The invention describes the use of micronized organic UV filters for preventing tanning and for lightening human skin and hair, and their use in cosmetic and pharmaceutical formulations.

The present invention relates to the use of mixtures of micronized organic UV filters for preventing tanning and for lightening human skin and hair and to their use in cosmetic and pharmaceutical formulations.
It is known that certain organic UV filters, for example sparingly soluble benzotriazole or triazine compounds, have excellent UV filter properties if they are in micronized form.
Particularly in Asiatic countries, there is great interest in light protection filters or mixtures of light protection filters which preserve the colour of the skin following solar irradiation and, moreover, are able to impart a lighter appearance to the skin.
The object of the present invention is therefore to find micronized organic UV filters which prevent tanning of the skin and at the same time are able to lighten the skin.
Surprisingly, we have now found that micronized organic UV filters or mixtures of at least two micronized UV filters can achieve this object.
The present invention therefore provides for the use of mixtures of micronized organic UV filters for preventing tanning and for lightening of human skin.
Suitable UV filters which can be used according to the invention are organic, sometimes sparingly soluble, compounds, for example triazine derivatives, in particular hydroxyphenyltriazine compounds or benzotriazole derivatives, amides containing a vinyl group, cinnamic acid derivatives, sulfonated benzimidazoles, Fischer base derivatives, diphenylmalonitriles, oxalylamides, camphor derivatives, diphenylacrylates, paraaminobenzoic acid (PABA) and derivatives thereof, salicylates, benzophenones and also other classes of substance known as UV filters.
Preferred triazine derivatives which can be used according to the invention correspond to the formula
in which
R1, R2 and R3, independently of one another, are hydrogen; OH; C1-C18alkoxy; xe2x80x94NH2; xe2x80x94NHxe2x80x94R4; xe2x80x94N(R4)2; xe2x80x94OR4,
R4 is C1-C5alkyl; phenyl, phenoxy, anilino or pyrrolo which are unsubstituted or substituted by one, two or three OH groups, carboxyl, xe2x80x94COxe2x80x94NH2, C1-C5alkyl or C1-C5alkoxy; a methylidenecamphor group; a group of the formula xe2x80x94(CHxe2x95x90CH)mC(xe2x95x90O)xe2x80x94OR4; a group of the formula
xe2x80x83or the corresponding alkali metal, ammonium, mono-, di- or tri-C1-C4alkylammonium, mono-, di- or tri-C2-C4alkanolammonium salts, or C1-C3alkyl esters thereof; or a radical of the formula (1a)
R5 is hydrogen; unsubstituted C1-C5alkyl or C1-C5alkyl substituted by one or more OH groups; C1-C5alkoxy; amino; mono- or di-C1-C5alkylamino; M; a radical of the formula
Rxe2x80x2, Rxe2x80x2 and Rxe2x80x2xe2x80x3, independently of one another, are unsubstituted C1-C14alkyl or C1-C14alkyl substituted by one or more OH groups;
R6 is hydrogen; M; C1-C5alkyl; or a radical of the formula xe2x80x94(CH2)m2xe2x80x94Oxe2x80x94T1;
M is a metal cation;
T1 is hydrogen; or C1-C8alkyl;
m is 0 or 1
m2 is 1 to 4; and
m3 is 2to 14.
Further preferred triazine derivatives which can be used according to the invention correspond to the formula
in which
R7 and R8, independently of one another, are C1-C18alkyl; C2-C18alkenyl; a radical of the formula xe2x80x94CH2xe2x80x94CH(xe2x80x94OH)xe2x80x94CH2xe2x80x94Oxe2x80x94T1; or
R7 and R8 are a radical of the formula (2a)
R9 is the direct bond; a straight-chain or branched C1-C4alkylene radical or a radical of the formula xe2x80x94Cm1H2m1xe2x80x94Oxe2x80x94;
R10, R11, and R12, independently of one another, are C1-C18alkyl; C1-C18alkoxy or a radical of the formula
R13 is C1-C5alkyl;
m1 is 1 to 4;
p1 is 0 to 5;
A1 is a radical of the formula
xe2x80x83or of the formula
R14 is hydrogen; C1-C10alkyl, xe2x80x94(CH2CHR16xe2x80x94O)n1xe2x80x94R15; or a radical of the formula xe2x80x94CH2xe2x80x94CH(xe2x80x94OH)xe2x80x94CH2xe2x80x94Oxe2x80x94T1;
R15 is hydrogen; M; C1-C5alkyl; or a radical of the formula xe2x80x94(CH2)m2xe2x80x94Oxe2x80x94(CH2)m3xe2x80x94T1;
R16 is hydrogen; or methyl;
T1 is hydrogen; or C1-C8alkyl;
Q1 is C1-C18alkyl;
M is a metal cation;
m2 and m3, independently of one another, are 1 to 4; and
n1 is 1 to 16.
Very particularly preferred triazine derivatives of the formula (2) correspond to the formulae
in which
R17 and R18, independently of one another, are C3-C18alkyl; or xe2x80x94CH2xe2x80x94CH(xe2x80x94OH)xe2x80x94CH2xe2x80x94Oxe2x80x94T1;
R19 is C1-C10alkyl or a radical of the formula
R20 is hydrogen; M; C1-C5alkyl; xe2x80x94NHxe2x80x94C1-C5alkyl; preferably xe2x80x94NH-tert-alkyl; or a radical of the formula xe2x80x94(CH2)mxe2x80x94Oxe2x80x94T2;
T1 and T2, independently of one another, are hydrogen; or C1-C5alkyl; and
m is 1 to 4.
Of very particular interest are compounds of the formula (2a) and (2b) in which
R17 and R18, independently of one another, are C1-C18alkyl; or xe2x80x94CH2xe2x80x94CH(xe2x80x94OH)xe2x80x94CH2xe2x80x94Oxe2x80x94T1;
R19 is C1-C10alkyl;
and compounds of the formula (2c) and (2d) in which
R17 and R18, independently of one another, are C1-C18alkyl or xe2x80x94CH2xe2x80x94CH(xe2x80x94OH)xe2x80x94CH2xe2x80x94Oxe2x80x94T1; and
T1 is hydrogen; or C1-C5alkyl.
Of the utmost interest are triazine compounds of the formula (2a)-(2d) in which R17 and R18 have the same meanings.
Further interesting triazine compounds which can be used according to the invention correspond to the formula
in which
R21 is C1-C30alkyl; C2-C30alkenyl; unsubstituted C5-C12cycloalkyl or C5-C12cycloalkyl mono- or polysubstituted by C1-C5alkyl; C1-C5alkoxy-C1-C12alkyl; amino-C1-C12alkyl; C1-C5monoalkylamino-C1-C12alkyl; C1-C5dialkylamino-C1-C12alkyl; a radical of the formula (3a)
xe2x80x83or (3b)
xe2x80x83in which
R22, R23 and R24, independently of one another, are hydrogen, xe2x80x94OH; C1-C30alkyl, C2-C30alkenyl,
R25 is hydrogen; or C1-C5alkyl;
m1 is 0 or 1; and
n1 is 1 to 5.
Preferred compounds correspond to the formula
r and s, independently of one another, are 0 to 20.
Examples of triazine derivatives which can be used according to the invention correspond to the formulae
and also 2,4,6-tris(diisobutyl-4xe2x80x2-aminobenzalmalonate)-s-triazine and 2,4-bis(diisobutyl-4-aminobenzalmalonate)-6-(4xe2x80x2-aminobenzylidenecamphor)-s-triazine.
Likewise preferred triazine compounds which can be used according to the invention are described in EP-A-654469, for example the compound of the formula
According to the invention, particularly suitable triazine compounds are those described, for example, in EP-A-0,818450, for example the compound of the formula
Very particularly preferred triazine derivatives which can be used according to the invention correspond to the formula
R27, R28 and R29, independently of one another, are a radical of the formula
R30 is hydrogen; alkali metal; an ammonium group xe2x80x94N(R33)4,
R33 is hydrogen; C1-C5alkyl; or a polyoxyethylene radical which has 1 to 10 ethylene oxide units and the terminal OH group can be etherified with a C1-C5alcohol;
R31 is hydrogen; xe2x80x94OH; or C1-C6alkoxy;
R32 is hydrogen or xe2x80x94COOR30; and
n is 0 or 1.
If R30 is alkali metal, this is in particular potassium or very particularly sodium. (R33)4 is in particular a mono-, di- or tri-C1-C4alkylammonium salt, a mono-, di- or tri-C2-C4alkanol-ammonium salt or a C1-C3alkyl ester thereof.
If R33 is a C1-C3alkyl group, this is in particular a C1-C2alkyl group, in particular a methyl group, and if R33 is a polyoxyethylene radical, then the latter contains in particular 2 to 6 ethylene oxide units.
Preferred benzotriazole compounds which can be used according to the invention correspond to the formula
T1 is C1-C5alkyl or, preferably, hydrogen; and
T2 is C1-C5alkyl, preferably t-butyl, or phenyl-substituted C1-C4alkyl, in particular xcex1,xcex1-dimethylbenzyl.
A further preferred class of benzotriazole compounds which can be used according to the invention corresponds to the formula
T2 is as defined in formula (26).
Other very particularly preferred benzotriazole compounds which can be used according to the invention correspond to the formula
T2 is as defined in formula (26) and is preferably methyl, t-butyl or isooctyl.
Preferred vinyl-containing amides which can be used according to the invention correspond to the formula
R33xe2x80x94(Y)mxe2x80x94COxe2x80x94C(R34)xe2x95x90C(R35)xe2x80x94N(R36)(R37),xe2x80x83xe2x80x83(29)
in which
R33 is C1-C5alkyl, preferably methyl or ethyl, or unsubstituted phenyl or phenyl substituted by one, two or three of the radicals OH, C1-C5alkyl, C1-C5alkoxy or COxe2x80x94OR33;
R34, R35, R36 and R37, independently of one another, are C1-C5alkyl, preferably methyl or ethyl; or hydrogen;
Y is xe2x80x94NH or xe2x80x94Oxe2x80x94; and
m is as defined above.
Preferred compounds of the formula (29) are 4-methyl-3-penten-2-one, ethyl 3-methyl-amino-2-butenoate, 3-methylamino-1-phenyl-2-buten-1-one and 3-methylamino-1-phenyl-2-buten-1-one.
Preferred cinnamides which can be used according to the invention correspond to the formula
R38 is hydrogen or C1-C5alkoxy, preferably methoxy or ethoxy;
R39 is hydrogen or C1-C5alkyl, preferably methyl or ethyl; and
R40 is xe2x80x94(CONH)m-phenyl, in which m is as defined above, and the phenyl group is unsubstituted or substituted by one, two or three of the radicals OH, C1-C3alkyl, C1-C3alkoxy or COxe2x80x94OR30.
R40 is preferably phenyl, 4-methoxyphenyl or the phenylaminocarbonyl group.
Further preferred cinnamic acid derivatives are 2-ethylhexyl 4-methoxycinnamate or isoamylate or inter alia the cinnamic acid derivatives disclosed in U.S. Pat. No. 5,601,811 and WO 97/00851.
Preferred sulfonated benzimidazoles which can be used according to the invention correspond to the formula
M is hydrogen or an: alkali metal, preferably sodium, an alkaline earth metal, for example magnesium or calcium, or zinc.
Preferred Fischer base aldehydes which can be used according to the invention correspond to the formula
R41 is hydrogen; C1-C5alkyl; C1-C18alkoxy; or halogen;
R42 is C1-C8alkyl; C5-C7cycloalkyl; or C6-C10aryl;
R43 is C1-C18alkyl or a radical of the formula (32a)
R44 is hydrogen; or a radical of the formula
R45 is
xe2x80x83C1-C18alkoxy; or a radical of the formula
R46 and R47, independently of one another, are hydrogen; or C1-C5alkyl;
R48 is hydrogen; C1-C5alkyl; C5-C7cycloalkyl; phenyl; phenyl-C1-C3alkyl;
R49 is C1-C18alkyl;
X is Hal; a radical of the formula (32c)
n is 0 or 1.
Further compounds which can be used with preference correspond to the formula
R50, R51, R52, R53, R54, independently of one another, are hydrogen, C1-C8alkyl or C5-C10cycloalkyl;
R55 is hydrogen; C1-C8alkyl; C5-C10cycloalkyl; hydroxyl; C1-C8alkoxy; COOR56; or
R56, R57 and R58, independently of one another, are hydrogen or C1-C6alkyl;
