive index polymers or spin on silicon dioxide glass materials.
Once a film of the photocurable composition is applied to the substrate, actinic radiation is directed onto the film in order to delineate the light transmissive region. That is, the position and dimensions of the light transmissive device are determined by the pattern of the actinic radiation upon the surface of the film on the substrate. The photopolymers of the invention are conventionally prepared by exposing the photocurable composition to sufficient actinic radiation. For purposes of this invention, xe2x80x9csufficient actinic radiationxe2x80x9d means light energy of the required wavelength, intensity and duration to produce the desired degree of polymerization action in the photocurable composition.
Sources of actinic light, exposure procedures, times, wavelengths and intensities may vary widely depending upon the desired degree of polymerization, the index of refraction of the photopolymer, and other factors known to those of ordinary skill in the art. The selection and optimization of these factors are well known to those skilled in the art.
Preferably the photochemical excitation is carried out with relatively short wavelengths (or high energy) radiation so that exposure to radiation normally encountered before processing (e.g., room lights) will not prematurely polymerize the polymerizable material. The energy necessary to polymerize the photocurable compositions of the invention generally ranges from about 5 mW/cm2 to about 200 mW/cm2 with typical exposure times ranging from 0.1 second to about 5 minutes.
After the photocurable composition has been polymerized to form a predetermined pattern on the surface of the substrate, the pattern is then developed to remove the non-image areas. Any conventional development method can be used such as flushing the non-irradiated composition with a solvent. Suitable solvents include polar solvents, such as alcohols and ketones. The most preferred solvents are acetone, methanol, tetrahydrofuran and ethyl acetate.
While the preferred embodiment of the invention involves photocuring the photocurable composition, as noted above, one skilled in the art will appreciate that many variations of the method within the scope of the claims are possible depending upon the nature of the curable composition. For example, the composition may be heat-cured in an oven or through another heat source such as microwave radiation. Alternately, the composition may be cured using a Lewis Acid catalyst. Depending upon the particular use, the photocurable composition may be partially cured before application to a surface and subsequently fully cured.
The present invention also provides for a polymer comprising one or more vinyl ether repeating units, alone or with other repeating units, wherein the vinyl ether repeating units have the formula:
wherein X and R are the same as described above with respect to Formula I. The vinyl ether repeating units are formed from the polymerization of compounds of Formula I.
In one embodiment, the polymer of the present invention may be a homopolymer comprising only a single vinyl ether repeating unit of Formula I, or the polymer may comprise two or more vinyl ether repeating units derived from different compounds of Formula I. In an alternative embodiment, the polymer of the present invention may include one or more second repeating units derived from other monomers, oligomers, or polymer compounds that have been copolymerized with a vinyl ether compound of the present invention, and which are disclosed above as additional curable compounds that may be included in the curable compositions of the present invention. The polymer of the present invention can contain as little as 0.01% by weight of the vinyl ether repeating unit or amounts in excess of 90% by weight.

Abstract: wherein R is a radical selected from R1xe2x80x94CnHmxe2x80x94, R1xe2x80x94CnHmxe2x80x94C(xe2x95x90O)xe2x80x94, R1xe2x80x94CnHmxe2x80x94CH[xe2x80x94Oxe2x80x94Xxe2x80x94Oxe2x80x94CHxe2x95x90CH2xe2x80x94], R1xe2x80x94CnHmxe2x80x94CH[xe2x80x94Oxe2x80x94Xxe2x80x94Oxe2x80x94CHxe2x95x90CH2xe2x80x94]C(xe2x95x90O)xe2x80x94, R1xe2x80x94CnHmxe2x80x94CH[xe2x80x94C(xe2x95x90O)xe2x80x94Oxe2x80x94Xxe2x80x94Oxe2x80x94CHxe2x95x90CH2xe2x80x94], R1xe2x80x94CnHmxe2x80x94CH[xe2x80x94C(xe2x95x90O)xe2x80x94Oxe2x80x94Xxe2x80x94Oxe2x80x94CHxe2x95x90CH2xe2x80x94]C(xe2x95x90O)xe2x80x94, R1xe2x80x94[CFClxe2x80x94CF2xe2x80x94]pCH2xe2x80x94 and HCFClxe2x80x94CF2xe2x80x94, wherein R1 is hydrogen, an unsubstituted or substituted fluorinated aliphatic radical, an unsubstituted or substituted fluorinated cyclic aliphatic radical, an unsubstituted or substituted fluorinated aromatic radical, an unsubstituted or substituted fluorinated araliphatic radical, or an unsubstituted or substituted fluorinated heterocyclic radical; n is an integer between 1 and 6, inclusive; nxe2x89xa6mxe2x89xa62n; p is an integer between 1 and 20, inclusive and X is an unsubstituted or substituted aliphatic radical, an unsubstituted or substituted cyclic aliphatic radical, an unsubstituted or substituted aromatic radical, an unsubstituted or substituted araliphatic radical, or an unsubstituted or substituted heterocyclic radical; provided that when R1 of R1xe2x80x94CnHmxe2x80x94 is an otherwise unsubstituted fluorinated aliphatic group, X is not ethylene or propylene. Curable compositions containing the vinyl ether compounds are also disclosed, as well as polymers polymerized from the vinyl ether compounds.


Systems and methods are provided for swellable material activation and monitoring in a subterranean well. A sensor system for use in a subterranean well includes a swellable material, and at least one sensor which is displaced to a wellbore surface in response to swelling of the swellable material. Another sensor system includes a sensor which detects swelling of a swellable material. A swellable well tool system includes a base pipe, a swellable material on an exterior of the base pipe, and eccentric weighting for inducing rotation of the swellable material about a longitudinal axis of the base pipe.

