FR2818536A1 - Composition for direct dyeing of keratinic fibers, especially human hair, includes an amphiphilic polymer comprising sulfo-functional ethylenically unsaturated monomer units and a hydrophobic portion - Google Patents

Abstract

Composition for dyeing keratinic fibers, comprising one or more direct dyes, comprises: (1) an amphiphilic polymer (I) comprising sulfo-functional ethylenically unsaturated monomer units; and (2) a hydrophobic portion. An Independent claim is also included for a method for lightening and dyeing keratinic fibers using a direct dye composition and an oxidizing composition, one or both of which comprises an amphiphilic polymer..

Description

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La présente invention concerne une composition de teinture directe des fibres kératiniques, en particulier des fibres kératiniques humaines et plus particulièrement les cheveux, comprenant au moins un colorant direct et au moins un polymère amphphie comportant au moins un monomère à insaturation éthylénique à groupement sulfonique, sous forme libre ou partiellement ou totalement neutralisée et en outre au moins une partie hydrophobe Il est connu de teindre les fibres kératiniques et en particulier les cheveux humains, avec des compositions de teinture contenant des colorants directs, en particulier des colorants benzéniques nitrés, des colorants azoïques acides, des colorants azoïques cationiques, des colorants anthraquinoniques, des colorants naturels. DIRECT DYEING COMPOSITION FOR KERATIN FIBERS BASED ON AMPHIPHILIC POLYMERS OF AT LEAST ONE SULFONICALLY GROUPED ETHYLENE UNATURATION MONOMER COMPRISING A HYDROPHOBIC PART

The present invention relates to a direct dyeing composition for keratinous fibers, in particular human keratinous fibers and more particularly the hair, comprising at least one direct dye and at least one amphophilic polymer comprising at least one ethylenically unsaturated monomer containing a sulphonic group, under free form or partially or totally neutralized and in addition at least one hydrophobic part It is known to dye keratinous fibers and in particular human hair, with dyeing compositions containing direct dyes, in particular nitrobenzene dyes, azo dyes acids, cationic azo dyes, anthraquinone dyes, natural dyes.

These dyes may be produced by direct application to the keratinous fibers of the composition containing the direct dye (s) or by application of a mixture made extemporaneously of a composition containing the direct dye (s) with a composition containing an oxidizing bleaching agent which is preferably hydrogen peroxide. This is called direct lightening.

To locate the hair coloring product on the hair so that it does not run on the face or outside the areas that we propose to dye, so far we have resorted to the use of traditional thickeners such as crosslinked polyacrylic acid, hydroxyethylcelluloses, waxes or mixtures of nonionic surfactants of HLB (Hydrophilic Lipophilic Balance), which, properly chosen, cause the gelling effect when they are diluted with water and / or surfactants.

However, the Applicant has found that the thickening systems mentioned above do not allow to obtain powerful and chromatic shades of low selectivities and good tenacity while ensuring a good cosmetic condition to the treated hair. Furthermore, it has also found that ready-to-use dyeing compositions containing the direct dye (s) and, in addition,

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 thickeners of the prior art did not allow a sufficiently precise application without sagging or drops in viscosity over time.

However, after important research conducted on the question, the Applicant has now discovered that it is possible to obtain direct dye compositions that do not flow and therefore remain well located at the point of application, and which also allow to obtain powerful and chromatic (luminous) shades with low selectivities and good toughness vis-à-vis chemical agents (shampoo, perms ...) or natural (light, perspiration ...) while bringing good hair cosmetic properties if one introduces (i) either into the composition containing at least one direct dye, or (ii) into the oxidizing composition used for direct lightening dyeing, or (iii) in both compositions, an effective amount of at least one amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free form or partially or completely neutralized, and in at least one hydrophobic part.

These findings are the basis of the present invention.

The subject of the present invention is therefore a direct dyeing composition for keratinous fibers, in particular for human keratinous fibers, and more particularly the hair, comprising, in a medium suitable for dyeing, at least one direct dye, which is characterized by the it also contains at least one amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free form or partially or totally neutralized and in addition at least one hydrophobic part.

Another subject of the invention relates to a ready-to-use composition for dyeing keratinous fibers which contains at least one direct dye, at least one oxidizing agent, and at least one amphiphilic polymer comprising at least one ethylenically unsaturated monomer. sulfonic group, in free form or partially or completely neutralized and in addition at least one hydrophobic part.

By "ready-to-use composition" is meant, within the meaning of the invention, the composition intended to be applied as it is to the keratinous fibers, that is to say that it may be stored as it is before use or result. extemporaneous mixing of two or more compositions.

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 The invention also relates to a process for the direct dyeing of keratinous fibers, in particular human keratinous fibers, and more particularly the hair, of applying to the fibers a composition containing, in a medium which is suitable for dyeing, at least one direct dye. and at least one amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free form or partially or totally neutralized form and in addition at least one hydrophobic part.

The invention also relates to a process for the direct dyeing of keratinous fibers, in particular human keratinous fibers, and more particularly the hair, of applying to the fibers an extemporaneous mixture of a dye composition containing, in a medium suitable for dyeing, at least one direct dye, and an oxidizing composition containing at least one oxidizing agent, the dye composition and / or the oxidizing composition containing at least one amphiphilic polymer comprising at least one monomer with at least one ethylenic unsaturation with sulfonic group, in free form or partially or completely neutralized and in addition at least one hydrophobic part.

The invention also relates to devices for direct dyeing and direct dyeing lightening keratin fibers or "kits" with two compartments.

A two-compartment device for direct dyeing according to the invention comprises a first compartment containing, in a medium suitable for dyeing, at least one direct dye and a second compartment containing at least one amphiphilic polymer comprising at least one ethylenically unsaturated monomer. sulfonic group, in free form or partially or completely neutralized and in addition at least one hydrophobic part.

