Patent Grant
8092553
The present application is related to a composition for the oxidation dyeing of keratin fibers.
It is known practice to dye keratin fibers, such as human hair, with dye compositions containing oxidation dyes, such as oxidation dye precursors and coloring modifiers.
Oxidation dye precursors, generally known as oxidation bases, are initially colorless or weakly colored compounds, which, in combination with oxidizing products, can give rise, via an oxidative condensation process, to colored and coloring compounds. They may be, in general, compounds such as ortho- or para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic bases.
It is also known that it is possible to vary the shades obtained with these oxidation bases by combining them with couplers or coloring modifiers, the latter generally being chosen from, for example, meta-diaminobenzenes, meta-aminophenols, meta-diphenols, and certain heterocyclic compounds such as indole compounds.
The variety of the molecules involved as oxidation bases and couplers may make it possible to obtain a rich range of colors.
The “permanent” coloring that may be obtained by virtue of these oxidation dyes, also called oxidation dyeing, should, moreover, meet a certain number of requirements. Thus, it should have no toxicological drawbacks, it should allow shades to be obtained in the desired strength, and it should show good fastness with respect to external attacks such as light, bad weather, washing, permanent-waving, perspiration, and rubbing.
The dyes should also allow white hair to be covered and, finally, should be as nonselective as possible, i.e. they should make it possible to obtain the smallest possible differences in coloring along the length of the same keratin fiber, which is generally differently sensitized (i.e. damaged) between its end and its root.
Attempts have been made, in the hair-dyeing field, to improve the dyeing properties by the use, for example, of adjuvants. However, the choice of these adjuvants may be tricky in so far as they should improve the dyeing properties of the dye compositions without being detrimental to the other properties of these compositions. For example, adjuvants should not be detrimental to the keratin fiber-lightening properties and the coloring application properties.
The present disclosure is related to novel compositions for the oxidation dyeing of keratin fibers which may not have the drawbacks of the prior art. For example, one objective of the present disclosure is to obtain compositions for the oxidation dyeing of keratin fibers, which have improved dyeing properties which may make it possible to achieve the desired lightening and which may be easy to mix and to apply. The term “improved dyeing properties” is intended to mean, for example, an improvement in the level of strength/intensity and/or homogeneity of the dyeing.
This objective may be achieved by virtue of the present disclosure, which relates to a composition for the oxidation dyeing of keratin fibers, for example, human keratin fibers such as the hair, the composition intended to be mixed at the time of use with an oxidizing agent, comprising:
The composition according to the present disclosure may be produced without difficulty. It may not exhibit untimely crystallization of the dyes, for example, of the para-aminophenols.
The composition in accordance with the present disclosure may exhibit, after mixing with an oxidizing agent, improved dyeing properties. For example, the composition of the disclosure, which may be applied without difficulty to the keratin fibers, may result in colorings which exhibit good strength and/or intensity and/or good homogeneity of the color along the fiber between the end and the root of the hairs (also referred to as coloring selectivity) and/or good chromaticity.
Finally, the colorings obtained may be fast and may withstand the various external attacks that keratin fibers may be subjected to.
The present disclosure is also related to a process for dyeing keratin fibers using the composition disclosed herein.
The present disclosure is also related to a multicompartment device for using the composition disclosed herein.
The present disclosure is also related to the use of the composition disclosed herein for the oxidation dyeing of keratin fibers.
The composition of the present disclosure contains at least one oxidation base chosen from para-aminophenols and the addition salts thereof with an acid. By way of example of the para-aminophenol salts, non-limiting mention may be made of the hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, acetates, alkyl sulphates, and alkyl sulphonates.
Among the para-aminophenols that can be used according to the disclosure, non-limiting mention may be made, by way of example, of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, and 4-amino-2-(β-hydroxyethylaminomethyl)phenol.
In at least one embodiment, the at least one oxidation base is chosen from para-aminophenol and 4-amino-3-methylphenol.
For example, the at least one oxidation base of the disclosure may be para-aminophenol.
According to at least one embodiment, the at least one oxidation base is for example present in an amount ranging from 1.5% to 10% by weight, such as from 1.5% to 5%, relative to the total weight of the composition.
The dipropylene glycol may for example be present in an amount ranging from 3.5% to 20% by weight, for example from 3.5% to 15%, such as from 5% to 15% by weight, relative to the total weight of the composition.
The composition according to the present disclosure comprises at least one additional dye precursor.
The at least one additional dye precursor is chosen from oxidation bases different than the at least one oxidation base chosen from para-aminophenols and the addition salts thereof with an acid, and couplers.
The at least one additional dye precursor may, for example, be chosen from oxidation bases chosen from those conventionally known in oxidation dyeing, among which non-limiting mention may be made of, for example, ortho- and para-phenylenediamines, double bases, ortho-aminophenols, heterocyclic bases, and also the addition salts thereof with an acid.
These oxidation bases may, for example, be cationic.
The para-phenylenediamines that can be used in the context of the present disclosure may, for example, be chosen from those of formula (I) below and the addition salts thereof with an acid:
Among the nitrogenous groups of formula (I) above, non-limiting mention may, for example, be made of amino, mono(C1-C4)alkylamino, di(C1-C4)alkylamino, tri(C1-C4)alkylamino, monohydroxy(C1-C4)alkylamino, imidazolinium, and ammonium radicals.
Among the para-phenylenediamines of formula (I) above, non-limiting mention may, for example, be made of para-phenylenediamine, para-toluoylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para- phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-methylaniline, N,N-bis(β-hydroxyethyl)- para-phenylenediamine, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-hydroxyethyl- para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine, N- (4′-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine and 2-methyl-1-N-β-hydroxyethyl-para-phenylenediamine, and the addition salts thereof with an acid.