The present disclosure relates generally to equipment utilized and operations performed in conjunction with a subterranean well and, in an embodiment described herein, more particularly provides for swellable material activation and monitoring in a subterranean well.
While it has been known for many years that swellable materials are useful in subterranean wells, "intelligent" swellables have not progressed much beyond equipping swellable packers with certain sensors to detect, for example, pressure in and about the swellable material. However, the ability of a swellable material to conform to the shape of the wellbore surface which it contacts opens up a variety of possibilities for mapping the wellbore surface to, for example, determine the wellbore geometry, detect changes in stresses about the wellbore, evaluate packer differential pressure sealing capability, etc.
Furthermore, improvements are needed in detection of packer setting, evaluation of material swelling, utilization of swellable materials in well operations, etc. For these reasons and others, the present disclosure provides advancements in the art of swellable material activation and monitoring in a subterranean well, which advancements may be utilized in a variety of different applications.

Swellable material activation and monitoring in a subterranean well


A solution for managing information using an identification tag is provided. For example, information relating to an item and/or one or more transfers of the item can be managed using an identification tag associated with the item. The identification tag can store and transmit an item identifier, such as an electronic product code (EPC), corresponding to the item, which can be obtained and stored in a data store. Access information for retrieving the item identifier and identification information for a party to the transfer can be used to generate a custom identifier that can be provided for storage on the identification tag in place of the item identifier. The custom identifier can subsequently be used to acquire information on the item and/or the transfer event.

Radio frequency identification (RFID) technology continues to provide many advantages and benefits to both consumers and businesses in areas such as tracking goods, inventory, and logistic applications. For example, some industrial and commercial applications employ RFID technology to associate customer profiles with their product preferences. In an illustrative application, an RFID tag writer can write information to an RFID tag associated with an item when the item is purchased by an individual. The information can include information that uniquely identifies the individual in a database managed by the seller. Subsequently, should the individual return to the seller with the item, an RFID tag reader can acquire the identification information for the item and the individual and quickly provide an associate with information regarding the purchase.
However, information embedded on an RFID tag also can be acquired by an unauthorized and/or unintended RFID reader and/or tracking system, e.g., as an individual moves from one location to another while carrying an item including the RFID tag. In this case, the data can provide a third party with unauthorized information about a particular individual, e.g., a group of items being worn/carried by the individual.

Information management using a custom identifier stored on an identification tag

International Business Machines Corporation


A bias circuit includes a replica circuit for an amplifier circuit using a cascode type inverter, and a generation circuit that generates a bias voltage that causes a drain voltage of an input stage transistor of the amplifier circuit to be a saturation drain voltage, based on an output voltage of the replica circuit, and supplies the generated bias voltage to a cascode element of the amplifier circuit and a cascode element of the replica circuit.

Hitherto, an optical logic input circuit that feeds back output of a CMOS inverter to input has been known. CMOS stands for Complementary Metal Oxide Semiconductor. In addition, an amplifier circuit such as TIA using a cascode type CMOS inverter has been known. TIA stands for Transimpedance Amplifier.
However, in the above-described related art, when the characteristics of transistors used in the cascode type CMOS inverter is varied by variation in manufacturing processes, there is the case of decreased the output voltage range of the amplifier circuit using the CMOS inverter. For example, when a threshold voltage of the transistors used in the cascode type CMOS inverter is low, the output voltage range of the amplifier circuit using the CMOS inverter becomes narrow.
The following is a reference document.
[Document 1] Japanese Laid-open Patent Publication No. 63-36612.

Bias circuit with a replica circuit for an amplifier circuit and a generation circuit supplying bias voltage to the replica and amplifier circuits and optical receiver


A food and condiment kit comprising a container with a top, a bottom, and an interior. A tray coupled to the top of the container includes at least one opening to receive a cup with a first end facing the bottom of the container. A ring with an interior edge and a plurality of clasps disposed around the interior edge is coupled to the first end of the cup. A cutting mechanism coupled to the ring protrudes towards the first end of the cup. A lining covers the open end of the cup sealing the contents of the cup from the contents of the container until the cup is rotated around the cutting mechanism to cut the lining and thereby release the contents therein.

Conventional food or beverage and condiment kits for on-the-go use include a container filled with food such as salad and a separate packet containing a condiment such as salad dressing. A user opens the salad dressing packets to dispense salad dressing throughout the container. Although convenient, these packets are cumbersome because they typically distribute the salad dressing over the top layers of the salad, often resulting in an uneven distribution of salad dressing throughout the container. Oftentimes, when a user reaches the bottom of the container after consuming most of the salad, there is not enough salad dressing for the bottom layers because the majority of the salad dressing has already coated the upper layers.
U.S. Pat. No. 6,386,443 to Szczerbinski discloses a combination food and condiment dispenser which provides a compartment for ketchup, or a similar topping, clipped to the top of a French fry container.
U.S. Pat. No. 6,302,268 to Michaeli discloses a salad container having an insert chamber for salad dressing. The salad dressing is injected into the container at the top of the salad. This does not provide even distribution of the salad dressing through the salad because the dressing is concentrated towards the upper portion of the container.
U.S. Pat. No. 5,076,425 to Plone discloses a dispensing stick for dispensing a substance into a container. The stick is combined with a dispensing lid for convenience.
U.S. Patent Application No. 2009/0008274 discloses a food container having a chamber for separating a condiment packet from the food and dispensing the contents of the packet by engaging a spring activated chamber that controls the alignment of the packet with the container. The chamber includes a plurality of openings that align with openings in the packet to controllably release the contents of the packet through the openings in the chamber wall.
Although the above inventions are useful for convenience and combining condiments with food items, a need exists for evenly distributing condiments, toppings, or additives throughout a container having a food or beverage. There is also a need for an economical and efficient apparatus of doing the same.