Other devices with 2 compartments for direct dye lightening according to the invention comprise a compartment which contains a dye composition containing, in a medium suitable for dyeing, at least one direct dye, and another compartment which contains an oxidizing composition containing in a medium suitable for dyeing, an oxidizing agent, at least one amphiphilic polymer according to the invention being present in the dye composition or the oxidizing composition, or in each of the two compositions.

But other features, aspects, objects and advantages of the invention will emerge even more clearly on reading the description and examples which follow.

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Amphiphilic Polymers According to the Invention The polymers in accordance with the invention are amphiphilic polymers comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free form or partially or totally neutralized and comprising at least one hydrophobic part.

Amphiphilic polymer is understood to mean any polymer comprising both a hydrophilic part and a hydrophobic part and in particular a fatty chain.

The hydrophobic part present in the polymers of the invention preferably comprises from 6 to 50 carbon atoms, more preferably from 6 to 22 carbon atoms and even more preferably from 12 to 18 atoms.

Preferably, the polymers in accordance with the invention are partially or completely neutralized with a mineral base (sodium hydroxide, potassium hydroxide, aqueous ammonia) or an organic base such as mono-, di- or tri-ethanolamine, aminomethylpropanediol, N- methylglucamine, basic amino acids such as arginine and lysine, and mixtures of these compounds.

They generally have a molecular weight, calculated by weight, ranging from 20,000 to 10,000,000, more preferably from 50,000 to 8,000,000 and even more preferably from 100,000 to 7,000,000.

The amphiphilic polymers according to the invention may be crosslinked or non-crosslinked.

When they are crosslinked, the crosslinking agents may be chosen from the olefinic polyunsaturated compounds commonly used for crosslinking the polymers obtained by radical polymerization.

diallyléther, les polyglycol-diallyléthers, le triéthylèneglycol-divinyléther, l'hydroquinonediallyl-éther, le diacrylate de tétraéthylèneglycol, la triallylamine, le méthylène-bisacrylamide, le triméthylol propane triacrylate, le tétra-allyloxy-éthane, le triméthylolpropane-diallyléther, le méthacrylate d'allyle, les éthers allyliques d'alcools de There may be mentioned, for example, divinylbenzene, diallyl ether, dipropylene glycol,

diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinonediallyl ether, tetraethylene glycol diacrylate, triallylamine, methylenebisacrylamide, trimethylol propane triacrylate, tetra-allyloxyethane, trimethylolpropane diallyl ether, methacrylate of allyl, the allyl ethers of alcohols

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la série des sucres, ou d'autres allyl-ou vinyl-éthers d'alcools polyfonctionnels, ou les mélanges de ces composés. On utilisera plus particulièrement le méthylène-bis-acrylamide, le méthacrylate d'allyle ou le triméthylol propane triacrylate (TMPTA). Le taux de réticulation variera en général de 0,01 à 10% en mole et plus particulièrement de 0, 2 à 2% en mole par rapport au polymère.

the series of sugars, or other allyl-or vinyl-ethers of polyfunctional alcohols, or mixtures of these compounds. Methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA) will be used more particularly. The degree of crosslinking will generally vary from 0.01 to 10 mol% and more particularly from 0.2 to 2 mol% relative to the polymer.

notamment parmi l'acide vinylsulfonique, l'acide styrènesulfonique, les acides (méth) acry ! amido (Ci-C22) aiky ! su ! foniques, tes acides N- (CI-C22) alkyl (méth) acrylamido (Cl- C22) alkylsulfoniques comme l'acide undécyl-acrylamido-méthane-sulfonique ainsl que leurs formes partiellement ou totalement neutralisées.

The ethylenically unsaturated monomers containing a sulfonic group are chosen

in particular from vinylsulfonic acid, styrenesulphonic acid, (meth) acrylic acids, amido (Ci-C22) aiky! su! and N- (C1-C22) alkyl (meth) acrylamido (C1-C22) alkylsulphonic acids such as undecyl-acrylamido-methanesulfonic acid and their partially or completely neutralized forms.

More preferably, the (meth) acrylamido (C 1 -C 22) alkylsulphonic acids, such as, for example, will be used! e! 'ac! of acry) amido-methane-su! fonic, acry acid! amido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acid -acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecyl-sulfonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and their partially or completely neutralized forms.

More particularly, use 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its partially or completely neutralized forms.

The amphiphilic polymers in accordance with the invention may especially be chosen from AMPS random amphiphilic polymers modified by reaction with a C6-C22 nmonoalkylamine or a di-n-alkylamine, and such as those described in the patent application WO00 / 31154 (forming part of the content of the description).

These polymers may also contain other hydrophilic ethylenically unsaturated monomers chosen, for example, from (meth) acrylic acids, their ss-substituted alkyl derivatives or their esters obtained with monoalcohols or

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mono-ou poly- alkylèneglycols, les (méth) acrylamides, la vinylpyrrolidone, l'anhydride maléique, l'acide itaconique ou l'acide maléique ou les mélanges de ces composés.

mono-or polyalkylene glycols, (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures thereof.