Among the para-phenylenediamines of formula (I) above, non-limiting mention may, for example, also be made of para-phenylenediamine, para-toluoylenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylene -diamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2-chloro-para-phenylenediamine and N,N-bis(β-hydroxyethyl)-para-phenylenediamine, and the addition salts thereof with an acid.
Use, for example, may be made of para-phenylenediamine, para-toluoylenediamine, N,N-bis(β-hydroxyethyl)-para-phenylenediamine, and the addition salts thereof with an acid.
As used herein, the term “double bases” is intended to mean compounds comprising at least two aromatic rings on which amino and/or hydroxyl groups are carried.
Among the double bases that can be used as the at least one additional dye precursor in the composition in accordance with the present disclosure, non-limiting mention may, for example, be made of those corresponding to formula (II) below and the addition salts thereof with an acid:
Among the nitrogenous groups in formula (II) above, non-limiting mention may, for example, be made of amino, mono(C1-C4)alkylamino, di(C1-C4)alkylamino, tri(C1-C4)alkylamino, monohydroxy(C1-C4)alkylamino, imidazolinium, and ammonium radicals.
Among the double bases of formulae (II) above, non-limiting mention may, for example, be made of N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine, N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine, N,N′-bis(4-methylaminophenyl)tetramethylenediamine, N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine and 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the addition salts thereof with an acid.
Among the double bases of formula (II), N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol and 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, or an addition salt thereof with an acid, may, for example, be used.
The ortho-aminophenols that can be used as the at least one additional dye precursor in the context of the present disclosure may for example be chosen from 2-aminophenol, 2-amino-1-hydroxy-5-methylbenzene, 2-amino-1-hydroxy-6-methylbenzene, and 5-acetamido-2-aminophenol, and the addition salts thereof with an acid.
Among the heterocyclic bases that can be used as the at least one additional dye precursor in the composition in accordance with the disclosure, non-limiting mention may, for example. be made of pyridine derivatives, pyrimidine derivatives, and pyrazole derivatives, and the addition salts thereof with an acid.
Among the pyridine derivatives, non-limiting mention may, for example, be made of the pyridine derivatives described, for example, in patents GB 1 026 978 and GB 1 153 196, for instance 2,5-diaminopyridine, 2-(4-methoxyphenyl)amino-3-amino- pyridine, 2,3-diamino-6-methoxypyridine, 2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine, and 3,4-diaminopyridine, and the addition salts thereof with an acid.
Among the pyrimidine derivatives, non-limiting mention may, for example, be made of the pyrimidine derivatives described, for example, in German patent DE 2 359 399 or Japanese patents JP 88-169 571 and JP 91-10659 or patent application WO 96/15765,for instance 2,4,5,6-tetraminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy- 4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine; 3-aminopyrazolo[1,5-a]pyrimidin-7-ol; 3-aminopyrazolo[1,5-a]pyrimidin-5-ol; 2-(3-aminopyrazolo[1,5-a]pyrimidin- 7-ylamino)ethanol; 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol; 2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)(2-hydroxyethyl)amino]ethanol; 2-[(7-aminopyrazolo[1,5-a]pyrimidin-3-yl)(2-hydroxyethyl)amino]ethanol; 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; 2,5,N7,N7-tetramethylpyrazolo[1,5-a]pyrimidine-3,7-diamine; 3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]pyrimidine; the addition salts thereof and tautomeric forms thereof, when a tautomeric equilibrium exists.
Among the pyrazole derivatives, non-limiting mention may, for example, be made of the pyrazole derivatives described in patents DE 3 843 892 and DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, for instance 4,5-diaminopyrazoles, such as, for example, 4,5-diamino-1-methylpyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole, 4,5-diamino-1,3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole, 4,5-diamino-1-β-hydroxyethyl)pyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole and 4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole; 3,4-diaminopyrazole; 4-amino-1,3-dimethyl-5-hydrazinopyrazole; 3,4,5-triaminopyrazoles such as, for example, 3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole; and the addition salts thereof with an acid.
For example, 4,5-diaminopyrazole, and for instance 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or an addition salt thereof may be used.
By way of pyrazole derivatives, non-limiting mention may also be made of diamino-N,N-dihydropyrazolopyrazolones and for example those described in application FR-A-2 886 136, such as the following pyrazole derivatives and the addition salts thereof: 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2- a]pyrazol-1-one, 2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydropyrazol-3-one, 4,5-diamino-1,2-di(2-hydroxyethyl)-1,2-dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H,6H-pyridazino[1,2-a]pyrazol-1-one, 4-amino-1,2-diethyl-5-(pyrrolidin-1-yl)-1,2-dihydropyrazol-3-one, 4-amino-5-(3-dimethylaminopyrrolidin-1-yl)-1,2-diethyl-1,2-dihydropyrazol-3-one, and 2,3-diamino-6-hydroxy-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one.
For example, 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or an addition salt thereof may be used.
As heterocyclic bases, 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or an addition salt thereof may, for example, be used.
As cationic oxidation bases that can be used in the compositions according to the disclosure, non-limiting mention may, for example, be made of the following cationic oxidation bases: para-phenylenediamines as, for example, described in patent applications FR-A-2 766 177 and FR-A-2 766 178, para-aminophenols as described, for example, in patent applications FR-A-2 766 177 and FR-A-2 766 178, ortho-phenylenediamines as described, for example, in patent applications FR-A-2 782 718, FR-A-2 782 716 and FR-A-2 782 719, ortho-aminophenols or double bases which are cationic, such as derivatives of bis(aminophenyl)alkylenediamine type, described in patent application FR-A-2 766 179, and also cationic heterocyclic bases, for example, bearing at least one quaternary nitrogen atom.