X and Y, independently of one another, are hydrogen, xe2x80x94CN; CO2R59; CONR59R60; or COR59; where the radicals X and Y may additionally be a C1-C8alkyl radical, a C5-C10alkyl radical, in particular phenyl, or a heteroaryl radical having 5 to 6 ring atoms, where, in addition, X and Y or
R50 together with one of the radicals X and Y can represent the radical to complete a 5- to 7-membered ring which may contain up to 3 heteroatoms, in particular oxygen and/or nitrogen, where the ring atoms may be substituted, in particular by exocyclically double-bonded oxygen (keto oxygen) and/or C1-C8alkyl and/or C5-C10cycloalkyl radicals, and/or may contain Cxe2x95x90C double bonds;
Z is hydrogen; ammonium; alkali metal ion; in particular lithium, sodium, potassium, 1/2 equivalents of alkaline earth metal ion, preferably calcium, magnesium or the cation of an organic nitrogen base used to neutralize the free acid group,
R59 and R60, independently of one another, are hydrogen, C1-C8alkyl or C5-C10cycloalkyl; and
n and m, independently of one another, are 0 or 1.
Preferred diphenylmalonitriles which can be used according to the invention correspond to the formula
R61 and R62, independently of one another, are C1-C12alkyl; or C1-C12alkoxy; and
n is 0-3.
Other organic UV filters which can be used according to the invention correspond to the formula
R63 and R64, independently of one another, are C1-C5alkyl, in particular ethyl.
Other preferred chemical compound classes of UV filters which can be used according to the invention are:
p-aminobenzoic acid derivatives (PABA), in particular 2-ethylhexyl 4-dimethylamino-benzoate;
salicylic acid derivatives, in particular 2-ethylhexyl salicylates; homosalates; and isopropyl salicylates;
benzophenone derivatives, in particular benzophenone-2, -3, and -4;
dibenzoylmethane derivatives, in particular 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-propane-1,3-dione or butylmethoxydibenzoylmethane;
diphenylacrylates, in particular 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, ethyl 2-cyano-3,3xe2x80x2-diphenylacrylate and 3-(benzofuranyl) 2-cyanoacrylate;
3-imidazol-4-ylacrylic acid and 3-imidazol-4-yl acrylate;
benzofuran derivatives, in particular the p-aminophenylbenzofuran derivatives published in EP-A-582,189, U.S. Pat. Nos. 5,338,539 and 5,518,713;
camphor derivatives, in particular 3-(4xe2x80x2-methyl)benzylidenebornan-2-one, 3-benzyidenebornan-2-one, N-[2(and 4)-2-oxyborn-3-ylidenemethyl)benzyl]acrylamide polymer, 3-(4xe2x80x2-trimethylammonium)benzylidenebornan-2-one methylsulfate, 3,3xe2x80x2-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxobicyclo[2.2.1]heptane-1-methanesulfonic acid) and salts thereof, 3-(4xe2x80x2-sulfo)benzylidenebornan-2-one and salts thereof; and
menthyl o-aminobenzoate.
The UV filters listed above can be used according to the invention as individual compounds or also, preferably, as mixtures.
Preference is given to using the following mixtures of organic UV filters:
mixtures of methylenebisbenzotriazolyltetramethylbutylphenol and octyltriazone;
mixtures of octyltriazone and methylenebisbenzotriazolyltetramethylbutylphenol;
mixtures of 2-[(2,4-methoxy)phenyl]-4,6-bis[(2-hydroxy-4-methoxy)phenyl]-(1,3,5)triazine and methylenebisbenzotriazolyltetramethylbutylphenol;
mixtures of methylenebisbenzotriazolyltetramethylbutylphenol and dioctylbutamidotriazone;
mixtures of methylenebisbenzotriazolyltetramethylbutylphenol and octyl-2,2xe2x80x2-methylenebis[6-(2H-benzotriazol-2-yl)-4-methylphenol,
mixtures of octyltriazone and trisresorcinyltriazine;
mixtures of 2,2xe2x80x2-methylenebis[6-(2H-benzotriazol-2-yl)-4-methylphenol, octyltriazone and the compound of the formula (36)
mixtures of 2,2xe2x80x2-methylenebis[6-(2H-benzotriazol-2-yl)-4-methylphenol, octyltriazone and the compound of the formula (37)
mixtures of methylenebisbenzotriazolyltetramethylbutylphenol, octyltriazone and the compound of the formula (38)
mixtures of methylenebisbenzotriazolyltetramethylbutylphenol and the compound of the formula (39)
mixtures of methylenebisbenzotriazolyltetramethylbutylphenol, dioctylbutamidotriazone and the compound of the formula (37).
In the radicals defined above, C1-C18alkyl are straight-chain or branched alkyl radicals, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.
C1-C18Alkoxy radicals are straight-chain or branched alkyl radicals, for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy or octadecyloxy.
C2-C18Alkenyl is, for example, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
The mixtures of micronized organic UV filters which can be used according to the invention can be prepared in different ways.
Firstly, at least two of the abovementioned organic UV filters can be mixed as individual substances in the preparation process of the microparticles (micronization).
Another preparation option involves thoroughly mixing the already micronized individual substances of the UV filters together.
A third preparation option involves melting together at least two of the abovementioned UV filters. Cooling the melt produces a homogeneous composite, which is micronized in the usual manner.
The homogeneous composites of at least two organic UV filters are also provided by the invention.
The invention further provides composites obtainable by fusing one or more inorganic micropigments into one or more organic UV filters.
Examples of micropigments are, for example, TiO2, ZnO, iron oxides or other inorganic oxides, mica or other suitable inorganic minerals, and also Ti, alkaline earth metal or zinc salts of organic acids.
In so doing, the undesired photocatalytic properties of some of these inorganic micropigments (TiO2, ZnO) can be simultaneously suppressed, and their positive properties can also be fully utilized.
The abovementioned inorganic UV filters are advantageously fused into methylenebisbenzotriazolyltetramethylbutylphenol. The resulting composite is then micronized in the usual manner.
The invention further provides composites obtainable by melting at least two electrically neutral organic UV filters with cationically or anionically charged compounds.
For this, cationically or anionically charged compounds are melted with the corresponding organic, electrically neutral UV filters and then cooled. This process permits, in the subsequent micronization step, the preparation of organic UV filter pigments having a permanent finishing of a positive or negative charge. Such a finishing effectively prevents aggregation of the micronized particles in the sunscreen preparations which can occur in cases where the particle diameter is  less than 1 xcexcm. An otherwise customary xe2x80x9ccoatingxe2x80x9d of these particles having a repelling effect then sometimes becomes superfluous.
Cationically or anionically charged compounds which can be used are UV filters and also other compounds which have one or more cationic or anionic groups, for example
N,N,N-trimethyl-4-(2-oxoborn-3-ylidenemethyl)aniline methylsulfate;
camphorbenzalkonium methosulfate;
fatty amines;
betaines, for example cocamidopropylbetaine;
quats, for example ricinoleamidopropyltrimonium methosulfate, Quarternium 18, or cetyltrimethylammonium bromide;
behenic acid and other organic acids, for example isostearic acid, citricmonoglyceride or sodium methyl cocoyl taurate;
phospholipids, for example phosphatidylcholine, phosphatidylserine or alkylamine oxide;
ceramides and pseudoceramides and phytosterols.
The last-named compounds impart an oleophobic finishing to the micronized UV filters.
The proportion of cationic or anionic compounds in the composite is between 0.001 and 5% by weight, preferably 0.01 to 3% by weight, based on the weight of the UV filter(s).
The invention further provides composites obtainable by melting at least one sparingly soluble or insoluble organic UV filter with antoxidants.
For this, the sparingly soluble or insoluble organic UV filter(s) is/are melted together with antioxidants, cooled and then micronized in the usual manner.
Suitable antioxidants which can be used according to the invention are all organic substances having scavenger properties which can be melted together with organic UV filters. This gives novel types of micropigments which simultaneously prevent tanning of the skin and offer antioxidative action on its surface. This property is desired for cosmetic sun protection since, under the influence of UV and light, harmful free radicals can be formed both in formulations and on the skin. These can, for example, lead to so-called Mallorca acne or to premature skin ageing. By finishing the micronized UV filters with antioxidants, not only is protection against UV damage and prevention of tanning achieved, but also protection against photochemical degradation of constituents in the sunscreen formulation.
The proportion of antioxidants in the composite is generally between 0.001 and 30% by weight, preferably 0.01 to 3% by weight, based on the weight of the UV filter(s).
A content of antioxidants is particularly advantageous in micropigments which, in addition to organic UV filters, comprise the abovementioned photocatalytically active inorganic micropigments, for example titanium dioxide, zinc oxide (including coated) or other suitable inorganic oxides, for example iron oxide.
Examples of antioxidants which may be listed are the following compounds:
tocopherols, for example xcex1-tocopherol (CAS 59-02-9), tocopheryl acetate, vitamin E succinate,
ellagic acid
propyl gallate (CAS 121-79-9)
N-butylated hydroxytoluene (BHT; CAS 128-37-0);
butylated hydroxyanisole (BHA);
2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)mesitylene (CAS 1709-70-2)
tetrakis[methylene-3(3xe2x80x2,5xe2x80x2-di-t-butyl-4xe2x80x2-hydroxyphenyl)propionate]methane (CAS 6683-19-8);
compound of the formula
compound of the formula
compound of the formula
vanillin;
ubiquinone;
ferulic acid and derivatives;
rutic acid and derivatives;
urocanic acid and derivatives; and
propolis.
Preference is given to using the following mixtures of antioxidants and organic UV filters:
mixtures of methylenebisbenzotriazolyltetramethylbutylphenol, octyltriazone, titanium dioxide and tocopherol,
mixtures of 2,2xe2x80x2-methylenebis[6-(2H-benzotriazol-2-yl)4-methylphenol, octyltriazone, trisresorcinyltriazine and vitamin E
mixtures of methylenebisbenzotriazolyltetramethylbutylphenol, octyltriazone, compound of the formula (103)
(xe2x80x9cFischer aldehydexe2x80x9d) and compound of the formula
The invention further provides composites obtainable by fusing meltable cosmetic, vegetable and pharmaceutical active ingredients into organic UV filters.
In general, micronized UV filters can be used as carriers of highly active substances, in particular cosmetic and/or pharmaceutical active substances. The advantage of such composites lies in the fact that it is possible for them to release the active substance(s) from the solid (slow release). A slow release also guarantees the uniform effectiveness of highly active active ingredients, for example antiinflammatories, care active ingredients or trace elements, for example Zn2+ or Mg2+, over the entire useful life of the UV pigments.