Portable food or beverage and condiment kit


A pump can include a plunger and a barrel, at one stroke extent flow being substantially restricted between the plunger and the barrel at spaced apart positions and a plunger interior passage in filtered communication with a fluid chamber between the positions, and at an opposite stroke extent the fluid chamber being in communication with the standing valve. A method can include displacing a plunger in one direction, thereby receiving filtered liquid into a fluid chamber, and b) displacing the plunger in an opposite direction, thereby transferring the liquid to a barrel interior passage. A system can include an actuator that reciprocates a rod string, and a pump including a plunger with a traveling valve, a barrel with a standing valve, and a filter that filters liquid which flows from a tubing string to a compression chamber disposed between the traveling valve and the standing valve.

This disclosure relates generally to equipment utilized and operations performed in conjunction with a subterranean well and, in one example described below, more particularly provides an artificial lift pump suitable for pumping fluids with entrained gas and particulates.
Reservoir fluids can sometimes flow to the earth's surface when a well has been completed. However, with some wells, reservoir pressure may be insufficient (at the time of well completion or thereafter) to lift the fluids (in particular, liquids) to the surface. In those circumstances, technology known as "artificial lift" can be employed to bring the fluids to or near the surface (such as, at a land-based wellsite, a subsea production facility or pipeline, a floating rig, etc.).
Various types of artificial lift technology are known to those skilled in the art. In one type of artificial lift, a subsurface pump is operated by reciprocating a string of "sucker" rods deployed in a well. An apparatus (such as, a walking beam-type pump jack or a hydraulic actuator) located at the surface can be used to reciprocate the rod string.
Therefore, it will be readily appreciated that improvements are continually needed in the arts of constructing and operating artificial lift systems. Such improvements may be useful for lifting oil, water, gas condensate or other liquids from wells, and may be particularly useful in situations in which the liquids are produced along with gas and particulates (such as sand, formation fines, proppant etc.).

This patent is subject to a terminal disclaimer.

Method of pumping fluid from a wellbore by a subsurface pump having an interior flow passage in communication with a fluid chamber via a filter positioned in a side wall of a plunger


A method with which a textile sheet having good mechanical properties in respect to relatively high values regarding tear propagation resistance can be produced. The textile sheets are used in areas that require relatively high tear propagation resistance. The textile sheets also have relatively high peak tensile values and/or elongation at break values. The method for the production of a tear propagation-resistant textile sheet comprises providing a starting textile sheet made of yarns, fibers or filaments formed of at least two elementary filaments and having an arrangement in cross-section like orange segments or pie slices with the segments or slices made of different polymers, and exposing the starting textile sheet to a compressing heat treatment, wherein the polymer segments are permeated and a substantially non-adhesive bond is achieved between the polymer segments. The textile sheet may comprise nonwoven materials having a specific tear propagation resistance of equal to or greater than 0.4 N per g/m2 (according to Zungen method, ASTM D 2261).

One method for the production of propagation tear-resistant nonwoven materials made of bicomponent fibers with an islands-in-the-sea configuration is known from the document WO 2006/107695A2 or US 2006/0223405A1. A nylon/polyethylene polymer pair described therein, having a weight ratio of 75:25 with various islands-in-the-sea configurations, has a maximum specific tear propagation resistance of 0.22 N per g/m2 after calendaring.
The object of the present invention is to provide a method by which textile sheets may be produced with relatively good mechanical properties in terms of relatively high values with regard specifically to tear propagation resistance. The textile sheet of the invention are usable in areas that require relatively high tear propagation resistance of the textile sheet. Preferably, the textile sheet also has relatively high maximum tensile force values and/or elongation at break values.

Tear propagation-resistant textile sheet material, method making and use thereof


A bearing component is prepared from a carburazing steel and having a surface hardness of 63 to 67 in terms of Rockwell hardness C and a surface retained austenite content of at least 20% to less than 25%. The bearing component is produced by a process including the step of carburizing and quenching a bearing component workpiece prepared from a carburizing steel and machined to a predetermined shape, the step of subjecting the resulting workpiece to a preliminary tempering treatment, the step of subjecting the tempered workpiece to a sub-zero treatment and the step of subjecting the treated workpiece to a main tempering treatment. Further, the bearing component is produced by another process including the step of carburizing and quenching a bearing component workpiece prepared from a carburizing steel and machined to a predetermined shape, the step of subjecting the resulting workpiece to a secondary hardening treatment and the step of subjecting the hardened workpiece to a main tempering treatment.

The present invention relates to bearing components, and more particularly to bearing components suitable for use in bearings which are used in oils contaminated with extraneous matter having a Rockwell C hardness (hereinafter referred to as "HRC") of about 58 to about 63.
When bearings are used in oils contaminated with extraneous matter which is about 58 to about 63 in HPC, such as metal particles or molding sand, the life of the bearing reduces generally to 1/5 to 1/10 of the calculated life thereof or shorter. To improve the life of bearings in the case where they are used in contaminated oils containing extraneous matter, the present applicant has already proposed a bearing steel which is prepared from a carburizing steel and which is characterized by having a surface hardness of 63 to 66 in terms of HRC, a surface retained austenite content of 25 to 50% and a carburized case free from secondary carbide precipitates (see Unexamined Japanese Patent Publication No. 115344/1990).
However, in the case where components made of the conventional bearing steel described are used for bearings, the bearings vary in life and are not always satisfactory to use actually.