In at least one embodiment, the cationic oxidation bases that can be used in the compositions according to the disclosure are cationic para-phenylenediamines.
For example, in at least one embodiment, cationic oxidation bases of para-phenylenediamine structure, at least one of the amine functions of which is a tertiary amine bearing a pyrrolidine ring, the molecule having at least one quaternized nitrogen atom, may be used. Such bases are, for example, described in document EP-A-1 348 695.
According to at least one embodiment, the at least one additional dye precursor is chosen from para-phenylenediamine oxidation bases, heterocyclic bases, and the addition salts thereof with an acid.
When the at least one dye precursor is chosen from oxidation bases, the composition according to the present disclosure may, for example, comprise a total amount of oxidation bases different from the at least one oxidation base ranging from 0.0005% to 12% by weight, relative to the total weight of the composition. For example, it may comprise a total amount of oxidation bases different from the at least one oxidation base ranging from 0.005% to 8% by weight, such as from 0.05% to 5% by weight, relative to the total weight of the composition.
The at least one additional dye precursor may be chosen from couplers chosen from those conventionally used in oxidation dyeing compositions, i.e. meta-aminophenols, meta-phenylenediamines, meta-diphenols, naphthols and heterocyclic, couplers such as, for example, indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1,3-benzodioxoles and quinolines, and the addition salts thereof with an acid.
The at least one additional dye precursor may be chosen from couplers chosen for example from 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, 1-amino-2-methoxy-4,5-methylenedioxybenzene, α- naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine, 3,6-dimethylpyrazolo-[3,2-c]-1,2,4-triazole, and 2,6-dimethylpyrazolo-[1,5-b]-1,2,4-triazole, and the addition salts thereof with an acid.
When the at least one additional dye precursor is chosen from couplers, the composition according to the present disclosure may for example comprise a total amount of couplers ranging from 0.0001% to 15% by weight, relative to the total weight of the composition. For example, it may comprise a total amount of couplers ranging from 0.001% to 10% by weight, such as from 0.01% to 8% by weight, relative to the total weight of the composition.
The at least one additional dye precursor may be chosen from oxidation bases and couplers present in the compositions of the disclosure in the form of addition salts, such as in the form of addition salts thereof with an acid.
The addition salts with an acid that can be used in the context of the present disclosure may, for example, be chosen from the hydrochlorides, the hydrobromides, the sulphates, the citrates, the succinates, the tartrates, the lactates, the acetates, the alkyl sulphates, and the alkyl sulphonates.
When the oxidation bases or the couplers contain at least one carboxylic acid or sulphonic acid function, addition salts with a base can be envisaged. The addition salts with a base that can be used in the context of the compositions of the present disclosure may then for example be those obtained with sodium hydroxide, potassium hydroxide, aqueous ammonia, or amines.
According to at least one embodiment of the present disclosure, the composition comprises at least one coupler.
The composition of the present disclosure may further comprise at least one alkaline agent. The at least one alkaline agent may, for example, be chosen from aqueous ammonia, alkali carbonates or bicarbonates, alkanolamines such as mono-, di- and triethanolamines, and also derivatives thereof, oxyethylenated and/or oxypropylenated ethylenediamines, sodium hydroxide, potassium hydroxide, amino acids, and for example, basic amino acids such as arginine or lysine, and the compounds of formula (III) below:
According to one embodiment, the composition may comprise as the at least one alkaline agent at least one organic amine, for example, at least one alkanolamine. When the composition comprises at least one alkaline agent including an alkanolamine and ammonium hydroxides or their addition salts thereof, the amount of organic amine(s) may for example be higher than the amount of ammoniac.
According to at least one embodiment, the composition may comprise a small amount of aqueous ammonia, or even no aqueous ammonia. According to this embodiment, the composition may, for example, comprise at least one alkanolamine, such as monoethanolamine.
The composition described herein may also comprise at least one direct dye that may for example be chosen from nitrobenzene dyes, azo direct dyes, methine direct dyes, and the addition salts thereof. The at least one direct dye may be nonionic, anionic, or cationic.
The composition may also comprise other solvents constituting the dyeing medium. This dyeing medium may for example comprise, in addition to the dipropylene glycol, water or a mixture of water and at least one organic solvent other than dipropylene glycol, which is for example water-soluble.
As examples of the at least one organic solvent, non-limiting mention may for example be made of alcohols such as ethyl alcohol, isopropyl alcohol, benzyl alcohol and phenylethyl alcohol, or glycols or glycol ethers such as, for example, monomethyl, monoethyl or monobutyl ethers of ethylene glycol, propylene glycol or its ethers, such as, for example, propylene glycol monomethyl ether, butylene glycol, hexylene glycol and also diethylene glycol alkyl ethers such as, for example, diethylene glycol monoethyl ether or diethylene glycol monobutyl ether. The at least one organic solvent may be present in an amount ranging from 0.01% to 35% by weight, such as from 0.1% to 25% by weight, relative to the total weight of the composition.
In at least one embodiment, the compositions described herein may contain at least one additional organic solvent chosen from ethanol, propylene glycol, and hexylene glycol.
At the time of use, the composition described herein may be mixed with an oxidizing agent, for example, by mixing the composition described herein with a composition comprising at least one oxidizing agent.
The at least one oxidizing agent may be chosen, for example, from peroxides such as hydrogen peroxide, urea peroxide, bromates or ferricyanides of alkali metals, and persalts such as perborates, percarbonates, and persulphates. As the at least one oxidizing agent, for example, use may also be made of at least one oxidoreduction enzyme such as laccases, peroxidases, and 2-electron oxidoreductases (such as uricase), optionally in the presence of their respective donor or cofactor.