Examples of active ingredients which can be used and which may be mentioned are:
active ingredients for antimicrobial finishing and simultaneous antiinflammatory action, for example triclosan or diclosan;
antiinflammatory active ingredients, for example farnesol, panthenol or avocado oil;
active ingredients having a deodorant or antiperspirant action, for example Zn ricinoleates and alkyl citrates,
undecylenic acid and derivatives thereof (e.g. diethanolamides)
zinc undecylate;
pyrithiones, for example sodium pyrithione;
fused-in fragrances or fragrance mixtures, for example menthol, geraniol etc., which impart a permanent odour which is uniform in intensity to these micropigments and the formulations which comprise them.
To prepare the micronized organic UV filters or the micropigment mixtures, it is possible to use all known processes which are suitable for the preparation of microparticles, for example:
wet grinding with a hard grinding medium, for example zirconium silicate and a protective surfactant or a protective polymer in water or a suitable organic solvent;
spray drying from a suitable solvent, for example aqueous or organic suspensions containing solvent, or true solutions in water, ethanol, dichloroethane, toluene, N-methylpyrrolidone etc.;
by expansion of supercritical liquids (e.g. CO2) in accordance with the RESS process (Rapid Expansion of Supercritical Solutions) in which the UV filter(s) is/are dissolved or expansion of liquid carbon dioxide together with a solution of one or more UV filters in a suitable organic solvent;
by reprecipitation from suitable solvents, including supercritical liquids (GASR process=Gas Anti-Solvent Recrystallizabon/PCA process=Precipitation with Compressed Antisolvents).
Grinding apparatuses which can be used for the preparation of the micronized organic UV absorbers according to the invention are, for example, a jet, ball, vibratory or hammer mill, preferably a high-speed stirred mill. Grinding preferably takes place using a grinding auxiliary, for example an alkylated vinylpyrrolidone polymer, a vinylpyrrolidone/vinyl acetate copolymer, an acyl glutamate, an alkyl polyglucoside, ceteareth-25 or, in particular, a phospholipid.
The resulting micropigments or mixtures of micropigments usually have an average particle size of from 0.02 to 2 nm, preferably 0.05 to 1.5 nm, and very particularly from 0.1 to 1.0 nm.
Because of their lipophilicity, they can, alone or together with other soluble organic UV absorbers, be readily incorporated into oil- and fat-containing cosmetic formulations, for example oils, O/W or W/O emulsions, wax pencils or gels, by known methods.
Surprisingly, formulations are obtained which have equal or improved protective action using less or even no soluble UV absorbers.
The invention further provides a cosmetic formulation comprising a mixture of micropigments, if desired one or more antioxidants and/or inorganic pigments and/or a cationic or anionic compound, and cosmetically compatible carriers or auxiliaries.
Cosmetic formulations according to the invention include various cosmetic compositions. In particular, the following compositions are, for example, suitable:
skincare compositions, for example skin washes and cleansers in the form of bar or liquid soaps, syndets or washing pastes,
bath preparations, for example liquid (foam baths, milks, shower preparations) or solid bath preparations, for example bath tablets or bath salts;
skincare compositions, for example skin emulsions, multiple emulsions or skin oils;
decorative bodycare compositions, for example face make-up in the form of day creams or powder creams, face powder (loose or pressed), blusher or cream make-up, eyecare compositions, for example eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lipcare compositions, for example lipstick, lip gloss, lip liner pencil, nailcare compositions, such as nail varnish, nail varnish remover, nail hardeners or cuticle removers;
personal hygiene care compositions, for example personal hygiene washing lotions or personal hygiene sprays;
footcare compositions, for example foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or products for removing calluses;
light protection compositions, such as sun milks, lotions, creams and oils, sun blocks or tropicals, pretanning preparations or aftersun preparations;
skin tanning compositions, for example self-tanning creams;
depigmentation products, for example preparations for skin bleaching or compositions for skin lightening;
insect-repelling compositions (xe2x80x9crepellentsxe2x80x9d), for example insect oils, lotions, sprays or sticks;
deodorants, such as deodorant sprays, pump sprays and deodorant gels, sticks or roller balls;
antiperspirants, for example antiperspirant sticks, creams or roller balls;
compositions for cleansing and caring for blemished skin, for example syndets (solid or liquid), peeling or exfoliation preparations or peeling masks;
depilatories in chemical form, for example depilatory powders, liquid depilatores, cream or paste depilatories, depilatories in gel form or aerosol foams;
shaving compositions, for example shaving soap, foaming shaving creams, nonfoaming shaving creams, foams, gels, preshave preparations for dry shaving, aftershaves or aftershave lotions;
fragrances, for example fragrance water (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, parfum), perfume oils or perfume creams;
compositions for dental, denture and mouth care, for example toothpastes, gel toothpastes, tooth powders, mouthwash concentrates, antiplaque mouthrinses, denture cleaners or denture adhesives;
cosmetic compositions for treating hair, for example hair cleansers in the form of shampoos, hair conditioners, haircare compositions, for example pretreatment compositions, hair tonic, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, compositions for shaping hair, for example waving agents for the preparation of permanent waves (hotwave, mildwave, coldwave), hair-smoothing preparations, liquid hair-setting compositions, hair mousses, hair sprays, bleaching agents, for example hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semipermanent or permanent hair colorants, preparations containing self-oxidizing dyes, or natural hair colorants, such as henna or camomile.
These listed end formulations can be in the form of various application forms, for example
in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W, PIT and all other types of microemulsions,
in the form of a gel,
in the form of an oil, a cream, milk or lotion,
in the form of a powder, a lacquer, a tablet or make-up,
in the form of a stick,
in the form of a spray (spray with propellant or pump spray) or an aerosol,
in the form of a foam, or
in the form of a paste.
The cosmetic formulations according to the invention can advantageously comprise further substances which absorb UV radiation in the UVB region. The total amount of filter substances here is 0.1 to 30% by weight, preferably 0.5 to 10% by weight, in particular 1 to 6% by weight, based on the total weight of the composition.
In particular, suitable additional UVB filters are oil-soluble, nonmicronized compounds, for example organic UV absorbers from the class of p-aminobenzoic acid derivatives, salicylic acid derivatives, benzophenone derivatives, dibenzoylmethane derivatives, diphenylacrylate derivatives, benzofuran derivatives, polymeric UV absorbers, comprising one or more organosilicon radicals, cinnamic acid derivatives, camphor derivatives, trianilino-s-triazine derivatives, phenylbenzimidazolesulfonic acid and salts thereof, menthyl anthranilate, benzotriazole derivatives, and/or an inorganic micropigment chosen from zinc oxide, mica or TiO2 coated with aluminium oxide or silicon dioxide.
Examples of compounds of p-aminobenzoic acid derivatives:
4-aminobenzoic acid (PABA); ethyldihydroxypropyl-PABA of the formula
in which m,n and x have the same meaning and are each at most 25;
octyldimethyl PABA of the formula
xe2x80x83or glycyl aminobenzoate of the formula
Examples of compounds of salicylic acid derivatives:
homomenthyl salicylate of the formula
xe2x80x83triethanolamine salicylate of the formula
xe2x80x83amyl p-dimethylamino-benzoate of the formula (10)
xe2x80x83octyl salicylate of the formula
xe2x80x83or 4-isopropylbenzyl salicylate of the formula
Examples of compounds of benzophenone derivatives:
benzophenone-3-(2-hydroxy4-methoxybenzophenone), benzophenone4-(2-hydroxy-4-methoxybenzophenone-5-sulfonic acid) or benzophenone-8-(2,2xe2x80x2-dihydroxy-4-methoxybenzophenone).
Examples of compounds of dibenzoylmethane derivatives:
butylmethoxydibenzoylmethane[1-(4-tert-butyl)-3-(4-methoxyphenyl)propane-1,3-dione].
Examples of compounds of diphenylacrylate derivatives:
octocrylene 2-ethylhexyl-2-cyano-3,3xe2x80x2-diphenylacrylate or etocrylene ethyl-2-cyano-3,3xe2x80x2-diphenylacrylate.
Examples of compounds of benzofuran derivatives:
3-benzofuranyl 2-cyanoacrylate, 2-(2-benzofuranyl)-5-tert-butylbenzoxazole or 2-(p-aminophenyl)benzofuran and, in particular, the compound of the formula
Examples of compounds of polymeric UV absorbers which comprise one or more organosilicon radicals:
benzylidenemalonate derivatives, in particular the compound of the formula
xe2x80x83in which
R24 is hydrogen or methoxy and
r is approximately 7; the compound of the formula
Examples of compounds of cinnamic esters:
octyl methoxycinnamate (2-ethylhexyl 4-methoxycinnamate), diethanolamine methoxycinnamate (diethanolamine salt of 4-methoxycinnamic acid), isoamyl p-methoxycinnamate (2-isoamyl 4-ethoxycinnamate), 2,5-diisopropyl methylcinnamate or a cinnamic acid amido derivative.
Examples of compounds of camphor derivatives:
4-methylbenzylidenecamphor [3-(4xe2x80x2-methyl)benzylidenebornan-2-one],
3-benzylidenecamphor (3-benzylidenebornan-2-one),
polyacrylamidomethylbenzylidenecamphor {N-[2(and 4)-2-oxyborn-3-ylidene-methyl)benzyl]acrylamide polymer}, trimoniumbenzylidenecamphor sulfate [3-(4xe2x80x2-trimethylammonium)benzylidenebornan-2-one methylsulfate], terephthalylidene-dicamphorsulfonic acid {3,3xe2x80x2-(1,4-phenylenedimethine)bis(7,7-dimethyl-2-oxobicyclo[2.2.1]heptane-1-methanesulfonic acid} or salts thereof, or benzylidene-camphorsulfonic acid [3-(4xe2x80x2-sulpho)benzylidenebornan-2-one] or salts thereof.
Examples of compounds of trianilino-s-triazine derivatives:
octyltriazine[2,4,6-trianilino(p-carbo-2xe2x80x2-ethyl-1xe2x80x2-oxy)-1,3,5-triazine, and the trianilino-s-triazine derivatives described in U.S. Pat. Nos. 5,332,568, 5,252,323, WO 93/17002 and WO 97/03642 and EP-A-0,517,104.
Examples of compounds of benzotriazoles:
2-(2-hydroxy-5-methylphenyl)benzotriazole.
The examples below serve to illustrate the invention without limiting it thereto. The cosmetic active substances are primarily given with their INCI name (INCI=International Nomenclature of Cosmetic Ingredients).