The preferred polymers of the invention are chosen from AMPS amphiphilic copolymers and at least one hydrophobic ethylenically unsaturated monomer comprising at least one hydrophobic part having from 6 to 50 carbon atoms and more preferably from 6 to 22 carbon atoms. carbon and more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.

monoalcools ou des mono-ou poty-a ! ky ! ènegiycois, tes (méth) acryiamides, ta vinylpyrrolidone, l'anhydride maléique, l'acide itaconique ou l'acide maléique ou les mélanges de ces composés. These same copolymers may also contain one or more ethylenically unsaturated monomers not containing a fatty chain, such as (meth) acrylic acids, their p-substituted alkyl derivatives or their esters obtained with

monoalcohols or mono-or poty-a! ky! ethylene, (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures of these compounds.

studied by fluorescence and dynamic light scattering-Macromolecules 2000, Vol. 33, W 10-3694-3704 ; - Solution properties of micelle networks formed by non-ionic moieties covalently bound to an polyelectrolyte : salt effects on rheological behavior-Langmuir, 2000,
Vol. 16, N'12, 5324-5332 ; - Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido)-2- methylpropanesulfonate and associative macromonomers-Polym. Preprint, Div. These copolymers are described in particular in patent application EP-A-750899, patent US 5089578 and in the following Yotaro Monshima publications: - Self-assembling amphiphilic polyelectrolytes and their nanostructures-Chinese
Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336. - Miscellanous formation of random copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as

studied by fluorescence and dynamic light scattering-Macromolecules 2000, Vol. 33, W 10-3694-3704; Solution properties of micelle networks formed by non-ionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior-Langmuir, 2000,
Flight. 16, N'12, 5324-5332; Stimuli responsive amphiphilic copolymers of sodium 2- (acrylamido) -2-methylpropanesulfonate and associative macromonomers-Polym. Preprint, Div.

 Polym. Chem. 1999, 40 (2), 220-221.

The hydrophobic monomers with ethylenic unsaturation of these particular copolymers are preferably chosen from the acrylates or acrylamides of formula (1) below.

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dans laquelle R1 et R3, identiques ou différents, désignent un atome d'hydrogène ou un radical alkyle linéaire ou ramifié en Ci-Ce (de préférence méthyle) ; Y désigne 0 ou NH, R2 désigne un radical hydrocarboné hydrophobe comportant au moins de 6 à 50 atomes de carbone et plus préférentiellement de 6 à 22 atomes de carbone et encore plus préférentiellement de 6 à 18 atomes de carbone et plus particulièrement de 12 à 18 atomes de carbone ; x désigne un nombre de moles d'oxyde d'alkylène et varie de 0 à 100.

in which R1 and R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y denotes O or NH, R2 denotes a hydrophobic hydrocarbon radical containing at least 6 to 50 carbon atoms and more preferably 6 to 22 carbon atoms and even more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms. carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.

The radical R2 is preferably chosen from linear C6-C1g (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (for example cyclododecane (C12) alkyl radicals. or adamantane (C10)); C 6 -C 18 alkyl perfluorinated radicals (for example the group of formula - (CH 2 h- (CF 2) g-CF 3), the cholesteryl radical (C 27) or a cholesteryl ester residue such as the cholesteryl oxyhexanoate group; polycyclic groups; aromatics such as naphthalene or pyrene.

Among these radicals, linear alkyl radicals, and more particularly the n-dodecyl radical, are more particularly preferred.

According to a particularly preferred form of the invention, the monomer of formula (1) comprises at least one alkylene oxide unit (x> 1) and preferably a chain

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polyoxyalkylenated. The polyoxyalkylene chain is preferably composed of ethylene oxide units and / or propylene oxide units and even more particularly ethylene oxide units. The number of oxyalkylenated units generally varies from 3 to 100 and more preferably from 3 to 50 and even more preferably from 8 to 25.

Among these polymers, mention may be made of: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of AMPS units and from 40 to 85% by weight of (C 8 -C 18) alkyl (meth) units acrylamide or (C 8 -C 16) alkyl (meth) acrylate units with respect to the polymer, such as those described in application EP-A-750 899; terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and from 5 to 80 mol% of n- (C6-C18) alkylacrylamide units, such as those described in US Patent 5089578.

Mention may also be made of copolymers of completely neutralized AMPS and of dodecyl methacrylate, as well as copolymers of uncrosslinked and crosslinked AMPS and ndodecylmethacrylamide, such as those described in the Morishima articles cited above.

dans laquelle X+ est un proton, un cation de métal alcalin, un cation alcalino-terreux ou l'ion ammonium, et de motifs de formule (ici) suivante : Copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of the following formula (here) are more particularly mentioned.

in which X + is a proton, an alkali metal cation, an alkaline earth cation or the ammonium ion, and units of the following formula (here):

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dans laquelle x désigne un nombre entier variant de 3 à 100, de préférence de 3 à 50 et plus préférentiellement de 8 à 25 ; R1 a la même signification que celle indiquée ci- dessus dans la formule (1) et R4 désigne un alkyle linéaire ou ramifié en C6-C22 et plus préférentiellement en C12-Cl8.

in which x denotes an integer ranging from 3 to 100, preferably from 3 to 50 and more preferably from 8 to 25; R1 has the same meaning as that indicated above in formula (1) and R4 denotes a linear or branched C6-C22 and more preferably C12-Cl8 alkyl.

Particularly preferred polymers are those where x = 25, R-) is methyl and R4 is n-dodecyl; they are described in the articles of Morishima mentioned above.

The molar concentration in% of the units of formula (II) and units of formula (here) will vary according to the desired cosmetic application and the rheological properties of the desired formulation. It preferably varies from 70 to 99 mol% of AMPS units and from 1 to 30 mol% of units of formula (here) relative to the copolymer and more particularly from 70 to 90 mol% of AMPS units and from 10 to 30 mol% of units of formula (III).

These copolymers can be obtained by conventional methods of radical copolymerization in the presence of one or more initiators such as, for example, azobisisobutyronitrile (AIBN), azobisdivaleronitrile, ABAH (2,2-azobis- [2-amidinopropane] hydrochloride) or dilauryl peroxide.