For instance, hydrogen peroxide may be used. The at least one oxidizing agent may for example be constituted of a solution of aqueous hydrogen peroxide, the titer of which may vary, for example, from 1 to 40 volumes, such as from 5 to 40 volumes.
According to at least one embodiment, the resultant composition after mixing with at least one oxidizing agent contains an amount of dipropylene glycol of greater than 0.5%.
According to at least one embodiment, the resultant composition after mixing with the at least one oxidizing agent contains at least 25% by weight of at least one fatty substance, such as at least 30% of at least one fatty substance.
The term “fatty substance” is intended to mean an organic compound which is insoluble in water at normal temperature (25° C.) and at atmospheric pressure (760 mmHg) (solubility less than 5%, for example, less than 1%, such as less than 0.1%). The fatty substances have, in their structure, at least one sequence of at least two siloxane groups or comprise at least one hydrocarbon-based chain containing at least 6 carbon atoms. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, ethanol, benzene, liquid petroleum jelly, and decamethylcyclopentasiloxane.
According to this embodiment, the composition comprises at least 25% by weight of at least one fatty substance other than fatty acids.
The at least one fatty substance may for example be chosen from lower alkanes, fatty alcohols, fatty acid esters, fatty alcohol esters, nonsilicone oils, such as mineral, plant, animal, or synthetic oils, nonsilicone waxes and silicones.
It is recalled that, for the purpose of the present disclosure, the alcohols, esters and fatty acids may for example have at least one saturated or unsaturated, linear or branched hydrocarbon-based group containing 6 to 30 carbon atoms, which is optionally substituted, for instance with at least one hydroxyl group (such as 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or nonconjugated carbon-carbon double bonds.
With regard to the lower alkanes, they contain from 6 to 16 carbon atoms and are linear or branched, optionally cyclic. By way of example, the alkanes may be chosen from hexane and dodecane and isoparaffins such as isohexadecane and isodecane.
As nonsilicone oils that can be used in the composition of the present disclosure, non-limiting mention may, for example, be made of:
The fatty alcohols that can be used in the composition of the present disclosure may be saturated or unsaturated, linear or branched, and contain 6 to 30 carbon atoms, such as from 8 to 30 carbon atoms; non-limiting mention may for example be made of cetyl alcohol, stearyl alcohol and the mixture thereof (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol, or linoleyl alcohol.
The wax(es) that can be used in the composition of the present disclosure may for example be chosen from carnauba wax, candelilla wax, esparto grass wax, paraffin wax, ozokerite, plant waxes such as olive wax, rice wax, hydrogenated jojoba wax or the absolute waxes of flowers such as the essential wax of blackcurrant blossom sold by the company Bertin (France), animal waxes, for instance beeswax, or modified beeswaxes (cerabellina); other waxes or waxy starting materials that can be used according to the present disclosure may for instance be marine waxes such as the product sold by the company Sophim under the reference M82, and polyethylene waxes or polyolefin waxes in general.
The esters may be esters of saturated or unsaturated, linear or branched C1-C26 aliphatic mono- or polyacids and of saturated or unsaturated, linear or branched C1-C26 aliphatic mono- or polyalcohols, the total carbon number of the esters being for example greater than or equal to 10.
Among the monoesters, non-limiting mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates; 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl myristate, butyl myristate, cetyl myristate, 2-octyldodecyl myristate, myrystyl myristate or stearyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, and 2-hexyldecyl laurate.
In the context of this variant, esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols and esters of mono-, di- or tricarboxylic acids and of C2-C26 di-, tri-, tetra- or pentahydroxy alcohols may also be used.
Non-limiting mention may also, for example, be made of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate, tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; and polyethylene glycol distearates.
Among the esters mentioned above ethyl palmitate, isopropyl palmitate, myristyl palmitate, cetyl palmitate, stearyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl myristate, butyl myristate, cetyl myristate or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate or cetyl octanoate may, for example, be used.
The composition may also comprise, as fatty ester, sugar esters and diesters of C6-C30, such as C12-C22, fatty acids. The term “sugar” is intended to mean oxygen-bearing hydrocarbon-based compounds containing several alcohol functions, with or without aldehyde or ketone functions, and which contain at least four carbon atoms. These sugars may be monosaccharides, oligosaccharides, or polysaccharides.
As suitable sugars, non-limiting mention may, for example, be made of sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, for example, alkyl derivatives, such as methyl derivatives, for instance methylglucose.
The sugar esters of fatty acids may be chosen, for example, from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30, such as C12-C22, fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or nonconjugated carbon-carbon double bonds.
The esters according to this embodiment may also be chosen from mono-, di-, tri- and tetraesters and polyesters, and mixtures thereof.
These esters may be, for example, oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates and arachidonates, or mixtures thereof such as, for instance, oleo-palmitate, oleo-stearate and palmito-stearate mixed esters.
For example, monoesters and diesters such as sucrose, glucose or methylglucose mono- or dioleates, stearates, behenates, oleopalmitates, linoleates, linolenates and oleostearates may be used.
By way of example, mention may be made of the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
By way of examples of esters or mixtures of esters of sugar and of fatty acid, non-limiting mention may also be made of the following:
the products sold under the names F160, F140, F110, F90, F70, SL40 by the company Crodesta, respectively denoting sucrose palmitostearates formed from 73% monoester and 27% diester and triester, from 61% monoester and 39% diester, triester and tetraester, from 52% monoester and 48% diester, triester and tetraester, from 45% monoester and 55% diester, triester and tetraester, from 39% monoester and 61% diester, triester and tetraester, and sucrose monolaurate;
The silicones that can be used in the composition of the present disclosure may be volatile or nonvolatile, cyclic, linear or branched silicones which are unmodified or modified with organic groups, having a viscosity from 5×10−6 to 2.5 m2/s at 25° C., such as 1×10−5 to 1 m2/s.