Use of mixtures of micropigments for preventing tanning and for lightening skin and hair

Abstract: The micronized UV filters used according to the invention cover a broad UV spectrum and therefore have excellent sunscreen properties.


A unit for transferring food products such as chocolates, whereby a conveyor feeds a compact sequence of mutually contacting products in a given direction to a transfer device by which the products are fed one by one, still in one direction, into respective peripheral seats on a conveyor wheel rotating about an axis perpendicular to the aforementioned direction; the transfer device being defined by a counter-rotating lobed wheel located on either side of the conveyor and defining a movable pocket for conveying each product.

1. Field of the Invention
The present invention relates to a unit for transferring food products, such as chocolates, between production machines
2. Discussion of the Background
Though the following description relates to the food industry, and more specifically to the transfer of chocolates or sweets between a manufacturing machine and a wrapping line, the same obviously also applies to the transfer between production machines of fragile, relatively small size products of any sort.
In the food industry, chocolate manufacturing machines are normally connected to the wrapping line via a transfer unit by which the chocolates coming off the machine are fed successively on a conveyor and in a first direction towards a stop member against which the chocolates are accumulated and engaged successively by a reciprocating pusher by which they are fed in a second direction, perpendicular to the first, into respective seats on a conveyor or wrapping wheel mounted for rotation about an axis parallel to the first direction.
Known transfer units of the aforementioned type present several drawbacks, foremost of which are the high noise level resulting from the presence of a reciprocating member as represented by the pusher, and the relatively low operating speed of the unit due to stoppage and the change in direction of the chocolates prior to being fed on to the conveyor wheel.

Unit for transferring food products, such as chocolates, between production machines

Azionaria Costruzioni Macchine Automatiche A.C.M.A. S.p.A.


A cantilever bushing assembly anchors the central torsional section of a vehicular stabilizer bar in a cantilevered manner relative to a vehicle understructure. The bushing assembly comprises a bracket having a pocket centered on a pocket axis that coincides with a longitudinal axis of the stabilizer bar. Two plastic outer cans are cooperatively slidable into the pocket. Each outer can has an anti-rotation lobe received in respective keyways formed in the pocket. A rubber buffer is bonded to each outer can. Each rubber buffer has a frusto-cylindrical inner bearing surface that forms an arcuate portion of an interior bushing diameter. The inner bearing surface is post-vulcanization bonded to the central torsional section of the stabilizer bar. An arched rate plate is embedded within each rubber buffer. The rubber buffers compress in the area of the inner bearing surfaces and constrict about the central torsional section of the stabilizer bar.

Field of the Invention. The invention relates generally to a bushing for a vehicular suspension system, and more particularly to a cantilever style bushing assembly for an anti-sway or stabilizer bar.
Description of Related Art. The suspension system of a motor vehicle typically includes at least one stabilizer bar, sometimes referred to as an anti-sway bar or anti-roll bar. The stabilizer bar transfers forces from one side of a vehicle to the other during uneven suspension travel. The most common situation is during a turning motion of the vehicle that occurs at speed such as a lane change or during cornering at an intersection. In these cases, the inside wheel moves downward (away from the wheel well) while the outside wheel moves upward (into the wheel well). This creates a vehicle "roll" condition. The stabilizer bar transfers wheel forces from the outside wheel to the inside wheel to improve vehicle stability, thus minimizing the "roll".
Stabilizer bars are typically configured as torsion bars having a central torsional section between opposing control ends. The control ends are associated with respective wheels. The central torsional section extends along a generally linear longitudinal axis that is transverse oriented relative to the vehicle fore and aft directions. The central torsional section has a generally circular cross-section centered about the longitudinal axis, which is attached to the vehicle frame via a pair of bushings captured in respective brackets. Each bushing supports the stabilizer bar and provides the mounting interface of the bar to the vehicle frame. FIG. 1 offers a simplified depiction of an exemplary suspension system for a motor vehicle, in which the central torsional section 24 of a stabilizer bar 20 is shown supported in a pair of bushings 22.
Stabilizer bar bushings 22 must be designed to address several functional requirements, which may include: a) acting as a bearing to allow some freedom of motion; b) providing a means to attach the stabilizer bar 20 to the vehicle frame; c) acting as an additional linear and torsional spring to improve stabilizer bar 20 efficiency; d) being free of self-generated noise; and e) meeting customer fatigue requirements.
During the freedom of motion mentioned above, the stabilizer bar 20 bends and twists, imparting both radial forces and torque through the bushings 22. The desired cross-car force transfer can only occur if the stabilizer bar 20 is supported to the vehicle frame at mounting points which adequately manage the foreseeable forces and torque. Rubber buffers in the bushings 22 are usually used at these mounting points to allow some freedom of motion and act as bearings. The elastic nature of the rubber buffer prevents the bar 20 from binding up which could otherwise lead to fatigue fractures or reduced efficiency of the bar 20.
Consider that when the stabilizer bar twists, torque is transferred to the bushings 22 through the metal-to-rubber interface between the stabilizer bar and the rubber buffer. In applications where the rotation angle is high (e.g., >30 degrees in both directions), slip can occur at this interface unless there is sufficient resistance. Slippage is of course dependent on the coefficient of friction. Some applications use an adhesive bond at the metal-to-rubber interface to prevent slip. Not only does a slippage along a metal-to-rubber interface cause a sudden decrease in torsional stiffness, but substantial unwelcome noise is also produced.
Most stabilizer bar bushings 22 are mounted from both sides directly to a vehicular crossmember or frame so that the forces that pass through the bar 20 and rubber buffers are applied to a rigid structure of the vehicle, as illustrated in FIG. 1. The bushing 22 centerline is often mounted directly in line to the frame and configured so that direct compression of the rubber buffer is achieved with the clamping force of the bracket mounting bolts. That is to say, the rubber buffer is advantageously squeezed around the stabilizer bar 20 by the same bolts used to attach the bushings 22 to the vehicle frame or other structural portion of the undercarriage. A sufficiently tight metal-to-rubber interface is easily achieved by the clamping force of the bracket mounting bolts in traditional designs where the bracket mounting bolts clamp the rubber buffer from both sides directly to the vehicular frame. That is to say, the clamping pressure creates sufficient friction in most cases to resist slippage. If/when slippage does occur at high rotation angles, the system is resigned to suffer a sudden decrease in torsional stiffness and likely also unwelcome noise. In some cases, the slippage can be controlled to a degree with the incorporation of a PTFE coated fabric liner, or low friction rubber.
In a limited number of vehicles, however, the packaging environment prohibits conventional attachments (FIG. 1) using bracket mounting bolts clamping on both sides of the rubber buffer. In these special cases, the bushing must be cantilevered from the frame mounting. Cantilevered mounting arrangements present particular engineering difficulties, because the rubber buffer of the bushing must be configured to what can fit in the environment and cannot rely on the bracket mounting bolts to supply the compression needed for a tight metal-to-rubber interface. In these cases, tight metal-to-rubber interfaces between stabilizer bar and bushing must be achieved with additional design features. Common applications include the use of a rubber-to-metal bonding agent.
The general characteristic of a bonded metal-to-rubber interface is that resistance to slip is greatly increased. Without any slip, all the twist is directly transferred to the full rubber section, thus adding cyclic fatigue exposure to the design. Prior art design solutions that bond the rubber bushing to the stabilizer bar 20 require the rubber to sustain the highest torsional fatigue. Various solutions have been able to achieve high radial stiffness by using thin rubber buffers, rate plates or radial precompression and confinement of the rubber buffer to prevent displacement but, but unfortunately have not been able to accommodate high strain at angular displacements over 30 degrees. As those of skill in the art will appreciate, in such cases the resulting high cyclic strain compromises fatigue life requirements for many vehicles and/or is ill-suited to accommodate a small package envelope.
Some prior art examples of cantilever design stabilizer bar bracket assemblies may be found in the Mercedes SL, Mercedes ML/GL and Porsche 968. Careful examination of these prior art cantilever bracket assemblies will show most are susceptible to sudden decreases in radial and/or torsional stiffness at high articulation angles, producing noise at high articulation angles, are expensive to manufacture, difficult to install and/or vulnerable to cyclic fatigue.
Mold-bonding is the technique of achieving an adhesively bonded metal-to-rubber interface concurrently with the rubber during an over-molding process. Typically, the outer metal surface of the stabilizer bar is coated with a suitable bonding agent, such as a heat activated adhesive or epoxy like those marketed by LORD Corporation/Parker-Hannifin Corporation. The coated portion of the stabilizer bar is placed into an injection mold, into which pressurized rubber is injected. Once the adhesive cures, the rubber is said to be "mold-bonded" to the outer surface of the stabilizer bar. Vulcanization of the rubber occurs either during the adhesive curing process or after the adhesive bond is cured. Since the components are permanently attached, the rubber stiffness directly contributes to the torsional and radial stiffness of the stabilizer bar 20.
One prior art example of a cantilevered bracket utilizing a mold-bonded metal-to-rubber interface can be found in the Tesla Model X. The mold-bonded rubber buffer of the Tesla Model X cantilevered design is subsequently bonded inside its aluminum bracket. During manufacture, the entire aluminum bracket is placed in a mold and the rubber is vulcanized to the bracket. In this case, vulcanization of the rubber occurs after the adhesive bond is fully cured. The stabilizer bar 20 of the Tesla Model X can be smaller and yet achieve the same vehicle roll stiffness as other prior art designs that allow slip between the bar 20 and the bushing 22. However, this design is expensive to manufacture and difficult to install.
While effective at improving metal-to-rubber interface, mold-bonding has certain disadvantages. One disadvantage is that is it impossible to pre-load, i.e., pre-compress, the rubber buffer before mold-bonding. This inability to pre-load removes from the designer the option of fine-tuning the compression characteristics of the metal-to-rubber interface. It is known that radial precompression of the rubber bushing can be used to effectively achieve higher radial stiffness and prevent displacement. The inability to pre-load also limits the quality of the metal-to-rubber interface to whatever pressures can be achieved during the injection molding process. It is well-known that bond quality is directly proportional to clamping pressure during the curing phase. Generally speaking, greater bond quality is achieved with the higher clamping pressures. Another disadvantage of the mold-bonding technique is that rubber is injection-molded at very high temperatures. As the rubber cools and solidifies, a degree of shrinkage occurs. Shrinkage has the undesirable effect of reducing compression in the rubber buffer, thereby working further against the first shortcoming, which is the inability to pre-load the rubber.
Thus, prior art bushing assemblies that must be carried in cantilever brackets are faced with this engineering challenge: how to optimize the metal-to-rubber interface between the rubber buffer and the stabilizer bar 20 while enabling high articulation (e.g., >30 degrees in both directions) and high radial stiffness (e.g., >10,000 N/mm) without slippage or noise? There is therefore a need in the art for an improved stabilizer bar bracket assembly of the cantilever type capable of sustaining high articulation, high radial stiffness and meanwhile producing little-to-no objectionable noise and that contributes to the torsional and radial stiffness of the stabilizer bar 20. While various prior art designs have been able to address one or at most two of these criteria, none have heretofore been able to concurrently satisfy all of these important factors.