The polymers in accordance with the invention are present in the compositions in concentrations ranging from 0.01 to 30% by weight, more preferably from 0.1 to 10% by weight and even more preferably from 0.5 to 2% by weight. .

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The direct dyes that can be used according to the invention are preferably chosen from neutral, acidic or cationic nitro-benzene direct dyes, acid or cationic neutral azo direct dyes, direct quinone and in particular neutral, acidic or cationic anthraquinone dyes, direct dyes. azines, triarylmethane direct dyes, direct indoamine dyes and natural direct dyes.

Among the benzene direct dyes that may be used according to the invention, the following compounds may be mentioned in a nonlimiting manner: -1,4-diamino-2-nitrobenzene -1-amino-2-nitro-4-p-hydroxyethylaminobenzene -1-amino- 2 Nitro-4-bis (p-hydroxyethyl) -aminobenzene -1,4-bis (p-hydroxyethylamino) -2-nitrobenzene -1-p-hydroxyethylamino-2-nitro-4-bis (p-hydroxyethylamino) benzene - 1-p-hydroxyethylamino-2-nitro-4-aminobenzene -1-p-hydroxyethylamino-2-nitro-4- (ethyl) (P-hydroxyethyl) -aminobenzene-1-amino-3-methyl-4- p-Hydroxyethylamino-6-nitrobenzene-1-amino-2-nitro-4-p-hydroxyethylamino-5-chlorobenzene -1,2-Diamino-4-nitrobenzene-1-amino-2-p-hydroxyethylamino-5-nitrobenzene 1,2-Bis- (β-hydroxyethylamino) -4-nitrobenzene-1-amino-2-tris- (hydroxymethyl) -methylamino-5-nitrobenzene-1-hydroxy-2-amino-5-nitrobenzene-1-hydroxyl- 2-amino-4-nitrobenzene-1-hydroxy-3-nitro-4-aminobenzene -1-hydroxy-2-amino-4,6-dinitrobenzene -1-p-hydroxyethyloxy-2- hydroxyethylamino-5-nitrobenzene-1-methoxy-2-p-hydroxyethyl amino-5-nitrobenzene-1-p-hydroxyethyloxy-3-methylamino-4-nitrobenzene-1-p, y-dihydroxypropyloxy-3-methylamino-4-nitrobenzene-1-p-hydroxyethylamino-4-p, y-dihydroxypropyloxy- 2-Nitrobenzene -1-P ,, [-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene-1-p-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene-1-p-hydroxyethylamino-3-methyl-2-nitrobenzene-1 -p-aminoethylamino-5-methoxy-2-nitrobenzene

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-1-Hydroxy-2-chloro-6-éthylamino-4-nitrobenzène -1-Hydroxy-2-chloro-6-amino-4-nitrobenzène -1-Hydroxy-6-bis- (P-hydroxyéthyl)-amino-3-nitrobenzène - 1-j3-hydroxyéthylamino-2-nitrobenzène - 1-Hydroxy-4-p-hydroxyéthylamino-3-nltrobenzène. Parmi les colorants directs azoïques utilisables selon l'invention on peut citer les colorants azoiques cationiques décrits dans les demandes de brevets WO 95/15144, WO-95/01772 et EP-714954 dont le contenu fait partie intégrante de invention.

1-Hydroxy-2-chloro-6-ethylamino-4-nitrobenzene -1-hydroxy-2-chloro-6-amino-4-nitrobenzene -1-hydroxy-6-bis (p-hydroxyethyl) -amino-3 -Nitrobenzene-1-β-hydroxyethylamino-2-nitrobenzene-1-hydroxy-4-p-hydroxyethylamino-3-n-tribenzene. Among the azo direct dyes that may be used according to the invention, mention may be made of the cationic azo dyes described in the patent applications WO 95/15144, WO-95/01772 and EP-714954, the content of which forms an integral part of the invention.

- chlorure de 1, 3-diméthyl-2-[[4- (diméthylamino) phényl]azo]-1 H-Imidazolium, - chlorure de 1, 3-diméthyl-2- [ (4-aminophényl) azo]-1 H-Imidazolium, - methylsulfate de 1-méthyl-4-[ (méthylphénylhydrazono) méthyl]-pyridinium. On peut également citer parmi les colorants directs azoïques les colorants suivants, décrits dans le COLOUR INDEX INTERNATIONAL 38 édition : - Disperse Red 17 -Acid Yellow 9 -Acid Black 1 - Basic Red 22 - Basic Red 76 -Basic Yellow 57 - Basic Brown 16 -Acid Yellow 36 -Acid Orange 7 -Acid Red 33 -Acid Red 35 -Basic Brown 17 -Acid Yellow 23 -Acid Orange 24 -Disperse Black 9. Among these compounds, mention may be made of the following dyes:

1,3-dimethyl-2 - [[4- (dimethylamino) phenyl] azo] -1H-imidazolium chloride; 1,3-dimethyl-2 - [(4-aminophenyl) azo] -1H chloride; Imidazolium, 1-methyl-4 - [(methylphenylhydrazono) methyl] pyridinium methylsulfate. Mention may also be made, among the azo direct dyes, of the following dyes, described in the COLOR INDEX INTERNATIONAL 38 edition: - Disperse Red 17-Acid Yellow 9-Acid Black 1 - Basic Red 22 - Basic Red 76-Basic Yellow 57 - Basic Brown 16 -Acid Yellow 36 -Acid Orange 7-Acid Red 33-Acid Red 35-Basic Brown 17-Acid Yellow 23 -Acid Orange 24 -Disperse Black 9.

There may also be mentioned 1- (4'-aminodiphenylazo) -2-methyl-4bis- (ss-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalenesulfonic acid.