The silicones that can be used in accordance with the present disclosure may be in the form of oils, waxes, resins, or gums.
For example, the silicone may be chosen from polydialkylsiloxanes, such as polydimethylsiloxanes (PDMS), and organomodified polysiloxanes comprising at least one functional group chosen from poly(oxyalkylene) groups, amino groups, and alkoxy groups.
The organopolysiloxanes are defined in greater detail in Walter Noll's “Chemistry and Technology of Silicones” (1968), Academie Press. They can be volatile or nonvolatile.
When they are volatile, the silicones may, for example, be chosen from those having a boiling point ranging from 60° C. to 260° C., such as:
Non-limiting mention may also be made of cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as VOLATILE SILICONE® FZ 3109 sold by the company Union Carbide, of formula:
Non-limiting mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetratrimethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1′-bis(2,2,2′,2′,3,3′-hexatrimethylsilyloxy)neopentane;
Nonvolatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with organofunctional groups above, and also mixtures thereof, may, for example, be used.
These silicones may for example be chosen from polydialkylsiloxanes, among which non-limiting mention may be made of polydimethylsiloxanes containing trimethylsilyl end groups. The viscosity of the silicones is measured at 25° C. according to ASTM standard 445 Appendix C.
Among these polydialkylsiloxanes, mention may be made, in a nonlimiting manner, of the following commercial products:
the SILBIONE® oils of the 47 and 70 047 series or the MIRASIL® oils sold by Rhodia, for instance the oil 70 047 V 500 000;
Non-limiting mention may also be made of polydimethylsiloxanes containing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of the 48 series from the company Rhodia.
In this category of polydialkylsiloxanes, non-limiting mention may also be made of the products sold under the names ABIL WAX® 9800 and 9801 by the company Goldschmidt which are poly(C1-C20)dialkylsiloxanes.
The silicone gums that can be used in accordance with the present disclosure may, for example, be polydialkylsiloxanes, such as polydimethylsiloxanes with high number-average molecular masses ranging from 200,000 to 1,000,000, used alone or as a mixture in a solvent. This solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane, and mixtures thereof.
Products that can, for example, be used in accordance with the present disclosure are mixtures such as:
The organopolysiloxane resins that can be used in accordance with the present disclosure may be crosslinked siloxane systems containing the following units:
R2SiO2/2, R3SiO1/2, RSiO3/2 and SiO4/2
Among these resins, non-limiting mention may be made of the product sold under the name DOW CORNING 593 or those sold under the names SILICONE FLUID SS 4230 and SS 4267 by the company General Electric, and which are silicones of dimethyl/trimethyl siloxane structure.
Non-limiting mention may also be made of the trimethylsiloxysilicate type resins sold, for example, under the names X22-4914, X21-5034, and X21-5037 by the company Shin-Etsu.
The organomodified silicones that can be used in accordance with the present disclosure may be silicones as defined above and may comprise in their structure at least one organofunctional group attached via a hydrocarbon-based group.
Besides the silicones described above, the organomodified silicones may be polydiarylsiloxanes, such as polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned previously.
The polyalkylarylsiloxanes may be chosen for example from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity ranging from 1×10−5 to 5×10−2 m2/s at 25° C.
Among these polyalkylarylsiloxanes, non-limiting mention may, by way of example, be made of the products sold under the following names:
Among the organomodified silicones, non-limiting mention may be made of polyorganosiloxanes comprising:
For example, the at least one fatty substance may be nonoxyalkylenated and nonglycerolated.
For example, the at least one fatty substance may be chosen from compounds that are liquid or pasty at ambient temperature and at atmospheric pressure.
For example, the at least one fatty substance may be a compound that is liquid at a temperature of 25° C. and at atmospheric pressure.
According to at least one embodiment, the at least one fatty substance may be chosen from liquid petroleum jelly, polydecenes, liquid esters of fatty acids or of fatty alcohols, and mixtures thereof; for example, the at least one fatty substance of the composition according to the present disclosure may be non-silicone-based.
The composition in accordance with the present disclosure may also comprise at least one adjuvant conventionally used in hair-dyeing compositions.
The term “adjuvant” is intended to mean an additive other than the abovementioned compounds.
As examples of adjuvants that can be used, non-limiting mention may be made of anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof; anionic, cationic, nonionic, amphoteric or zwitterionic polymers, inorganic or organic thickeners, such as anionic, cationic, nonionic and amphoteric associative polymeric thickeners, other than the associative celluloses according to the present disclosure; antioxidants or reducing agents, penetrating agents; sequestering agents; fragrances; buffers; dispersing agents; conditioning agents such as, for example, volatile or nonvolatile silicones, which may be modified or unmodified; film-forming agents; ceramides; preservatives; opacifiers; and antistatic agents.
The above adjuvants may in general be present in an amount, for each of them, ranging from 0.01% to 20% by weight, relative to the weight of the composition.
Of course, those skilled in the art will take care to select the optional adjuvant(s) mentioned above in such a way that the beneficial properties intrinsically associated with the compositions according to the present disclosure are not, or not substantially, impaired by the addition(s) envisaged.
The pH of the composition in accordance with the present disclosure may, for example, range from 3 to 12, for instance, from 5 to 11, such as from 7 to 11. It may be adjusted to the desired value via use of acidifying or basifying agents normally used in the dyeing of keratin fibers, or alternatively via use of conventional buffer systems.
The alkaline agents may, for example, be those previously described herein.
Among the acidifying agents, non-limiting mention may be made, as examples, of inorganic or organic acids such as hydrochloric acid, ortho-phosphoric acid, carboxylic acids such as tartaric acid, citric acid or lactic acid, and sulphonic acids.