Bearing components and process for producing same


Integrated circuit (IC) structures including asymmetric, recessed source and drain regions and methods for forming are provided. In an example, the IC structure includes a substrate, a gate structure over the substrate, first and second spacers contacting respective, opposite sidewalls of the gate structure, and source and drain regions on opposite sides of the gate structure. In one configuration, the source region includes an upper source portion having a first lateral width, and a lower source portion having a second lateral width greater than the first lateral width, and the drain region includes an upper drain portion having a third lateral width, and a lower drain portion having a fourth lateral width that is substantially the same as the third lateral width.

For integrated circuit (IC) structures used in certain applications, for example, radio frequency (RF) applications, high source and drain resistance and/or high gate to source and drain capacitance reduces device performance. Techniques in addressing such issues with resistance and capacitance include source and drain region geometry tuning and/or doping profile tuning. However, conventional methods for reducing source and drain resistance often simultaneously increase the gate to source and drain capacitance. Similarly, techniques for reducing gate to source and drain capacitance often simultaneously increase source and drain resistance, thereby degrading drive performance.

Integrated circuit structure including asymmetric, recessed source and drain region and method for forming same


A charging device is provided. A charging device includes a charging section and a discharge product adsorption removal section. The charging section includes a shield case having a shield opening, a discharge electrode, and a rotation shaft which is parallel to a rotation axis of a photoreceptor. The discharge product adsorption removal section has an adsorption layer that adsorbs a discharge product and is disposed downward in a vertical direction of the photoreceptor. The charging section is displaceable about an axial line of the rotation shaft from a position where the shield opening opposes to the photoreceptor to a position where the shield opening opposes to the discharge product adsorption removal section.

1. Field of the Invention
The present invention relates to a charging device and an image forming apparatus provided with the device apparatus.
2. Description of the Related Art
In an image forming apparatus of an electrophotographic type, a charging device of a corona discharge type is used as a charging section which uniformly charges a photoreceptor which is an image bearing member to bear an electrostatic latent image thereon. Such a charging device of a corona discharge type is provided with a shield case having an opening opposing to a photoreceptor and a discharge electrode disposed in a stretched manner inside the shield case whose discharging surface is a linear, a pin array, or a needle shape. The charging device is a so-called corotron which charges a photoreceptor uniformly by applying high voltage to the discharge electrode so that a corona discharge is generated, or a so-called scorotron which provides a grid electrode between the discharge electrode and the photoreceptor so as to charge the photoreceptor uniformly by applying desired voltage to the grid electrode.
In the charging device of a corona discharge type, a discharge product such as nitrogen oxide (NOx) is produced. To be specific, by the energy released from the charging device along with the discharge of electrons, nitrogen molecule (N2) present in the air is dissociated into nitrogen atom (N), and the nitrogen atom is combined with oxygen molecule (O2) to thereby generate nitrogen oxide (nitrogen dioxide: NO2).
When nitrogen oxide is generated in this manner, the nitrogen oxide is adhered to the photoreceptor as ammonium salt (ammonium nitrate), which will be a cause of an abnormal image. In particular, in a case where an organic photoreceptor (OPC) is used as the photoreceptor, the image defection such as white voids or image deletion easily occurs by the nitrogen oxide.
To solve such a problem, Japanese Unexamined Patent Publication JP-A 2003-122187 discloses an image forming apparatus with a configuration in which a brush roller containing zeolite is caused to abut on an upward side of a photoreceptor. Furthermore, JP-A 2003-122187 discloses an image forming apparatus with a configuration in which a plate-like member containing zeolite is arranged on the upward side of the photoreceptor so as to oppose to the photoreceptor.
According to the image forming apparatus disclosed in JP-A 2003-122187, zeolite contained in the brush roller and the plate-like member has a property to adsorb the nitrogen oxide and the ammonium nitrate, and thereby it is possible to adsorb and remove the ammonium nitrate adhered on a surface of the photoreceptor with the brush roller to be frictionally sliding thereon, and adsorb and remove the discharge product such as nitrogen oxide floated in the air in a vicinity of the photoreceptor with the plate-like member. Thereby, it is possible to suppress occurrence of the image defection caused by the discharge product such as the ammonium nitrate adhered to the photoreceptor, nitrogen oxide floated in the air in the vicinity of the photoreceptor, and the like.
However, in the image forming apparatus disclosed in JP-A 2003-122187, since the brush roller containing zeolite adsorbs and removes the ammonium nitrate adhered on the photoreceptor by frictionally sliding thereon, there is a possibility that a scratch occurs on a surface of the photoreceptor and thereby the image defection due to the scratch occurs. Furthermore, in the image forming apparatus disclosed in JP-A 2003-122187, since the plate-like member containing zeolite is arranged on an upward side of the photoreceptor, it is impossible to remove the discharge product that flows toward downward side along the surface of the photoreceptor. Therefore, the image forming apparatus disclosed in JP-A 2003-122187 is not capable of sufficiently preventing occurrence of the image defection such as white voids or image deletion caused by the discharge product such as nitrogen oxide. Moreover, in the case of the charging device with a configuration in which the discharge electrode is provided in a stretched manner inside the shield case, the discharge product is retained at high concentrations in an inner space of the shield case after discharge operation, however, a configuration in which the discharge product retained in the inner space of the shield case is able to be removed without degrading charging performance is not disclosed in JP-A 2003-122187.