Among the quinone direct dyes, mention may be made of the following dyes: Disperse Red 15

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-1-N-méthylmorpholiniumpropylamino-4-hydroxyanthraquinone - 1-Aminopropylamino-4-méthylaminoanthraquinone -1-Aminopropylaminoanthraquinone - 5-p-hydroxyéthyl-1, 4-diaminoanthraquinone -2-Aminoéthylaminoanthraquinone - 1, 4-Bis- (ss, y-dihydroxypropylamino)-anthraquinone. -Solvent Violet 13 -Acid Violet 43 -Disperse Violet 1 -Disperse Violet 4 -Disperse Blue 1 -Disperse Violet 8 -Disperse Blue 3 -Disperse Red 11 -Acid Blue 62 -Disperse Blue 7 -Basic Blue 22 -Disperse Purple 15 -Basic Blue 99 as well as the following compounds:

-1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone-1-aminopropylamino-4-methylaminoanthraquinone -1-aminopropylaminoanthraquinone-5-p-hydroxyethyl-1,4-diaminoanthraquinone -2-aminoethylaminoanthraquinone-1,4-bis- (ss, y- dihydroxypropylamino) anthraquinone.

Among the azine dyes include the following compounds: -Basic Blue 17 - Basic Red 2.

Among the triarylmethane dyes that can be used according to the invention, mention may be made of the following compounds: - Basic Green 1 - Acid blue 9 - Basic Violet 3 - Basic Violet 14 - Basic Blue 7 - Acid Violet 49 - Basic Blue 26 - Acid Blue 7

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Parmi les colorants indoaminiques utilisables selon l'invention, on peut citer les composés suivants : - 2-ss-hydroxyéthlyamino-5- [bis- (ss-4'-hydroxyéthyl) amino] anilino-1, 4-benzoquinone -2-0-hydroxyéthylamino-5- (2'-méthoxy-4'-amino) anilino-1, 4-benzoquinone - 3-N (2'-Chtoro-4'-hydroxy) phényi-acétytamino-6-méthoxy-1, 4-benzoquinone imme -3-N (3'-Chloro-4'-méthylamino) phényl-uréido-6-méthyl-1, 4-benzoquinone imine - 3- [4'-N- (Ethyl, carbamylméthyl)-amino]-phényl-uréido-6-méthyl-1, 4-benzoquinone imine Parmi les colorants directs naturels utilisables selon l'invention, on peut citer la lawsone, la juglone, l'alizarine, la purpurine, l'acide carminique, l'acide kermésique, la purpurogalline, le protocatéchaldéhyde, l'indigo, l'isatine, la curcumine, la spinulosine, l'apigénidine. On peut également utiliser les extraits ou décoctions contenant ces colorants naturels et notamment les cataplasmes ou extraits à base de henné.

Among the indoamine dyes that may be used according to the invention, mention may be made of the following compounds: 2-ss-hydroxyethlyamino-5- [bis- (ss-4'-hydroxyethyl) amino] anilino-1,4-benzoquinone -2-0 hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1,4-benzoquinone-3-N (2'-chloro-4'-hydroxy) phenyl-acetylamino-6-methoxy-1,4 benzoquinone imme-3-N (3'-chloro-4'-methylamino) phenyl-ureido-6-methyl-1,4-benzoquinone imine-3- [4'-N- (ethyl, carbamylmethyl) amino] phenyl -ureido-6-methyl-1,4-benzoquinone imine Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna.

The direct dye (s) preferably represent from 0.001 to 20% by weight approximately of the total weight of the ready-to-use composition and even more preferentially from 0.005 to 10% by weight approximately.

In said composition, the ratio of active materials of the concentrations of the direct dye (s) to the amphiphilic polymers according to the invention is between 0.01 and 1000 and preferably between 1 and 10.

More particularly, the compositions according to the invention may further contain at least one amphoteric or cationic polymer.

Cationic Polymers For the purposes of the present invention, the expression "cationic polymer" denotes any polymer containing cationic groups and / or ionizable groups in cationic groups.

The cationic polymers that may be used in accordance with the present invention may be chosen from all those already known per se as improving the cosmetic properties of the hair, namely in particular those described in the patent application EP-A-337 354 and in the French patents 2 270 846.2 383 660.2 598 611.2 470 596 and 2 519 863.

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 The preferred cationic polymers are chosen from those containing units containing primary, secondary, tertiary and / or quaternary amine groups which may either be part of the main polymer chain or may be borne by a lateral substituent directly connected thereto.

The cationic polymers used generally have a number-average molecular weight of between about 500 and 5 × 10 6, and preferably between about 103 and 3 × 10 6.

Among the cationic polymers, mention may be made more particularly of polyamine, polyaminoamide and quaternary polyammonium polymers. These are known products. They are in particular described in French Pat. Nos. 2,505,348 or 2,542,997. Among said polymers, mention may be made of: (1) homopolymers or copolymers derived from acrylic or methacrylic esters or amides and comprising at least one of the units of the following formulas (1), (II), (III) or (IV):

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 in which: R3, which may be identical or different, denote a hydrogen atom or a CH3 radical; A, which may be identical or different, represent a linear or branched alkyl group of 1 to 6 carbon atoms, preferably 2 or 3 carbon atoms or a hydroxyalkyl group of 1 to 4 carbon atoms; R4, R5, R6, which may be identical or different, represent an alkyl group having from 1 to 18 carbon atoms or a benzyl radical and preferably an alkyl group having from 1 to 6 carbon atoms; R1 and R2, identical or different, represent hydrogen or an alkyl group having 1 to 6 carbon atoms and preferably methyl or ethyl; X denotes an anion derived from a mineral or organic acid such as a methosulphate anion or a halide such as chloride or bromide.