The composition according to the present disclosure may be in various forms, such as in the form of liquids, creams or gels, or in any other form suitable for dyeing keratin fibers, such as human hair.
The present disclosure also relates to a process for dyeing keratin fibers, comprising:
The process of the present disclosure is thus a process wherein the composition disclosed herein is mixed with a composition comprising at least one oxidizing agent, and the resultant mixture is applied to the keratin fibers. The color may be revealed at acidic, neutral, or alkaline pH and the at least one oxidizing agent may be added just at the time of use or it may be used simultaneously with or sequentially to the other elements of the composition disclosed herein.
After a leave-on time which may range, for example, from 1 to 60 minutes, such as from 5 to 45 minutes, the keratin fibers may be rinsed, optionally washed with shampoo and rinsed again, and then dried.
The process of the present disclosure can be carried out using 2 or 3 compositions, wherein one composition comprises at least one oxidation base as defined herein, at least one additional dye precursor, dipropylene glycol, and, optionally, at least one alkaline agent; and a second composition comprises at least one oxidizing agent and, optionally, at least one fatty substance, it being possible for the at least one fatty substance to be completely or partly contained in a third composition.
Thus, the present disclosure is also related to a multicompartment dyeing device or dyeing “kit” comprising:
According to another embodiment, the multicompartment dyeing device disclosed herein comprises
In at least one embodiment, the composition comprising the at least one fatty substance may be anhydrous. For the purpose of the present disclosure, the term “anhydrous composition” is intended to mean a cosmetic composition having a water content of less than 5% by weight, for example, less than 2% by weight, such as less than 1% by weight, relative to the weight of the anhydrous composition. It should be noted that this water may, for example, be bound water, such as the water from the crystallization of the salts or traces of water absorbed by the starting materials used in the preparation of the compositions according to the present disclosure.
The present disclosure is also related to the use of a composition as defined above, for the oxidation dyeing of keratin fibers, for example human keratin fibers such as the hair.
The present disclosure is further related to a method for making a composition for the oxidation dyeing of keratin fibers comprising combining:
The examples which follow are intended to illustrate the present disclosure without, however, limiting the scope thereof.
In these examples, all the amounts are indicated as percent by weight of active material (AM) relative to the total weight of the composition, unless otherwise indicated.
The following compositions were prepared:
For each of Examples 1 and 2, compositions 1, 2, and 3 were mixed at the time of use in the following proportions: 10 g of composition 1 with 4 g of composition 2 and 16 g of composition 3. The resultant mixture was applied to locks of natural grey hair containing 90% of white hairs, in a bath ratio of 10 g of mixture per 1 g of hair. After a leave-on time of 30 minutes, the hair was rinsed, washed with a standard shampoo, and dried.
The hair coloring was evaluated visually. The results obtained are provided in the following table:
Compositions 2 and 3 of Example 2 were mixed weight for weight, and the resultant mixture was applied to natural or permanent-waved grey hair containing 90% white hairs, in a bath ratio of 10 g of mixture per 1 g of hair.
After a leave-on time of 30 minutes, the hair was rinsed, washed with a standard shampoo, and dried. A relatively nonselective coloring was obtained.
| Number | Date | Country | Kind |
|---|---|---|---|
| 08 07306 | Dec 2008 | FR | national |
This application claims benefit of U.S. Provisional Application No. 61/150,450, filed Feb. 6, 2009. This application also claims benefit of priority under 35 U.S.C. §119 to French Patent Application No. 0807306, filed Dec. 19, 2008.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3100739 | Kaiser et al. | Aug 1963 | A |