Charging device and image forming apparatus


The innovation process describes the process and results for fabrication of a magnetron sputter deposited fully dense electrolyte layer (8YSZ/GDC/LSGM) embedded in a high performance membrane electrolyte assembly (MEA) (Unit Cell) of Solid Oxide Fuel Cell. A single cell with airtight electrolyte layer (8YSZ/GDC/LSGM) is prepared via thin film technique of magnetron sputter deposition, combined with SOFC-MEA processing methods (such as tape casting, lamination, vacuum hot pressing, screen printing, spin coating, and plasma spray coating) and sintering optimization conditions. The gas permeability of the electrolyte layer is below 1×10−6 L/cm2/sec and the open circuit voltage/power density of the single cell performance test exceeds 1.0 V and 500 mW/cm2.

1. Field of the Invention
The invention relates to a manufacturing process for the electrolyte layer of solid oxide fuel cell. Especially it relates to a manufacturing process for a membrane, i.e. magnetron sputtering. It is also combined with the manufacturing process for membrane electrode assembly (MEA), like tape casting, lamination, vacuum hot pressing, screen printing, spin coating or plasma spray coating et al. and optimized sintering technology in a novel process for fully dense electrolyte to produce air-tight electrolyte layer for solid oxide fuel cell.
2. Description of the Prior Art
With rising oil price and consciousness of environmental protection, renewable energy technology has become one of the most important technological development in this century. Solid oxide fuel cell is a power generation system that has high efficiency, low pollution and diversified energy sources. Its simple material composition, modulized structure and sustainable and stable power generation ability make it the power generation system of the most potential.
Electrolyte supported cell (ESC) has its operation temperature between 800˜1000° C. Its electrolyte substrate thickness is around 150˜300 μm. This is the first generation of SOFC-MEA. Anode supported cell (ASC) has its operation temperature between 650˜800° C. Its electrolyte substrate thickness is around 10 μm. This is the second generation of SOFC-MEA. (NiO+8YSZ) (NiO, Nickel Oxide YSZ, Yttria-Stabilized Zirconta) is the anode material for ASC/ESC, while the main cathode material is LSM (Strontium doped lanthanum-magnetite) and LSCF (LSCF, Lanthanum Strontium Cobalt Ferrite) with thickness between 30˜60 μm. New electrolyte materials and cathode materials are under development in many research laboratories in the world. They all hope to develop new materials so the operation temperature for SOFC-MEA will drop to 500˜700° C. Then the components for SOFC Stack, like Inter-connector etc., can change from ceramic materials to metal materials, which are not only easy for manufacturing but also increase mechanical stability and durability, and also reduce overall cost. The development for this technology in universities and national laboratories emphasize material development and expect to develop novel materials to reduce resistance, increase ion conductivity and improve SOFC power generation.

Process for fabrication of a sputter deposited fully dense electrolyte layer embedded in a high performance membrane electrolyte assembly of solid oxide fuel cell


A cluster of processing systems wherein each system is set to operate at a unique operating frequency. Each unique frequency is set to differ from each other by at least a predetermined frequency differential or bandwidth. When clustered, the radiated emissions will not add. Rather, the RF energy is distributed over the predetermined frequency bandwidth and in so doing achieve a reduction of measured RF energy at any singular frequency. By using RF energy dispersal in aggregate systems, the need for special or additional RF shielding is precluded. Current design and manufacturing techniques can continue to be used. Thus, reducing the overall cost of implementing aggregated systems.

This invention pertains to the aggregation of computer systems and other devices requiring a clock or oscillator and, more particularly, to the mitigation of electromagnetic interference of the aggregation.
Devices that have embedded oscillators or clocks inherently emit electromagnetic energy. The energy is emitted at frequencies related to the fundamental frequency of the oscillator or clock. This emitted energy is both undesirable and parasitic to other devices. The related frequencies can be of any component of the oscillator frequency including the fundamental frequency and any harmonics thereof. The harmonic components of the fundamental frequency occur at multiples of the fundamental and at sums and differences between any two or more components.
Devices which have embedded oscillators or clocks require testing for compliance to several government agenciesxe2x80x9d established requirements. One such agency is the Federal Communications Commission. The established requirements maintain that emissions for any given device remain below a given threshold. The threshold corresponds to an amount of energy per predefined frequency bandwidth which energy could reasonably interfere with a neighboring device. The testing device used in order to determine compliance is usually a spectrum analyzer which sweeps all frequencies of interest and which reports the detected level of emissions per the predefined bandwidth throughout the sweep of frequencies.
Devices are currently produced with a fixed set of one or more oscillators which function as time keepers or clocks. These devices usually take the form of an electronics board assembled in a case with other ancillary parts and creating a working device. As singular elements, each completed device is certified to comply with the defined set of government agency requirements. When clustering and operating more than one of these devices in close proximity, the result is an integrated higher level system. It is this integrated system, the aggregation, when operating, that cannot be expected to meet the original agenciesxe2x80x9d criteria for each of the elements it is composed of. The problem is that the aggregation of systems generally exceeds the allowed energy/frequency levels set by one or more agencies.
An aggregation of devices is provided in which a subset or all of the devices are designed to operate in close proximity of each other. The subset or all of the devices are provided with a programmable oscillator or clock. The devices are linked through an inter-device link. Each proximate device contains a clock frequency controller which couples the inter-device link and the programmable oscillator or clock and which controls the frequency of the programmable oscillator or clock. The frequency of each proximate device is set to operate at a unique operating frequency. Each unique frequency is set to differ from each other by at least a predetermined frequency differential.