- les terpolymères méthacrylate de diméthyl amino éthyle/vinylcaprolactame/ vinylpyrrolidone tel que le produit vendu sous la dénomination GAFFIX VC 713 par la société ISP, The polymers of the family (1) may also contain one or more units derived from comonomers which may be chosen from the family of acrytamides, methacrylamides, diacetones acrylamides, acrylamides and methacrylamides substituted on the nitrogen by lower alkyls (CI-C4). , acrylic or methacrylic acids or their esters of vinyllactams such as vinylpyrrolidone or vinylcaprolactam, vinyl esters. Among these polymers of family (1), mention may be made of: - copolymers of acrylamide and of dimethylaminoethyl methacrylate quaternized with methyl sulphate or with a dimethyl holognide, such as that sold under the name HERCOFLOC by the company Hercules, - the copolymers of acrylamide and methacryloyloxyethyltrimethylammonium chloride described for example in the patent application EP-A-080976 and sold under the name BINA QUAT P 100 by the company CIBA GEIGY, - the copolymer of acrylamide and methacryloyloxyethyltrimethylammonium methosulphate sold under the name Reten by the company Hercules, - vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate quaternized or otherwise, such as the products sold under the name "GAFQUAT" by the company ISP as for example "GAFQUAT 734" or "GAFQUAT 755" or products referred to as "COPOLYMER 845,958 and 937". These polymers are described in detail in French Patents 2,077. 143 and 2.393. 573

dimethylaminoethyl methacrylate / vinylcaprolactam / vinylpyrrolidone terpolymers, such as the product sold under the name GAFFIX VC 713 by the company ISP,

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- les copolymère vinylpyrrolidone/méthacrylamidopropyl dimethylamine commercialisés notamment sous la dénomination STYLEZE CC 10 par ISP, - et les copolymères vinylpyrrolidone/méthacrylamide de diméthylaminopropyle quaternisés tel que le produit vendu sous la dénomination"GAFQUAT HS 100"par la société ISP.

the vinylpyrrolidone / methacrylamidopropyl dimethylamine copolymers sold in particular under the name STYLEZE CC 10 by ISP; and the quaternized vinylpyrrolidone / dimethylaminopropyl methacrylamide copolymers, such as the product sold under the name GAFQUAT HS 100 by the company ISP.

(2) The cellulose ether derivatives comprising quaternary ammonium groups described in French Patent 1,492,597, and in particular the polymers sold under the names "JR" (JR 400, JR 125, JR 30M) or "LR" (LR 400, LR 30M) by Union Carbide Corporation. These polymers are also defined in the CTFA dictionary as quaternary ammoniums of hydroxyethylcellulose reacted with an epoxide substituted by a trimethylammonium group.

(3) Cationic cellulose derivatives such as cellulose copolymers or cellulose derivatives grafted with a water-soluble quaternary ammonium monomer. and described in particular in US Pat. No. 4,131,576, such as hydroxyalkyl celluloses, such as hydroxymethyl, hydroxyethyl or hydroxypropyl celluloses grafted in particular with a salt of methacryloylethyltrimethylammonium, methacrylmidopropyltrimethylammonium, dimethyldiallylammonium.

The marketed products corresponding to this definition are more particularly the products sold under the name "Celquat L 200" and "Celquat H 100" by the company National Starch.

(4) The cationic polysaccharides described more particularly in US Pat. Nos. 3,589,578 and 4,031,307, such as guar gums containing cationic trialkylammonium groups. For example, guar gums modified with a salt (eg chloride) of 2,3-epoxypropyltrimethylammonium are used.

Such products are marketed in particular under the trade names JAGUAR C13 S, JAGUAR C 15, JAGUAR C 17 or JAGUAR C162 by the company MEYHALL.

(5) Polymers consisting of piperazinyl units and straight or branched chain alkylene or hydroxyalkylene divalent radicals, optionally interrupted by oxygen, sulfur or nitrogen atoms or by aromatic or heterocyclic rings,

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 as well as the oxidation and / or quaternization products of these polymers. Such polymers are especially described in French Patents 2 162. 025 and 2. 280. 361.

(6) Water-soluble polyamino amines prepared in particular by polycondensation of an acidic compound with a polyamine; these polyaminoamides can be crosslinked by an epihalohydrin, a diepoxide, a dianhydride, an unsaturated dianhydride, a bis-unsaturated derivative, a bis-halohydrin, a bis-azetidinium, a bis-haloacyldiamine, a bis-alkyl halide or else with an oligomer resulting from the reaction of a bifunctional compound which is reactive with a bis-halohydrin, a bisazetidinium, a bis-haloacyldiamine, an alkyl bis-halide, a epilhalohydrin, a diepoxide or a bis-unsaturated derivative: the crosslinking agent being used in proportions ranging from 0.025 to 0.35 mole per amine group of the polyaminoamide; these polyaminoamides can be alkylated or if they contain one or more tertiary amine functions, quaternized. Such polymers are in particular described in French Patents 2 252 840 and 2 368. 508.

(7) Polyaminoamide derivatives resulting from the condensation of polyalkylene polyamines with polycarboxylic acids followed by alkylation with difunctional agents. Mention may be made, for example, of adipic acid-diacoylaminohydroxyalkyldialoylene triamine polymers in which the alkyl radical contains from 1 to 4 carbon atoms and preferably denotes methyl, ethyl or propyl. Such polymers are described in particular in French Patent 1,583. 363.

Among these derivatives, mention may be made more particularly of the adipic acid / dimethylaminohydroxypropyl / diethylene triamine polymers sold under the name "Cartaretine F, F4 or F8" by the company Sandoz.