A method is described for the preparation of polymorphic forms of water-soluble derivatives of probucol compounds having the following formula

Probucol is a well-known antioxidant that is related to antioxidant compounds such as 2-(3)-tertiary butyl-4-hydroxyanisole, 2,6-di-tertiary butyl-4-methylphenol and the like. These compounds are used in food and food products to prevent oxidative deterioration.
Probucol is represented by the following structural formula

The preparation of this compound is a multistep process, typically starting by reacting a solution of the appropriately-substituted 4-mercaptophenol with acetone, in the presence of a catalytic amount of a strong acid. Probucol precipitates from the reaction mixture and is readily separated and purified. The reaction is described in detail in U.S. Pat. No. 3,862,332 (Barhhart et al).
Similarly, probucol and certain of its derivatives are also described in U.S. Pat. No. 3,485,843 (Wang), U.S. Pat. No. 3,576,833 (Neuworth) and U.S. Pat. No. 4,985,465 (Handler).
Probucol and its derivatives possess pharmaceutical properties that include antiatherogenesis, lipid lowering and the like. But probucol and numerous of its derivatives are poorly soluble in body fluids.
In order to avoid the low water solubility problems associated with probucol utilization in the body, more water-soluble derivatives have been prepared. Thus, U.S. Pat. No. 5,262,439 (Parthasarathy) discloses a class of water-soluble probucol derivatives having one or more ester groups replacing the phenolic hydroxyl group of the probucol molecule. Some of the compounds disclosed in this reference have polar or charged functionalities attached to the ester group, e.g., the groups carboxylic acid, amide, amino, and aldehyde. The method disclosed for preparing these water-soluble probucol compounds involves the reaction of probucol with the carboxylic acid anhydride compound bearing the desired polar or charged functionality in the presence of a catalyst.
Similarly, U.S. Pat. No. 6,323,359 also discloses water soluble derivatives of probucol. The compounds set forth in this patent are produced by a process involving the reaction of a probucol or the probucol compound with a base, such as an alkali metal or ammonium hydroxide or alkoxide to form a mono or dianion salt. The salt is then reacted with a carboxylic acid anhydrides to produce the desired water soluble derivative of probucol or probucol compound. See also U.S. Pat. No. 6,548,699.
Recently, the preparation of use of certain phosphorous-containing strong bases has been reported. See, for example, U.S. Pat. No. 5,051,533. These compounds, termed prophosphatranes, have the following formula:
wherein R, R′ and R″ are hydrogen or C1 to C8 alkyl.
The prophosphatranes are bicyclic, nonionic bases in which the phosphorous atom functions as the site of electron pair donation. Since the conjugate acid of these compounds have a very high pKa value, the use of prophosphatranes in reactions that have been previously reserved for ionic bases such as sodium hydride, potassium tert-butoxide, etc. have proved fruitful. Thus, prophosphatrane compounds have been shown to be effective in reactions such as dehydrohalogenation, nitroaldol and alcohol silylation. Recently, in the presence of stoichiometric amounts of the prophosphatrane where R and R′ in the above formula are methyl, acetic anhydride (as well as benzoic anhydride) has been shown to react with acid-labile or sterically hindered alcohols to produce acylated alcohols in good yield. See D'Sa et al, J. Org. Chem., 1996, 61, 2963.
The prior art processes used to produce water soluble derivatives of probucol or probucol compounds are disadvantageous, since they are not effective in producing the desired derivatives in any appreciable yields.
The use of prophosphatranes in the preparation of water soluble derivatives of probucol or probucol compounds has not been suggested.
Accordingly, it is desirable to have available a process to efficiently prepare probucol derivatives in high yields.

Process for the preparation of probucol derivatives

Abstract: where R1, R2, R3, R4, R5, R6, Z and Z′ are defined herein.


A mechanism to process units of data associated with a dependent data stream using different threads of execution and a common data structure in memory. Accessing the common data structure in memory for the processing uses a single read operation and a single write operation. The folding of multiple read-modify-write memory operations in such a manner for multiple multi-threaded stages of processing includes controlling a first stage, which operates on the same data unit as a second stage to pass context state information to the second stage for coherency.

Network processors often use parallel processes to achieve high performance when processing data units, e.g., packets or cells, from multiple streams of traffic. The data units to be processed may be related to each other, for example, data units associated with the same flow. If multiple processes need to access common data structures in memory, the benefits of parallelism can be lost as the processing of the data units instead occurs in a serialized manner. The serialized processing can cause memory latency efficiency and significant performance degradation.

Folding for a multi-threaded network processor


The present invention provides a rapid coulometric analysis for the quantitative determination of a sample substance with high reproducibility without any application of voltage etc. from the outside, as well as a galvanic cell and a device for use in said coulometric analysis. According to the present invention, a wide variety of components can be analyzed by selection of electroactive substance introduced into the galvanic cell. The present invention enables a simple and easy analysis for food components such as glutamic acid, ascorbic acid, etc., water quality such as COD, etc.

For the quantitative determination of a sample substance, conventional electroanalysis using electrolysis involves measuring electrical changes occurring in a reaction (e.g., oxidation, reduction, etc.) of the substance under application of constant voltage or current, and in recent years, electrically conductive porous electrodes have been applied to such analysis.
Conventional electroanalysis using ion electrodes is a method in which an ion passing through a separating membrane is detected and in which an equilibrium potential between ions resulting from a sample substance and an electrode membrane is electrically measured by each electrode immersed as a detector in a sample solution. Another conventional electroanalysis using conductive porous electrodes is a method in which a sample is directly electrolyzed in a detection chamber with a conductive porous substance impregnated with an electrolyte, as described e.g. in Japanese Published Unexamined Patent Application 195,358/89. According to this patent application, however, electrical energy should be supplied from the outside, and a long time is required for the stabilization of the measurement device.
Conventional analysis by a reaction via a mediator makes use of a reaction e.g. from nicotinamide adenine dinucleotide (NAD) to reduced nicotinamide adenine dinucleotide (NADH) by dehydrogenase. For such a method, a glutamic acid assay kit (manufactured by BMY Co., Ltd.), for example, is commercially available for the quantitative determination in colorimetry of glutamic acid by glutamate dehydrogenase.
However, the aforesaid electroanalysis by ion electrodes have problems such as a long measurement time due to a slow rate of ion transfer through a separating membrane and a slow response rate of reaching equilibrium, etc., and troublesome procedures such as the step of washing required after each measurement, etc.
The above electroanalysis by electrolysis also has a problem. Electrolysis of a sample substance needs constant voltage or current from an external power source. Such application of voltage, however, causes the electrodes to be in a nonequilibrium state where so-called "capacitative current" occurs. Therefore, every time voltage is applied, a long stabilization time is required for measurement by electrolysis. Another problem is that the device should be made complex because of the necessity of constant voltage or current generating units, etc.
Furthermore, the above-mentioned measurement by enzyme reaction via a mediator requires the troublesome procedures of forming e.g. NADH with an enzyme, then reacting it with diaphorase etc., and measuring its absorbance. There are also practical problems: e.g., a refrigerator is required for storage of enzyme etc., and a sensor intended for use at room temperature cannot used for enzyme. In addition, it is not possible to accurately determine the absorbance where a colored substance is present in the sample.