RF energy dispersal in systems consisting of aggregated computing elements as subsystems

International Business Machines Corporation


An image forming apparatus includes a main body of the image forming apparatus; at least one image forming unit disposed in the main body; a light scanning unit that is disposed in the main body and scans light to form an electrostatic latent image on a photosensitive medium of the at least one image forming unit; a window open-closing shutter that is disposed to slidably move on a surface of the light scanning unit from which light emits, and moves between an open position where a light moving path is opened and a blocking position where the light moving path is blocked; a shutter operating lever that is disposed in the main body, and activates the window open-closing shutter to be positioned at either of the open position and the blocking position; and a pressure member that is disposed in the main body and presses the shutter operating lever.

1. Field
The following description relates to an image forming apparatus. More particularly, the present disclosure relates to an image forming apparatus having a window open-closing shutter and a shutter operating lever that can selectively open and close a window member of a light scanning unit that scans light to form an electrostatic latent image.
2. Description of the Related Art
Generally, an electro-photographic image forming apparatus, such as a copy machine, a light printer, a facsimile machine, or a multifunctional product, for example, includes a light scanning unit scanning light corresponding to printing data for forming an electrostatic latent image on a photosensitive medium.
The light scanning unit uses an optical deflector, such as a rotating polygon mirror, to periodically deflect light emitted from a light source, and uses an −θ lens to focus the light on a surface of the photosensitive medium having photosensitivity, such as a photosensitive drum, to form an electrostatic latent image thereon.
The light scanning unit may include a window open-closing shutter that can selectively open and close a window member from which light is emitted to prevent the window member from being contaminated by developer and paper dust generated during printing.
However, in order to perform an open-closing operation, the window open-closing shutter of the conventional light scanning unit uses a separate driving apparatus and a power transmitting apparatus, such as gears or cams, to transmit power generated by the driving apparatus to the window open-closing shutter. Accordingly, the light scanning unit having the window open-closing shutter has a complex structure and a high material cost, and, due to the difficulty of assembly and repair, management fees of the image forming apparatus are increased.
Accordingly, the light scanning unit may be formed to have no window open-closing shutter. However, if there is no window open-closing shutter, when an image forming unit or a waste developer receptacle is separated from an image forming apparatus, developer is scattered so as to contaminate the window member of the light scanning unit, which results in an adverse effect on image quality.

Image forming apparatus having a window open-closing shutter


Various embodiments of the present disclosure provide a fuel cell system configured to modulate the flow of oxidant through the fuel cell system to maintain a desired temperature at the fuel cell stack. The fuel cell system is configured to control the flow of oxidant to maintain the desired temperature in the fuel cell stack based on temperature measurements of fluid outside of the fuel cell stack.

A fuel cell is an electrochemical conversion device that produces electricity by oxidizing a fuel. A fuel cell typically includes an anode, a cathode, and an electrolyte between the anode and the cathode. A fuel cell system usually includes multiple fuel cells electrically connected to one another in series via interconnects (sometimes collectively referred to as a "fuel cell unit") and several components configured to provide the fuel to the anodes of the fuel cells and an oxidant to the cathodes of the fuel cells. The oxygen in the oxidant is reduced at the cathode into oxygen ions that diffuse through the electrolytes into the anodes. The fuel is oxidized at the anodes, which produces electrons that flow through an electrical load.
Solid oxide fuel cell (SOFC) systems (and other high-temperature fuel cell systems) require a relatively high operating temperature, such as 1000 degrees Celsius, to maintain low internal electrical resistance and achieve optimal performance. Accordingly, there is a need for systems and methods for controlling high-temperature fuel cell systems to maintain a desired temperature in the fuel cell stack.

System and method for fuel cell stack temperature control


A scraper system to remove and deflect debris and soil from a disc gang mounted on an agricultural implement is provided. The scraper system includes a mounting bracket member supported at a common axle in support of the disc gang. The mounting bracket member is aligned generally parallel to and located forward of the common axle, and is mounted at a forward end of an elongated carry member supported from the common axle. The elongated carry member is generally aligned perpendicular relative to the common axle. A scraper blade is supported by a scraper arm mounted at the mounting bracket member and is located above the common axle. The location of the scrapper blade and the scraper arm allows a deflector plate to be located at the rearward end of the carry member.