| 3369970 | McLaughlin et al. | Feb 1968 | A |
| 3629330 | Brody et al. | Dec 1971 | A |
| 3861868 | Milbrada | Jan 1975 | A |
| 4138478 | Reese et al. | Feb 1979 | A |
| 4170637 | Pum | Oct 1979 | A |
| 4226851 | Sompayrac | Oct 1980 | A |
| 4357141 | Grollier et al. | Nov 1982 | A |
| 4366099 | Gaetani et al. | Dec 1982 | A |
| 4488564 | Grollier et al. | Dec 1984 | A |
| 4725282 | Hoch et al. | Feb 1988 | A |
| 4826681 | Jacquet et al. | May 1989 | A |
| 4845293 | Junino et al. | Jul 1989 | A |
| 5021066 | Aeby et al. | Jun 1991 | A |
| 5259849 | Grollier et al. | Nov 1993 | A |
| 5364414 | Lang et al. | Nov 1994 | A |
| 5817155 | Yasuda et al. | Oct 1998 | A |
| 6010541 | De La Mettrie | Jan 2000 | A |
| 6074439 | De La Mettrie et al. | Jun 2000 | A |
| 6129770 | Deutz et al. | Oct 2000 | A |
| 6156713 | Chopra et al. | Dec 2000 | A |
| 6165444 | Dubief et al. | Dec 2000 | A |
| 6190421 | Rondeau et al. | Feb 2001 | B1 |
| 6206935 | Onitsuka et al. | Mar 2001 | B1 |
| 6238653 | Narasimhan et al. | May 2001 | B1 |
| 6251378 | Laurent et al. | Jun 2001 | B1 |
| 6260556 | Legrand et al. | Jul 2001 | B1 |
| 6277154 | Lorenz | Aug 2001 | B1 |
| 6277155 | De La Mettrie et al. | Aug 2001 | B1 |
| 6365136 | Lauscher et al. | Apr 2002 | B1 |
| 6423100 | Lang et al. | Jul 2002 | B1 |
| 6447552 | Golinski | Sep 2002 | B1 |
| 6645258 | Vidal et al. | Nov 2003 | B2 |
| 6660045 | Hoeffkes et al. | Dec 2003 | B1 |
| 6695887 | Cottard et al. | Feb 2004 | B2 |
| 6800098 | Allard et al. | Oct 2004 | B1 |
| 7135046 | Audousset | Nov 2006 | B2 |
| 7153331 | Desenne et al. | Dec 2006 | B2 |
| 7217298 | Legrand et al. | May 2007 | B2 |
| 7285137 | Vidal et al. | Oct 2007 | B2 |
| 7442215 | Audousset et al. | Oct 2008 | B2 |
| 7458993 | Cottard et al. | Dec 2008 | B2 |
| 7494513 | Kravtchenko et al. | Feb 2009 | B2 |
| 7575605 | Legrand | Aug 2009 | B2 |
| 7651533 | Legrand | Jan 2010 | B2 |
| 7651536 | Cottard et al. | Jan 2010 | B2 |
| 7740663 | De La Mettrie et al. | Jun 2010 | B2 |
| 7766977 | Cottard et al. | Aug 2010 | B2 |
| 7799095 | Mario et al. | Sep 2010 | B2 |
| 20020189034 | Kitabata et al. | Dec 2002 | A1 |
| 20030064494 | Kumar et al. | Apr 2003 | A1 |
| 20030190297 | Narasimham et al. | Oct 2003 | A1 |
| 20030226217 | Bowes et al. | Dec 2003 | A1 |
| 20040103488 | Yamashita et al. | Jun 2004 | A1 |
| 20040105830 | Boswell et al. | Jun 2004 | A1 |
| 20040181883 | Legrand et al. | Sep 2004 | A1 |
| 20040221400 | Cotteret et al. | Nov 2004 | A1 |
| 20040226110 | Legrand | Nov 2004 | A1 |
| 20040235700 | Legrand et al. | Nov 2004 | A1 |
| 20050129652 | Keller et al. | Jun 2005 | A1 |
| 20050165705 | Lauper et al. | Jul 2005 | A1 |
| 20050196367 | Ohta et al. | Sep 2005 | A1 |
| 20060042023 | Machida | Mar 2006 | A1 |
| 20060075580 | Chan et al. | Apr 2006 | A1 |
| 20060137111 | Au et al. | Jun 2006 | A1 |
| 20060242773 | Kravtchenko et al. | Nov 2006 | A1 |
| 20060260071 | Legrand | Nov 2006 | A1 |
| 20060265817 | Legrand | Nov 2006 | A1 |
| 20070006397 | Schmenger et al. | Jan 2007 | A1 |
| 20070033743 | Kravtchenko | Feb 2007 | A1 |
| 20070104672 | Decoster et al. | May 2007 | A1 |
| 20070169285 | Narasimhan et al. | Jul 2007 | A1 |
| 20070275927 | Philippe | Nov 2007 | A1 |
| 20070277331 | Goldstein et al. | Dec 2007 | A1 |
| 20080016627 | Cottard et al. | Jan 2008 | A1 |
| 20080071092 | Vidal et al. | Mar 2008 | A1 |
| 20080229512 | Syed et al. | Sep 2008 | A1 |
| 20080256724 | Bolton et al. | Oct 2008 | A1 |
| 20090007347 | Cottard et al. | Jan 2009 | A1 |
| 20090060855 | Boche et al. | Mar 2009 | A1 |
| 20090151086 | Brun | Jun 2009 | A1 |
| 20090151087 | Mario et al. | Jun 2009 | A1 |
| 20090158533 | Hercouet | Jun 2009 | A1 |
| 20090162309 | Hercouet et al. | Jun 2009 | A1 |
| 20090191142 | Hercouet et al. | Jul 2009 | A1 |
| 20100162492 | Hercouet et al. | Jul 2010 | A1 |
| 20100175705 | Hercouet et al. | Jul 2010 | A1 |
| 20100186177 | Hercouet et al. | Jul 2010 | A1 |
| 20100199441 | Hercouet et al. | Aug 2010 | A1 |
| Number | Date | Country |
|---|---|---|
| 1 268 421 | May 1990 | CA |
| 2 573 567 | Mar 2006 | CA |
| 507 713 | Jul 1971 | CH |
| 20 05 076 | Aug 1970 | DE |
| 38 14 356 | Sep 1988 | DE |
| 38 14 685 | Sep 1988 | DE |
| 43 09 509 | Sep 1994 | DE |