Coulometric analysis method and a device therefor


A biometric key having a key body incorporating a biometric sensor. There is also provided a receptor body for engagement with the biometric key, wherein the reader has a slot for retention of the key. When the key engages with the receptor body, a signal representing a biocode of data generated by the biometric sensor is forwarded to processing means for granting access to an authorised user to a facility accessible by the biometric key.

Currently keys are used for a wide variety of applications that comprise a mechanical or electromechanical cipher, which carries coded information. One example of the latter is keys described in European Patent 472495 which has a specific mechanism located on opposed edges of the key which co-operates with a corresponding mechanism built into a mating lock cylinder before a locking system incorporating the lock cylinder may be opened.
While such keys are simple to use, it will be appreciated that the level of security is not high because there are no means currently available for verifying that the person using the key is an authorised user. This means that while a conventional mechanical or electromechanical lock operated by a key presents physical access to a building such a key may be readily copied or it may be lost or given to other persons who may then gain access to the building on an unauthorised basis. Thus, physical access to the building is provided by those in control of the key.
Conventional biometric control systems are well known and refer to encoding of a person's specific biometric features into a memory of the biometric control apparatus with an external process (e.g. storage memory, matching algorithm and return signal). A coded version of an authorised biometric feature can be stored. When verification is required, it is necessary for the user to present his biometric characteristic feature to the biometric control apparatus, which then compares the biometric characteristic feature with the authorised biometric feature. If a match occurs, then the biometric control system permits access to a facility controlled by the biometric control system.
Biometrically secured control systems for preventing unauthorised use of vehicles are described in U.S. Pat. No. 5,867,802. This reference describes a method and system for restricting use of a vehicle to person(s) whose fingerprints match biometric data stored within a memory in the control system of the vehicle. A user's digitised fingerprints are stored in a ROM in the BIOS of a microcontroller or in a ROM accessed by a microcontroller. The microprocessor's primary task is that of executing instructions, which are related to the operation of the vehicle such as regulation of the fuel flow rate, and other tasks. Before the microprocessor can execute its instructions related to the primary task, it must complete and exit a conditional loop of instructions that relate to validating the user's "real input" biometric data. Real scanned fingerprints must be compared with fingerprints(s) stored in ROM. If the result of the comparison is a match, then the operating loop is satisfied and the microprocessor can execute its instructions relating to operation of the vehicle. In U.S. Pat. No. 5,607,802 use is made of a conventional fingerprint scanning device and related circuitry coupled to the microprocessor. A key operated ignition switch is coupled to the microprocessor to provide a signal for providing power to the microprocessor before it may control operations related to the vehicle.
Another example of biometrically secured control systems is described in U.S. Pat. No. 5,915,936 which refers to a firearm which incorporates a pressure sensor for sensing grasping of a butt section of the firearm by a palm of the user as well as a scanning sensor for scanning a palm print of the user and generating a data signal representative of the scanned palm print after actuation of the pressure sensor. The firearm can only be used by authorised users wherein a memory unit stores data signals representative of the authorised users.
U.S. Pat. No. 5,987,155 refers to a biometric information input device having an integral smart card reader. The device provides co-operative operation of the smart card and the input device to provide user specific processing of biometric information provided by the user. Examples of biometric input devices referred to in this reference are those incorporating a microphone or those which comprise a contact imaging device such as a fingerprint scanner.
The abovementioned prior art references are illustrative of biometric control systems which can only be operated upon use of a vehicle ignition key as described in U.S. Pat. No. 5,867,802, a pressure sensor in the case of U.S. Pat. No. 5,915,936 or a smart card in the case of U.S. Pat. No. 5,987,155. It therefore will be appreciated that such conventional biometric control systems are non-versatile in being restricted to a specific application, and also require the use of additional structure relative to the specific application. Thus for example the biometric input device of U.S. Pat. No. 5,987,155 requires as an essential component a card slot for acceptance of the smart card.
It is an object of the present invention to provide a biometric key, which may reduce the disadvantages of the prior art, discussed above.


An optical system for a locally powered optical communication network includes a first trunk terminal emitting an optical signal, a second trunk terminal receiving the optical signal, a communication trunk, an intermediate unit and a power source. The communication trunk is disposed along a floor of a body of water and couples the first trunk terminal to the second trunk terminal. The communication trunk transmits the optical signal from the first trunk terminal to the second trunk terminal. The intermediate unit is connected to the communication trunk between the first and second trunk terminals. The intermediate unit receives the emitted optical signal from the first trunk terminal, amplifies the received optical signal and sends the amplified optical signal to the second trunk. The power source is connected to and powers the intermediate unit and is located at or near a surface of the body of water.

Submarine optical communication cables are optical cables laid on the sea bed connecting land-based stations. The optical communication cables carry signals across the ocean allowing for cable communication over the sea between different continents. Each transoceanic submarine optical cable includes multiple (up to eight) pairs of fibers; each pair has one fiber in each direction. The submarine optical communication cable is divided into multiple sections, each section connected to the other section by a submarine repeater. As the signals are carried across the ocean, the signals may lose some of their power. Each submarine repeater comprises multiple Erbium Doped Fiber Amplifiers (EDFA), one amplifier for the signal in each direction of each fiber. Each EDFA has a gain sufficient to compensate for the loss experienced by the signal during its propagation in the previous section of fiber. A typical length of cables (i.e., fiber) section between repeaters is about 60 km. Atypical Trans-Pacific cable with a length of 10,000 km has about 150-180 repeaters. Therefore, the repeaters ensure that the land-based station receiving the signal, from another land-based station, understands the signal. In other words, the repeaters increase the power of the signal to compensate for any loss during the signal propagation. The increased power translated to higher capacity because the clearer and more precise the optical signal is, the more complex signals may be sent from one land-based station to another.
Referring to FIG. 1, an optical communication system 10 includes first and second trunk terminals 110, 120 (also referred to as stations) coupled to a communication trunk 102. The communication trunk may include one or more repeaters 150. The repeaters 150 are powered by a constant current, typically 1 Ampere by power feeding equipment, e.g., power source 112 located by the shore. Due to nonzero electrical resistivity of copper, even with large copper area conductor having a resistance as low as 1 Ohm/kilometer, power feeding voltage drops by 60 Volt at each section of cable, so that about half of power feeding voltage is lost due to heat dissipation in copper for Trans-Pacific cable. In some examples, each power source 112 can provide power feed voltage of up to 15 kilovolts. Further increase of power feeding voltage to higher that 15 kV may result in a fault during cable operation, which has a lifetime of 25 years. The power feeding equipment 112 powers the repeaters 150 by a power cable 113, such as a copper cable. With half of power feeding voltage lost due to heat dissipation in copper cable, and due to large number of repeaters, 150-180, voltage drop at each repeater is limited to below 50 Volt. Typical output power launched into a submarine fiber is 17 dBm (50 mW) for each direction. Assuming highly efficient conversion from electrical into optical of 30% in diode laser and 10% efficiency of EDFA pumped by diode laser, each EDFA requires about 2 Volts power drop at constant current of 1 A. Thus 50V power feed voltage per repeater limits the number of EDFAs in the repeater to 20-25, i.e., supporting compensation of loss for not more than 10-12 fiber pairs. Most of subsea cables today have six fiber pairs. Thus, the power feeding of repeaters from the shores limits further growth of capacity of trans-oceanic submarine cables.

Locally powered optical communication network


A combustion power tool having a first combustion chamber, a second combustion chamber, an igniter, a partition, and a driving mechanism. Flammable gas is introduced or charged into the first and second combustion chamber. The igniter is disposed in the first combustion chamber. The partition separates the first combustion chamber from the second combustion chamber. Communication holes are formed in the partition at different angles with respect to the longitudinal direction of the first combustion chamber. The communication holes communicate the first combustion chamber with the second combustion chamber. The driving mechanism performs a predetermined processing work by utilizing an explosive combustion pressure. The combustion pressure is generated when flammable gas in the first combustion chamber is explosively burned by the igniter and when the burning front of the flammable gas in the first combustion chamber propagates to the second combustion chamber via the communication holes of the partition thereby explosively burning flammable gas in the second combustion chamber.

1. Field of the Invention
The present invention relates to a power tool such as a nailing machine, and more particularly, to a combustion power tool that performs a predetermined processing work by utilizing a high pressure impact force generated upon explosive combustion of flammable gas.
2. Description of the Related Art
Japanese Patent Publication Nos. 1-34753 (D1) and 5-55278 (D2) disclose an example of a combustion power tool. The known power tool is powered by a piston/cylinder-type internal combustion engine. In the reference D1, a fan is disposed within a combustion chamber where a combustion gas is burned. The fan serves to facilitate mixture of fuel and air and diffusion of the mixture within the combustion chamber, thereby expediting combustion. On the other hand, in the reference D2, a plurality of combustion chambers are provided and divided by partitions that have lattice-like communication holes. Each of the combustion chambers has a fuel injection hole, such that fuel and air can be efficiently mixed in each of the combustion chambers and the mixture can be efficiently diffused within the combustion chamber.
According to the reference D1, because the rotary fan is disposed within the combustion chamber, the mechanism of the power tool is complicated. According to the reference D2, although a technique for efficiently generating and diffusing the mixture within each of the combustion chambers is disclosed, further improvements are desired in order to improve the combustion efficiency of the mixture and to simplify the exhaust system for the combustion gas.


In an autostereoscopic display, a cylindrical lens focuses collimated light emitted from pixels of a display array, and a scanning device sequentially provides the light to openings in a display screen. The image information is provided in the display area at a rate corresponding to the frequency of the scanning of the openings in the display screen to provide the autostereoscopic image.