Agricultural soil preparation equipment typically includes a disc configuration to be used for breaking up and smoothing the surface of cultivated fields in preparation for planting. The disc configuration is usually drawn by a tractor or other source of motor power, multiple disc configurations are often employed, where the forward disc configuration initially breaks up lumps and clods and a rear disc configuration reduces the fragments to still smaller size and smoothing the ground.
A typical disc configuration includes a main frame with several disc gang assemblies suspended therefrom. The disc gangs are generally mounted at an angle with respect to the forward direction of travel. Each gang assembly comprises a plurality of equally spaced disc blades mounted on an axle for rotation about a common axis. The axle is supported by a series of C-shaped spring elements configured to allow the disc gangs to flex with the contour of the landscape as the agricultural implement is drawn by the tow vehicle.
In wet weather or in heavy, sticky soil conditions, earth tends to cling to the disc blades. In order to smooth the ground properly, it is desirable that this earth be removed frequently or even continuously. Otherwise the accumulation of soil and residue adhering to the discs can adversely affect disc operation. To eliminate the accumulation of soil and residue, scraper devices have been developed to keep the surfaces of the discs near their circumferences clear of the soil and residue.
U.S. Pat. No. 4,127,179 discloses a scraper mechanism for a disc gang harrow. The scraper mechanism includes a scraper blade supported from a mounting bracket fixedly attached to a tool bar of an agricultural implement to be towed. The scraper blade is generally aligned in a downward direction so as to bias against the disc blade. The disc gang is suspended from the toolbar by a series of bearing-supporting arms which carry bearing assemblies at their lower end and rotatable support of a common shaft. The scraper blades are rigidly supported to the toolbar and likewise tend to bounce in relation to the disc gang. Also, the vertically aligned scraper blades tend to yield and break from miscellaneous forces (e.g., contact with debris flow caused by cutting action of the disc blade) associated with operation in the field. When the mounting bracket or fastener breaks, the scraper arm and attached scraper blade are usually lost in the field. Also, soil and residue flow tend to be carried from the rear of the rotating blades to up and forward over the top of the disc gang spools and be trapped behind the disc gang cushion spring and on the top of the gang bearing assembly. When this happens, the soil and residue mixture can be compacted between the disc blades and the cushion spring and prevent the proper operation of the disc gang.


A method for controlling the speed of a work vehicle towing an implement that is movable between a working position, in which ground engaging tools of the implement are configured to perform a field operation, and a transport position, in which the ground engaging tools are raised relative to the ground. The method may include monitoring, with a computing device, an implement weight supported by the implement while the implement is in the transport position. The method may further include comparing, with the computing device, the implement weight to a predetermined threshold weight. Additionally, the method may include, when the implement weight differs from the predetermined threshold weight, adjusting, with the computing device, a maximum speed limit for the work vehicle.

A wide range of implements are known, are presently in use, and are particularly designed for towing behind a work vehicle. For example, agricultural implements, such as planters, typically include multiple row units distributed across a width of the implement and a configured to be towed behind a tractor. In a working position of the planter, each row unit is configured to deposit seeds at a desired depth beneath the soil surface, thereby establishing rows of planted seeds. For example, each row unit may include a ground engaging tool or opener (e.g., an opener disc) that forms a seeding path for seed deposition into the soil. As the implement travels across a field, the opener excavates a trench into the soil, and seeds are deposited into the trench. When the planter is moved into a transport position, the planter is raised such that the row units no longer engage the ground (i.e., the ground engaging tools of the planter are raised relative to the ground).
Agricultural implements have tires that are rated to carry a certain weight at speeds up to a maximum rated speed. As the weight of the implement increases (e.g., due to heavier loads), the maximum rated speed of the implement tires begins to drop. Typically, the maximum rated speed of the implement tires is much lower than the maximum speed of the work vehicle. During an agricultural operation, such as a planting operation, the agricultural implement is typically towed by the work vehicle at speeds well below the maximum rated speed and load of the implement tires to preserve the quality of the agricultural operation. As such, the towing speed during an agricultural operation usually does not come close to the maximum rated speed or load of the implement tires. However, during transport, the implement is not limited by the quality of the agricultural operation. As such, the implement may be towed at higher speeds during transport, which may include speeds above the maximum rated speed for the load on implement tires.
Currently, there is no way to prevent an operator of the work vehicle from towing the agricultural implement at speeds above the maximum rated speed for the load on the implement tires. While more robust tires could be selected that would allow the work vehicle to safely tow the loaded implement at speeds closer to the maximum speed of the work vehicle, such tires may be prohibitively expensive.
Accordingly, a system and method for controlling the speed of a work vehicle towing an implement would be welcomed in the technology.

System and method for controlling the speed of a work vehicle towing an implement


A device for monitoring adherence of a patient to a prescribed regimen is provided. The device has a pulmonary delivery device fluid, an adapter in communication with the delivery device and a dispenser in fluid communication with the adapter. A pressurized drug, contained in the pulmonary delivery device, can be delivered from the pulmonary delivery device to the patient through the adapter and the dispenser. A sensor is mounted to the adapter or the dispenser for detecting a temperature or pressure change caused by the movement of the drug from the pulmonary delivery device to the patient and generating a feedback signal based on the change. The feedback signal is further processed for generating a signal indicating a successful deliver of the drug to the patient.

It has been consistently documented that poor adherence to a prescribed inhaled therapy has led to detrimental outcome. For example, non-adherence of a prescribed inhaled medicine regimen has resulted in an estimate that it is the fourth highest cause of death in the United States. In England alone, it has been estimated that the direct cost to the National Health Service associated with unused medicine amounts to over 300 million pounds with a concomitant increase of over 500 million pounds per year in healthcare costs arising from failing to adhere to the prescribed treatment. Particularly, with respect to asthma, there are currently 5.4 million people in the United Kingdom receiving treatment for asthma, and it has been estimated that over 130 million pounds per year treatment cost savings can be realized in England, if interventions were made to ensure that all patients were at least 80% adherent to their prescribed regimen. Inhaler therapy forms a major part of treatment of patients with COPD. Therefore, it imperative to contemplate a device and method for ensuring the patients' adherence to a prescribed regimen.

Device and method for monitoring adherence to inhaled therapy


A system and method for automatically provisioning a composite telecommunications product comprising a plurality of sub-products or services in response to a single customer order are provided. A composite telecommunications product may comprise, for example, Internet Access (IA), Voice over Internet Protocol (VoIP), and Internet Protocol Television (IPTV) services bundled together as a single product. The present invention allows all three sub-products to be automatically provisioned in response to a single customer order for the composite product.