| 195 27 121 | Jan 1997 | DE |
| 197 23 538 | Sep 1998 | DE |
| 197 12 980 | Oct 1998 | DE |
| 197 54 281 | Jun 1999 | DE |
| 198 15 338 | Sep 1999 | DE |
| 198 42 071 | Mar 2000 | DE |
| 100 08 640 | Aug 2000 | DE |
| 199 09 661 | Sep 2000 | DE |
| 199 62 869 | Jun 2001 | DE |
| 100 28 723 | Dec 2001 | DE |
| 100 56 266 | May 2002 | DE |
| 101 48 571 | Apr 2003 | DE |
| 101 48 671 | Apr 2003 | DE |
| 20 2005 008 307 | Jul 2005 | DE |
| 10 2005 011 459 | Sep 2006 | DE |
| 10 2005 032 798 | Jan 2007 | DE |
| 10 2006 012 575 | Feb 2007 | DE |
| 10 2005 059 647 | Jun 2007 | DE |
| 10 2006 020 050 | Oct 2007 | DE |
| 10 2006 061 830 | Jun 2008 | DE |
| 0 166 100 | Jan 1986 | EP |
| 0 193 471 | Sep 1986 | EP |
| 0 424 261 | Apr 1991 | EP |
| 0 890 355 | Jan 1999 | EP |
| 1 023 891 | Aug 2000 | EP |
| 1 142 563 | Oct 2001 | EP |
| 1 166 749 | Jan 2002 | EP |
| 1 219 285 | Jul 2002 | EP |
| 1 291 006 | Mar 2003 | EP |
| 1 314 418 | May 2003 | EP |
| 1 321 132 | Jun 2003 | EP |
| 1 374 842 | Jan 2004 | EP |
| 1 430 873 | Jun 2004 | EP |
| 1 449 512 | Jun 2004 | EP |
| 1 438 951 | Jul 2004 | EP |
| 1 486 195 | Dec 2004 | EP |
| 1 488 781 | Dec 2004 | EP |
| 1 550 656 | Jul 2005 | EP |
| 1 568 354 | Aug 2005 | EP |
| 1 570 833 | Sep 2005 | EP |
| 1 598 052 | Nov 2005 | EP |
| 1 707 184 | Oct 2006 | EP |
| 1 716 839 | Nov 2006 | EP |
| 1 716 840 | Nov 2006 | EP |
| 1 733 759 | Dec 2006 | EP |
| 1 762 222 | Mar 2007 | EP |
| 1 792 602 | Jun 2007 | EP |
| 1 813 254 | Aug 2007 | EP |
| 1 862 198 | Dec 2007 | EP |
| 1 870 085 | Dec 2007 | EP |
| 1 902 703 | Mar 2008 | EP |
| 1 927 377 | Jun 2008 | EP |
| 1 944 009 | Jul 2008 | EP |
| 2 005 939 | Dec 2008 | EP |
| 2 011 473 | Jan 2009 | EP |
| 2 011 474 | Jan 2009 | EP |
| 2 018 848 | Jan 2009 | EP |
| 2 047 841 | Apr 2009 | EP |
| 2 072 034 | Jun 2009 | EP |
| 2 072 035 | Jun 2009 | EP |
| 2 072 036 | Jun 2009 | EP |
| 2 198 842 | Jun 2010 | EP |
| 2 198 843 | Jun 2010 | EP |
| 2 198 849 | Jun 2010 | EP |
| 1 517 715 | Mar 1968 | FR |
| 2 132 214 | Nov 1972 | FR |
| 2 402 446 | Apr 1979 | FR |
| 2 496 458 | Jun 1982 | FR |
| 2 616 324 | Dec 1988 | FR |
| 2 769 835 | Apr 1999 | FR |
| 2 779 949 | Dec 1999 | FR |
| 2 803 196 | Jul 2001 | FR |
| 2 842 101 | Jan 2004 | FR |
| 2 870 724 | Dec 2005 | FR |
| 2 874 323 | Feb 2006 | FR |
| 2 892 623 | May 2007 | FR |
| 2 910 309 | Jun 2008 | FR |
| 2 911 499 | Jul 2008 | FR |
| 2 912 903 | Aug 2008 | FR |
| 2 912 904 | Aug 2008 | FR |
| 2 912 906 | Aug 2008 | FR |
| 2 915 886 | Nov 2008 | FR |
| 2 919 499 | Feb 2009 | FR |
| 2 925 304 | Jun 2009 | FR |
| 2 925 307 | Jun 2009 | FR |
| 2 925 308 | Jun 2009 | FR |
| 2 925 309 | Jun 2009 | FR |
| 2 925 311 | Jun 2009 | FR |
| 2 940 054 | Jun 2010 | FR |
| 1 288 128 | Sep 1972 | GB |
| 2 003 938 | Mar 1979 | GB |
| 1 554 331 | Oct 1979 | GB |
| 2 065 177 | Jun 1981 | GB |
| 2 142 348 | Jan 1985 | GB |
| 2 170 830 | Aug 1986 | GB |
| 2 188 948 | Oct 1987 | GB |
| 2 217 735 | Nov 1989 | GB |
| 58-035106 | Mar 1983 | JP |
| 59-106413 | Jun 1984 | JP |
| 1-165514 | Jun 1989 | JP |
| 10-101537 | Apr 1998 | JP |
| 2001-233748 | Aug 2001 | JP |
| 2001-302471 | Oct 2001 | JP |
| 2003-095984 | Apr 2003 | JP |
| 2003-238370 | Aug 2003 | JP |
| 2004-262886 | Sep 2004 | JP |
| 2006-282524 | Oct 2006 | JP |
| 2008-74705 | Apr 2008 | JP |
| WO 9111985 | Aug 1991 | WO |
| WO 9701323 | Jan 1997 | WO |
| WO 9704739 | Feb 1997 | WO |
| WO 9712587 | Apr 1997 | WO |
| WO 9803150 | Jan 1998 | WO |
| WO 0128508 | Apr 2001 | WO |
| WO 0141723 | Jun 2001 | WO |
| WO 0143709 | Jun 2001 | WO |
| WO 0160327 | Aug 2001 | WO |
| WO 02089748 | Nov 2002 | WO |
| WO 03053329 | Jul 2003 | WO |
| WO 03084495 | Oct 2003 | WO |
| WO 2005025525 | Mar 2005 | WO |
| WO 2005055966 | Jun 2005 | WO |
| WO 2006026851 | Mar 2006 | WO |
| WO 2007006418 | Jan 2007 | WO |
| WO 2007096027 | Aug 2007 | WO |
| WO 2008021641 | Feb 2008 | WO |
| WO 2008096497 | Aug 2008 | WO |
| WO 2008138844 | Nov 2008 | WO |
| WO 2009010883 | Jan 2009 | WO |
| WO 2009080667 | Jul 2009 | WO |
| WO 2009080668 | Jul 2009 | WO |
| WO 2009080669 | Jul 2009 | WO |
| WO 2009080670 | Jul 2009 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20100154139 A1 | Jun 2010 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61150450 | Feb 2009 | US |