An autostereoscopic display device of the type described in the opening paragraph is known from U.S. Pat. No. 5,969,850.
Basically, a three dimensional impression can be created by using stereo pairs (two different images directed at the two eyes of the viewer), holographic techniques, or multiple planes in the displays. With the multiplanar techniques, a volumetric image is constructed, in which the 2D pixels are replaced by so-called voxels in a 3d volume. A disadvantage of most multiplanar displays is that the voxels produce light, but do not block it. This leads to transparent objects, giving quite literally a ghostly and unpleasant appearance to the displayed images.
Stereoscopic displays do not suffer from this problem. There are several ways to produce stereo images. The images may be time multiplexed on a 2D display, but this requires that the viewers wear glasses with e.g. LCD shutters. When the stereo images are displayed at the same time, the images can be directed to the appropriate eye by using a head mounted display, or by using polarized glasses (the images are then produced with orthogonally polarized light). The glasses worn by the observer effectively route the views to each eye. Shutters or polarizer's in the glasses are synchronized to the frame rate to control the routing. To prevent flicker, the frame rate must be doubled or the resolution halved with respect to the two dimensional equivalent image. A disadvantage with such as system is that the two images produce only a limited "look around" capability. Furthermore, glasses have to be worn to produce any effect. This is unpleasant for those observers who are not familiar with wearing glasses and a potential problem for those already wearing glasses, since the extra pair of glasses do not always fit.
Instead of near the viewers eyes, the two stereo images can also be split at the display screen by means of splitting screen such as a parallax barrier, as e.g. shown in U.S. Pat. No. 5,969,850.
Although these displays are autostereoscopic in the sense that no special glasses are required to view the 3D image, they often work only for one viewer at a fixed position in space. The viewing zone is very narrow. Outside the viewing zone, the observer sees multiple images or a stereo inversion, leading to a very unpleasant view. In practice this means that for many application, for instance in living rooms, the viewing zone is so small that the viewer has to be seated at one particular spot to be able to see a 3D image. Solution which offer multi-view images do so at the cost of resolution.
The device known from United States Patent U.S. Pat. No. 5,969,850 offers a solution to the narrow viewing zone problem by using a dynamic parallax barrier, i.e. a parallax barrier wherein the barrier slits move across the screen.
Although it is possible to obtain a multiview autostereoscopic display in the manner described in U.S. Pat. No. 5,969,850, a drawback of the above described principle is a lack of efficiency. Only a small amount of the light emitted passes the dynamic parallax barrier. For instance, if we use a parallax barrier display with 1000 slots (so, 1000 subframes), we have a horizontal resolution of 1000 pixels. However, the light shines on the whole backside of the parallax barrier and the latter blocks 99:9% of the light. So, for a television application we need at least a very high light intensity to get a sufficiently bright picture. Although the efficiency can be improved by making several slots of the dynamic barrier transparent at the same time, the principle problem of a very poor efficiency remains and in order to be able to use several slots the amount of different viewing directions has to be compromised


The present invention relates to a process for obtaining a catalyst of high activity based on a mixture of supports, more specifically, the mixture of supports being Al2O3 plus MgCl2, intended for the production of polyolefins. The catalyst of the present invention involves the use of a spherical support based on special alumina that serves as a porous matrix, which is impregnated, by precipitation, with magnesium chloride by dissolving the latter in ethers and/or alcohols.

The use of a catalyst on an industrial scale requires that it meets some basic requirements for good operational stability of the polymerization process.
It is already known from the literature that catalysts of polyolefins, having a mechanism of coordination polymerization, faithfully reproduce the original morphology of the catalyst (replication effect).
However, it was observed during the process of development of monofilament fibber based on a particular polyethylene resin, said monofilament possessing special characteristics of high performance and which can be processed in conventional extrusion equipment, that the catalyst displayed considerable difficulties in the implementation of stages that involve large-scale preparation of the polymer. These difficulties mainly occur in relation to the mixed catalyst obtained by grinding, which leads to an irregular morphology.
However, this irregular morphology combined with the high activity of the catalyst leads to an uncontrolled polymerization reaction, when conditions of high partial pressure are used, which in turn is reflected in stages of polymerization and processing of the polymer and leads to problems, mainly owing to formation of agglomerates in the reactor.
The industrial implementation of catalyst based on mixing by grinding, especially for the catalyst of alumina and magnesium, presents a kinetics polymerization of difficult control and, as noted above, the consequence is the formation of agglomerates. This problem makes it difficult to use in continuous processes as its application is only feasible with addition of anti-agglutinant agents. Another way of avoiding these problems is to use smaller charges of monomer. Depending on the "class" of polyethylene desired and on the use of these smaller charges, the commitment of productivity resulting from these measures may make impracticable the industrial implementation of the catalyst. An example of this is the synthesis of a polyethylene fibber "class" where, formation of agglomerates resulting from the extremely high initial activity and the poor morphology resulting from the grinding process, continuous operation of industrial plant becomes impracticable.
Researches continue being developed, searching for a catalyst that displays versatility. A desirable quality in the implementation of an industrial catalyst consists of its capacity for production of different "classes" of products without needing to change the catalytic system, which greatly simplifies operation of the system.

Catalyst and process for obtaining catalyst of high activity


The toner for developing an electrostatic charge image has a sharp particle size distribution, an improved cleaning property even if the toner has small particle diameter, and a stable charging property, developing property and transfer property regardless of change of environment. By use of the toner, a highly precise image may be obtained.. In a toner for developing an electrostatic charge image prepared by a wet process, the dielectric loss factor of the toner particles is 100 or less. In addition, when the toner particles are dissolved in an organic solvent and mixed with deionized water, the electrical conductance of the solution is desirably 100 ms or less and the surface tension thereof is desirably 20 mN or more. The toner may be obtained by forming agglomerated particles with stirring in a dispersion in which resin particles are dispersed to granulate; heating the toner particles to Tg or higher of the binder resin; stirring; and cleaning. With a wet process, the added stabilizing agent such as a surfactant can be removed.

1. Field of Invention
The present invention relates to a toner used for the development of an electrostatic image formed by an electrophotographic method or an electrostatic recording method using a developer. The present invention also relates to a method of preparing the toner, a developer for electrostatic charge image using the toner, and an image formation method using the developer for electrostatic charge image.
2. Description of Related Art
Methods for visualizing image information via an electrostatic charge image, such as an electrophotographic method, are currently used in various fields. In the electrophotographic method, an electrostatic charge image is formed on a photosensitive element via a charging and an exposure process; the image is developed with a developer containing toner; and the image is visualized via a transfer process and a fixing process.
As the developer, there are two-component-type developers containing toner and carrier and one-component-type developers containing only magnetic toner or non-magnetic toner. Toner particles in both of these types of developers are generally prepared by a kneading and pulverizing method, in which a thermoplastic resin is melted and kneaded with a pigment, a charge controller and a release agent such as a wax; cooled; finely pulverized; and classified. In order to improve the flowability and cleaning property of the toner particles prepared by the kneading and pulverizing method, inorganic or organic fine particles are added to the surface of the toner particles as needed.
Toner particles prepared by known kneading and pulverizing methods generally have an amorphous shape without a homogeneous surface composition. Although the shape and surface composition of toner particles change slightly depending on the pulverizability of the materials used and conditions of the pulverizing process, it is difficult to intentionally control these elements. In addition, when toner particles are prepared using a material with a particularly high pulverizability, the particles are often pulverized more finely in the developing device due to mechanical forces such as shearing force and the shape of the toner particles is thereby altered.
As a consequence, in the two-component-type developer, the pulverized toner particles adhere to the carrier surface so that the charge deterioration of the developer is accelerated. In addition, in the one-component-type developer, the particle size distribution of toner particles is expanded such that the pulverized toner particles are scattered or the developing property is lowered based on the change in toner shape, resulting in a deteriorated image quality.
In addition, when the toner particles have an amorphous shape, even if an auxiliary agent for improving flowability is added, the flowability may be insufficient. In addition, the fine particles of the auxiliary agent for improving flowability may move to the concave portions of the amorphous toner particles and be buried therein during operation due to mechanical forces such as the shearing force. As a result, flowability of the toner decreases over time and/or the developing property, transfer property, and cleaning property are deteriorated. Furthermore, if such toner is recollected by cleaning to return to the developer, the image quality tends to be further deteriorated. In order to prevent these problems, increasing the amount of the auxiliary agent for improving flowability has been considered. However, this may involve problems in that spots on the photosensitive element may be generated and the auxiliary agent for improving flowability may be scattered.
On the other hand, in a case of a toner containing a release agent such as wax, the release agent may be exposed on the toner particle surface depending upon the combination with a thermoplastic resin. Particularly in the case of a toner combining a resin that has a high-molecular-weight component that provides the resin with elasticity and that is not easily pulverized and a vulnerable wax such as polyethylene, exposures of the vulnerable wax such as polyethylene on the toner particle surface is often observed. Although such a toner has an advantage in the releasing property at fixing or in cleaning of untransferred toner on the photosensitive element, reliability as a developer is decreased since polyethylene on the surface of the toner particles easily falls off the toner particles due to forces in the developing device such as the shearing force and transfers to the developing roll, the photosensitive element, and the carrier, etc., causing dirt.
Under such circumstances, in recent years, as a means for preparing a toner whose particle shape and surface composition are intentionally controlled, toners have been prepared extensively with a wet process. As the wet process, there are several methods that are often used, namely, a wet sphering method capable of controlling shape of toner particles, a suspension granulating method capable of controlling surface composition of toner particles, a suspension polymerization method capable of controlling even the internal composition of toner particles, and an emulsion polymerization agglomeration method. However, other wet methods have also been used.
In recent years, one of the bigger problems associated with having toner prepared by the wet process is adding a so-called surfactant or dispersing agent (which is also referred to as "stabilizing agent" hereinafter) to greater or less degrees so as to control or keep the toner particle diameter. If the above-mentioned stabilizing agent is added at the time of toner particle production, the stabilizing agent remains in the toner liquid at the time the reaction is completed. A large amount of the stabilizing agent even remains on the surface of the toner particles.
If the stabilizing agent remains in the toner, it may lower the charging and the resistance of the toner. In particular, the stabilizing agent may have a negative influence at high temperature and humidity. Thus stable developing and transfer properties of toner may not be attained. Therefore, the advantages of the wet process, in that the particle diameter distribution of the toner particles can be made sharp and a highly precise image can be realized by making toner particles having small particle size, may be damaged. In addition, pollution on the surface of the toner leads to decreases in the flowability and preservation property and to decreases in reliability. Thus, a cleaning process to remove the stabilizing agent from toner particles is conducted, particularly after toner particles are formed by a wet process.
Most of the known methods for removing stabilizing agents from toner particles involve washing the toner particles with water. However, it is impossible to completely remove the stabilizing agent adhered to the surface of toner particles by these methods. In addition, a large amount of stabilizing agent floating in a solution cannot be easily separated. In addition, the amount of water required for cleaning is huge if the stabilizing agent is decreased as much as possible. Further, such as with toner prepared by an emulsion polymerization agglomeration method, the stabilizing agent that remains inside the toner theoretically cannot be removed.