(8) The polymers obtained by reacting a polyalkylene polyamine comprising two primary amine groups and at least one secondary amine group with a dicarboxylic acid chosen from diglycolic acid and saturated aliphatic dicarboxylic acids having from 3 to 8 carbon atoms. The molar ratio between the polyalkylene polyamine and the dicarboxylic acid is between 0.8: 1 and 1.4: 1; the polyaminoamide resulting therefrom being reacted with epichlorohydrin in a molar ratio of epichlorohydrin relative to the secondary amine group of the polyaminoamide of between 0.5: 1 and 1.8: 1. Such polymers are described in particular in the patents US 3,227. 615 and 2. 961.347.

Polymers of this type are in particular marketed under the name "Hercosett 57" by the company Hercules Inc. or under the name "PD 170" or

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"Delsette 101"par la société Hercules dans le cas du copolymère d'acide adipque/époxypropyt/diéthytène-triamine. (9) Les cyclopolymères d'alkyl diallyl amine ou de dialkyl diallyl ammonium tels que les homopolymères ou copolymères comportant comme constituant principal de la chaîne des motifs répondant aux formules (V) ou (VI) :

formules dans lesquelles k et t sont égaux à 0 ou 1, la somme k + t étant égale à 1 ; Rg désigne un atome d'hydrogène ou un radical méthyle ; R7 et R8, indépendamment l'un de l'autre, désignent un groupement alkyle ayant de 1 à 22 atomes de carbone, un groupement hydroxyalkyl dans lequel le groupement alkyle a de préférence 1 à 5 atomes de carbone, un groupement amidoalkyle inférieur (Cl-C4), ou R7 et Ra peuvent désigner conjointement avec l'atome d'azote auquel ils sont rattachés, des groupement hétérocycliques, tels que pipéridinyle ou morpholinyle ; R7 et Ra indépendamment l'un de l'autre désignent de préférence un groupement alkyle ayant de 1 à 4 atomes de carbone ; y- est un anion tel que bromure, chlorure, acétate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. Ces polymères sont notamment décrits dans le brevet français 2.080. 759 et dans son certificat d'addition 2.190. 406.

"Delsette 101" by the company Hercules in the case of the adipic acid / epoxypropyl / diethylenetriamine copolymer. (9) cyclopolymers of alkyl diallyl amine or of dialkyl diallyl ammonium, such as homopolymers or copolymers comprising, as main constituent of the chain, units corresponding to formulas (V) or (VI):

formulas in which k and t are 0 or 1, the sum k + t being equal to 1; Rg denotes a hydrogen atom or a methyl radical; R7 and R8, independently of each other, denote an alkyl group having 1 to 22 carbon atoms, a hydroxyalkyl group in which the alkyl group preferably has 1 to 5 carbon atoms, a lower amidoalkyl group (Cl -C4), or R7 and Ra may designate, together with the nitrogen atom to which they are attached, heterocyclic groups, such as piperidinyl or morpholinyl; R7 and Ra, independently of one another, preferably denote an alkyl group having 1 to 4 carbon atoms; y- is an anion such as bromide, chloride, acetate, borate, citrate, tartrate, bisulfate, bisulfite, sulfate, phosphate. These polymers are described in particular in French Patent 2,080. 759 and in his certificate of addition 2.190. 406.

Among the polymers defined above, mention may be made more particularly of the homopolymer of dimethyldiallylammonium chloride sold under the name "Merquat 100" by Calgon (and its counterparts of low weight average molecular weight) and the copolymers of sodium chloride. diallyldimethylammonium and acrylamide sold under the name "MERQUAT 550".

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formule (VII) dans laquelle : R10, R11, R12 et Ri3, identiques ou différents, représentent des radicaux aliphatiques alicycliques, ou arylaliphatiques contenant de 1 à 20 atomes de carbone ou des radicaux hydroxyalkylaliphatiques inférieurs, ou bien Rio. Pu, R12 et R13, ensemble ou séparément, constituent avec les atomes d'azote auxquels ils sont rattachés des hétérocycles contenant éventuellement un second hétéroatome autre que l'azote ou bien Rio, Ru, Ri2 et R13 représentent un radical alkyle en Cl-C6 linéaire ou ramifié substitué par un groupement nitrile, ester, acyle, amide ou-CO-0-R--D ou-CO-NH- R14-D où R14 est un alkylène et D un groupement ammonium quaternaire ; A1 et B1 représentent des groupements polyméthyléniques contenant de 2 à 20 atomes de carbone pouvant être linéaires ou ramifiés, saturés ou insaturés. et pouvant contenir, liés à ou intercalés dans la chaîne principale, un ou plusieurs cycles aromatiques, ou un ou plusieurs atomes d'oxygène, de soufre ou des groupements sulfoxyde, sulfone. disulfure, amino, alkylamino, hydroxyle, ammonium quaternaire. uréido, amide ou ester, et X désigne un anion dérivé d'un acide minéral ou organique ;