The rapid advances in communications technologies of recent years have greatly expanded the service options available to telecommunications consumers. Today consumers have choices over the types of services they choose to employ, as well as the technology platforms on which they elect to receive such services. Just a small sampling of the types of services consumers may take advantage of include voice communication, email, instant messaging, text messaging, internet access, audio and video broadcast services, and so on. Voice services may be provided over traditional land lines, wirelessly via a cellular telephone network, or over packet switched networks using Internet Protocols. Audio and video, traditionally broadcast wirelessly over the public airwaves as radio and television signals, are now available via broadband cable networks or as streaming media over the internet using Internet Protocols as the media transport layer. In sum, there are many different communications services available today. Likely there will be many more available in the near future. And there will be ever more flexible ways of delivering communications services to customers.
The proliferation of new services and the new mechanisms for delivering them provide great opportunities for telecommunications service providers. New services provide opportunities for new sales. In this environment the ability to quickly develop and roll out new telecommunications products and services will be a great competitive advantage. What is more, customers typically rely on a suite of telecommunications products and services to meet their communications needs. Often it is more convenient for customers to purchase or subscribe to a single umbrella product that is a composite of all of the individual products and services the customer needs. For example, a customer may wish to receive internet access, voice communications and television service from a single source and delivered via an IP network connection. Preferably the customer will purchase all three services as a single composite product that incorporates internet access (IA), voice over internet protocol service, and internet protocol television service (IPTV). For convenience, the composite product may be given its own descriptive name. For example, the product including IA, VoIP, and IPTV may be referred to as "Triple Play" based on the three services incorporated into a single product.
For customer service, accounting, and other business reasons, it is desirable to treat a composite telecommunications product such as the Triple Play product as a single product as opposed to an aggregation of individual products sold separately. Operationally, however, each service must be individually provisioned and activated whenever a customer purchases the composite product.
An end-to-end solution for provisioning the sub-products and services associated with a composite telecommunications services product is desirable. Preferably such a system would be capable of provisioning and activating multiple services and telecommunications products based on a single customer order for a single composite product. Such a system should be capable of monitoring the provisioning of each service and reporting exceptions, as well as reporting when all provisioning tasks for all of the services are complete.

Network layer integration for supporting internet access, voice over internet protocol, and internet protocol television services


An accessory connecting shelf for video and camera includes a horizontal orientated connecting plate (1) having double-step connecting pieces. A screwed connecting through hole (3) is provided in the higher connecting piece (2) at the inside end of the connecting plate for connecting a video and camera apparatus, and a chute (5) is provided in the lower connecting fpiece (4) at its outside end. An arc support (6) is connected to the chute, wherein the lower end of the arc support is connected with the lower connecting piece by a connecting screw (7) passing through the chute, and the upper end of the arc support is provided with an arc chute (9). Hot shoe holders (10) are provided within the arc chute for connecting accessories. The present invention not only enables several hot shoe holders to be installed simultaneously to connect several accessories, but also can flexibly adjust various orientations to meet the requirements of different shooting angles.

a) Field of the Invention
The present invention relates to an accessory connecting shelf for video and camera.
b) Background of the Invention
Currently, in order to achieve certain effects or realize some functions, a commonly used small-size video or camera needs to be installed with some accessories when videos or pictures are being taken, such as flash, video light, microphone, and the like. In order to install such accessories, nowadays, the commonly used tool is a flat-plate connecting shelf. However, only one accessory can be installed on the flat-plate connecting shelf once, and moreover the directional angle of the accessory cannot be changed, rendering the use thereof inconvenient. Generally, a viewfinder of a small-size home video camera can be folded and placed on a side of the video camera, so it may hamper the opening of the viewfinder and in turn influence normal usage of the video camera if the flat-plate connecting shelf is used for installing the accessory.

Accessory connecting shelf for video and camera


Digital ink strokes may be fragmented to form a training data set. A neighborhood graph may be formed as a plurality of connected nodes. Relevant features of the training data may be determined in each fragment such as local site features, interaction features, and/or part-label interaction features. Using a conditional random field which may include a hidden random field modeling parameters may be developed to provide a training model to determine a posterior probability of the labels given observed data. In this manner, the training model may be used to predict a label for an observed ink stroke. The modeling parameters may be learned from only a portion of the set of ink strokes in an unsupervised way. For example, many compound objects may include compositional parts. In some cases, appropriate compositional parts may be discovered or inferred during training of the model based on the training data.

MRFs model the joint distribution, i.e., p(y,x), over both the observed image data x and the image fragment labels y. However, if the ultimate goal is to obtain the conditional distribution of the image fragment labels given the observed image data, i.e., p(y|x), then conditional random fields ("CRFs") may model the conditional distribution directly. Conditional on the observed data x, the distribution of the labels y may be described by an undirected graph. From the Hammersley-Clifford Theorem and provided that the conditional probability of the labels y given the observed data x is greater than 0, then the distribution of the posterior probability of the labels given the observed data P(y|x) may factorize according to the following equation:
                              P                                (                              y                                            x            )                          =                              1                          Z                                            (                x                )                                                                                O              ~                        c                                                        Y              c                                                  (                                                y                  c                                ,                x                            )                                                          (        1        )
The product of the above equation runs over all connected subsets c of nodes in the graph, with corresponding label variables denoted yc associated with observed data denoted x, and a normalization constant denoted Z(x) which is often called the partition function.
Markov random fields ("MRFs") have been used to model spatial distributions such as those arising in image analysis. For example, patches or fragments of an image may be labeled with a label y based on the observed data x of the patch.