Toner for developing electrostatic charge image, method of preparing the toner, developer for electrostatic charge image and image formation method


Methods and apparatus for realizing a short URL service are provided. According to a long URL, a short URL and long URL information are generated and stored. The long URL information contains the long URL and an information ID, and the information ID corresponds to the short URL via a pre-set corresponding mechanism to provide a corresponding relationship there-between. When a target long URL is acquired based on the short URL, the long URL in the long URL information is obtained as the target long URL according to the corresponding relationship between the short URL and the information ID. The target long URL obtained according to the short URL is updated by updating the long URL in the long URL information.

Uniform Resource Locator (URL) or a website address is a standard internet resource address. A general form of URL can be: <URL accessing method>://<host computer>:<port>/<path>, for example, https://mail.qq.com/cgi-bin/loginpage, which provides a webpage for login of QQ emails.
A whole URL often contains a large amount of characters. It is less convenient to use and spread the whole URL, especially in an environment requiring limited word counts. For example, microblog requires a limited word count of 140 words or less. Citing the whole URL may occupy a great length. Short URL services are desired and have been promoted.
The short URL service is also called short website address service. Conventional long URLs having large amount of characters may be converted into short URLs with less amount of characters according to a pre-set algorithm. For example, a long URL for accessing QQ email box can be https://mail.qq.com/cgi-bin/loginpage, which is converted by a short URL service to provide a short URL: http://url.cn/2GmfZ3. Thus, when the user inputs a conventional long URL into QQ microblog, corresponding short URL with less character can be displayed on the microblog. The short URL occupies less word count and is suitable for use in an environment with limited word counts.
Currently, when using a short URL service to convert a long URL into a short URL, the converted short URL can only correspond to the original long URL. Once the original long URL has been changed for any possible reasons, the short URL is useless and cannot be used to refer back to information related to the original long URL. Resources are thus wasted.

Methods and apparatus for realizing short URL service

TENCENT TECHNOLOGY (SHENZHEN) COMPANY LIMITED


An aqueous ink to be used in an ink jet recording containing a green pigment having a copper phthalocyanine skeleton, wherein a proportion of the Kα-line intensity of a chlorine atom to the Kα-line intensity of a bromine atom obtained by subjecting the green pigment to X-ray fluorescence analysis is 3.3 or more to 10.0 or less.

1. Field of the Invention
The present invention relates to a method to fully use a green pigment having a copper phthalocyanine skeleton as a coloring material of an aqueous ink, and also relates an aqueous ink (hereinafter referred to as "ink"), an ink set, and an ink jet recording method, an ink cartridge, a recording unit and an ink jet recording apparatus using the ink.
2. Description of the Related Art
It has been well known to use an ink (pigment ink) containing a pigment as a coloring material in order to improve the light fastness, gas fastness and water fastness of an image obtained by an ink jet recording method. However, pigments are generally poor in color developability compared with dyes. In color images formed with inks of three primary colors of cyan, magenta and yellow, an image formed with pigment inks has a clearly narrow color reproduction range when dye inks and pigment inks are compared. In view of the above-mentioned circumstances, there is a demand to develop a method to form a color image which has a excellent in color balance and to be able to achieve a broad color reproduction range.
It is thus conducted to form an image with inks of red, green and blue in addition to the inks of three primary colors of cyan, magenta and yellow (see Japanese Patent Application Laid-Open Nos. 2001-354886 and 2004-155826 and International Publication No. 2002/100959 Pamphlet). At this time, C.I. Pigment Green 7 and C.I. Pigment Green 36 that are halogenated phthalocyanine pigments are often used as coloring materials for ink jet green inks (see Japanese Patent Application Laid-Open Nos. 2000-355665, 2004-339355, 2002-332440 and 2003-012982).

Aqueous ink, ink-jet recording method, ink cartridge, recording unit and ink jet recording apparatus


A devices cage comprises a first wall having m parallel channels across a length of the first wall and a second wall having n parallel channels across a length of the second wall. In some embodiments, n is at least equal to m. Each parallel channel is equal to a diameter of a head of a drive mounting screw. The first wall comprises at least one bridge positioned across each m parallel channel and at least one clamp spring integrally coupled to a top of each m parallel channel. The second wall also comprises at least one bridge positioned across each n parallel channel. Each end of the m parallel channel extends at an inwards slant toward a center of the first wall. The inwards slant terminates at a circular area around configured in a dome shape with a flat top.

An m-unit cage is used to hold together m drives such as optical disk drives (ODDs), floppy disk drives (FDDs), hard disk drives (HDDs), and other drives. Separate securing plates and a plurality of screws are used to fasten the drives to the m-unit cage. For example, FIGS. 1A-1B illustrate a three-unit cage 100 for holding together two ODDs 105 and one FDD 110. The two ODDs 105 are positioned above the FDD 110. The three-unit cage 100 is built using an ODD securing plate 115 and a FDD securing plate 120, as illustrated in FIGS. 1C-1D, respectively. Both the ODD securing plate 115 and the FDD securing plate 120 are typically formed in a single stamping operation on sheet metal and are separate from the three-unit cage 100. As illustrated in FIG. 1C, the ODD securing plate 115 comprises a ledge 125 along a top, a pair of supports 130 located at bottom opposite ends, and two pairs of contact springs 140. A first pair of contact springs 140 is located on a top surface of the ODD securing plate 115 near the ledge 125. A second pair of contact springs 140 is located at the bottom of the ODD securing plate 115. Both pairs of contact springs 140 depress against ODD screws that are attached to the ODD. As illustrated in FIG. 1D, the FDD securing plate 120 comprises a bar 145 and a pair of contact springs 140′ located at a bottom of the bar 145. The pair of contact springs 140′ depresses against FDD screws that are attached to the FDD. The ODD securing plate 115 and the FDD securing plate 120 may have additional holes to attach the plates 115, 120 to the three-unit cage 100 and/or other accessories by using additional screws.
FIG. 2A illustrates a one-unit cage 200 for holding a HDD 205. The one-unit cage 200 is built using a HDD securing plate 210, as illustrated in FIG. 2B. The HDD securing plate 210 is typically formed in a single stamping operation on sheet metal and is separate from the one-unit cage 200. As illustrated in FIG. 2B, the HDD securing plate 210 comprises a bar 215, two ledges 220 located at a top opposite ends of the bar 215, and a pair of contact springs 225 located at a bottom of the bar 215. The pair of contact springs 225 depresses against HDD screws that are attached to the HDD. The HDD securing plate 210 may have additional holes to attach the plate 210 to the one-unit cage 200 and/or other accessories by using additional screws.
Prior art cages and securing plates suffer from a number of shortcomings. For example, contact springs of the securing plates do not provide enough clamping force or friction to prevent drives within a cage from vibrating. As such, when the drives vibrate within the cage, the cage rattles, creating disturbing and often loud noises. Typically, the clamping force exerted by one contact spring against a device is 0.85 kgf. In addition, since the securing plates are separate components from the cage, use of the securing plates is an extra cost. Furthermore, the securing plates can be lost or misplaced.
The present invention addresses at least these limitations in the prior art.

Combination devices clamp spring designed with devices cage


A firearm comprising a frame, a barrel joined to the frame, and a cartridge magazine selectively joinable to the frame; at least one cartridge contained within the cartridge magazine with the cartridge having a casing and at least one projectile, the casing having a cartridge case flange at one end and a mouth on the opposite end; and mechanism for lifting in selective communication with the cartridge and the barrel, with the mechanism for lifting having a ramp that is located adjacent to the end of the cartridge at the cartridge case flange, where the ramp acts selectively on the flange and casing; an extractor rib and barrel rib cooperating to keep extractor locked during cartridge ignition and unlocked substantially after ignition.

Automatic and semi-automatic firearms require manipulation of the next cartridge. The manipulation normally occurs through springs applying a force against the cartridge. Opening the chamber to eject a shell or spent cartridge stores energy in the slide spring and the magazine spring to a point where the springs release to "kick" a fresh cartridge into place. This type of mechanism, which is found in most semi-automatic firearms, lacks a positive grip on the cartridge, and usually has a feeding ramp in front of the cartridge, leading to numerous cartridge handling errors made more acute as the springs degrade.
One of these errors is known as a "feed ramp jam", where the bullet tip stops against the feeding ramp surface, preventing the bolt from fully reaching battery position. Self-defense bullets, such as hollow-points are more prone to feed ramp jams due to their sharp corners on the tip.
Another error is incurred when the cartridge gets ahead of the extractor so that the slide will not fully go into battery.
Another error is known as "rim-lock", where cartridge rims catch on each other in the magazine, which stops the slide from reaching its battery position.
Yet another error, known as "failure to extract", is where the spent case remains in the chamber after ignition. It can be caused by percussion gases making the extractor lose its grip on the cartridge.
Another drawback of traditional feed systems is that they leave little room for the barrel. Short barrels do not provide enough burn time for propellant inside of the barrel, so instead the propellant burns on the outside, significantly increasing muzzle flash and noise. Short barrels also reduce bullet energy.
The most common cartridge feeding system is depicted in Hiram Maxim's 1885 U.S. Pat. No. 317,162, where positive control of the cartridge is not exercised.
Past examples of controlled or "positive" cartridge manipulation include U.S. Pat. No. 395,791 to Hiram S. Maxim dated Jan. 8, 1889. However, its design was bulky and not a practical solution for smaller weapons such as pistols.
Another example is GB Pat. No. 25,656 dated Sep. 27, 1906 to Mars Automatic Pistol Syndicate discloses a "pull-back"-style mechanism in a pistol. However, the gun's feed mechanism did not positively control the cartridge at all times, nor did it have means of arresting or trapping the upward motion of the cartridge to prevent feed failures.
Blow-forward feeding systems maximized barrel length, but never implemented positive cartridge manipulation. One example is U.S. Pat. No. 580,935 to C. J. Ehbets on Apr. 20, 1897.
Rotating barrel weapons have not taken advantage of the barrel rotation to lock the extractor closed during ignition. One example of a rotating barrel gun without extractor-locking is found in U.S. Pat. No. 4,984,504 to Pier G. Beretta on Jan. 15, 1991.
What is needed is a compact cartridge feeding system that eliminates the need for the front feed ramp of traditional cartridge feeding systems, and benefits from the positive nature of rearward-feeding systems that grasp a cartridge from the magazine, controls its motion at all times, and does not release it until during ejection from the firearm. What is also needed is a feeding mechanism that maximizes barrel length. What is additionally needed is an extractor that locks against the cartridge rim during ignition.

Firearm with cartridge pick-and-place mechanism