Ai, Rl et R12 peuvent former avec les deux atomes d'azote auxquels ils sont rattachés un cycle pipérazinique ; en outre si Al désigne un radical alkylène ou hydroxyalkylène linéaire ou ramifié, saturé ou insaturé, B1 peut également désigner un groupement- (CH2) n-CO-D-OC-(CH2)n- dans lequel D désigne : a) un reste de glycol de formule :-0-Z-O-, où Z désigne un radical hydrocarboné linéaire ou ramifié ou un groupement répondant à l'une des formules suivantes : - (CH2-CH2-0) x-CH2-CH2- -[CH2-CH(CH3)-O]y-CH2-CH(CH3)- où x et y désignent un nombre entier de 1 à 4, représentant un degré de polymérisation défini et unique ou un nombre quelconque de 1 à 4 représentant un degré de polymérisation moyen ; b) un reste de diamine bis-secondaire tel qu'un dérivé de pipérazine ; (10) The quaternary diammonium polymer containing recurring units having the formula:

wherein R10, R11, R12 and R13, identical or different, represent aliphatic alicyclic or arylaliphatic radicals containing 1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, or Rio. Pu, R12 and R13, together or separately, constitute, with the nitrogen atoms to which they are attached, heterocycles optionally containing a second heteroatom other than nitrogen, or else Rio, Ru, Ri2 and R13 represent a C1-C6 alkyl radical. linear or branched chain substituted with a nitrile, ester, acyl, amide or -CO-O-R-D or -CO-NH-R14-D group where R14 is alkylene and D is a quaternary ammonium group; A1 and B1 represent polymethylene groups containing from 2 to 20 carbon atoms which may be linear or branched, saturated or unsaturated. and may contain, bound to or intercalated in the main chain, one or more aromatic rings, or one or more oxygen atoms, sulfur or sulfoxide groups, sulfone. disulfide, amino, alkylamino, hydroxyl, quaternary ammonium. ureido, amide or ester, and X denotes an anion derived from a mineral or organic acid;

A 1, R 1 and R 12 can form with the two nitrogen atoms to which they are attached a piperazine ring; in addition, if Al denotes a linear or branched, saturated or unsaturated alkylene or hydroxyalkylene radical, B1 can also denote a group - (CH2) n -CO-D-OC- (CH2) n- in which D denotes: a) a radical glycol composition of formula: -O-ZO-, where Z denotes a linear or branched hydrocarbon radical or a group corresponding to one of the following formulas: - (CH 2 -CH 2 -O) x -CH 2 -CH 2 - - [CH 2 - CH (CH 3) -O] y -CH 2 -CH (CH 3) - where x and y denote an integer of 1 to 4, representing a defined and unique degree of polymerization or any number of 1 to 4 representing a degree of polymerization way ; b) a bis-secondary diamine residue such as a piperazine derivative;

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c) un reste de diamine bis-primaire de formule : -NH-Y-NH-, où Y désigne un radical hydrocarboné linéaire ou ramifié, ou bien le radical bivalent - CH2-CH2-S-S-CH2-CH2- ; d) un groupement uréylène de formule :-NH-CO-NH-.

c) a bis-primary diamine residue of formula: -NH-Y-NH-, where Y denotes a linear or branched hydrocarbon radical, or alternatively the divalent radical - CH2-CH2-SS-CH2-CH2-; d) a ureylene group of formula: -NH-CO-NH-.

Preferably, X- is an anion such as chloride or bromide These polymers have a number average molecular weight generally between 1000 and 100000.

Polymers of this type are described in French patents 2,320. 330, 2.270. 846.2. 316.271, 2.336. 434 and 2.413. 907 and US Patents 2,273. 780.2. 375.853, 2.388. 614.2. 454,547, 3.206. 462.2. 261. 002, 2.271. 378.3. 874.870, 4. 001. 432, 3.929. 990.3. 966.904, 4.005. 193.4. 025,617, 4,025. 627.4. 025,653, 4,026. 945 and 4.027. 020.

dans laquelle R10, R11.R12 et R13, identiques ou différents, désignent un radical alkyle ou hydroxyalkyl ayant de 1 à 4 atomes de carbone environ, n et p sont des nombres entiers variant de 2 à 20 environ et, X- est un anion dérivé d'un acide minéral ou organique. It is more particularly possible to use polymers which consist of recurring units corresponding to the following formula (VIII):

in which R10, R11.R12 and R13, which are identical or different, denote an alkyl or hydroxyalkyl radical having from 1 to 4 carbon atoms, n and p are integers ranging from 2 to approximately 20 and, X- is an anion derived from a mineral or organic acid.

dans laquelle p désigne un nombre entier variant de 1 à 6 environ. D peut être nul ou peut représenter un groupement- (CHr-CO-dans lequel r désigne un nombre égal à 4 ou à 7, X- est un anion ; (11) Quaternary polyammoniums consisting of repeating units of formula (IX):

wherein p denotes an integer ranging from 1 to about 6. D can be zero or can represent a group - (CHr-CO- in which r is a number equal to 4 or 7, X- is an anion;

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De tels polymères peuvent être préparés selon les procédés décrits dans les brevets U. SA no 4 157 388, 4 702 906, 4 719 282. Ils sont notamment décrits dans la demande de brevet EP-A-122 324.

Such polymers can be prepared according to the processes described in U.S. Patent Nos. 4,157,388, 4,702,906 and 4,719,282. They are described in particular in patent application EP-A-122,324.

Among them, there may be mentioned, for example, the products "Mirapol A 15", "Mirapol AD1", "Mirapol AZ1" and "Mirapol 175" sold by Miranol.

(12) Quaternary polymers of vinylpyrrolidone and of vinylimidazole such as, for example, the products sold under the names Luviquat FC 905, FC 550 and FC 370 by the company B. A. S. F.

(13) Polyamines such as Polyquart H sold by HENKEL, referenced under the name "POLYETHYLENE GLYCOL (15) TALLOW POLYAMINE" in the CTFA dictionary (14) Crosslinked polymers of methacryloyloxyalkyl (C1-C4) trialkyl (C1-C4) salts ) Ammonium such as polymers obtained by homopolymerization of dimethylaminoethyl methacrylate quaternized with methyl chloride, or by copolymerization of acrylamide with dimethylaminoethyl methacrylate quaternized with methyl chloride, the homo or copolymerization being followed by crosslinking with a compound with olefinic unsaturation, in particular methylenebisacrylamide. It is more particularly possible to use a crosslinked acrylamide / methacryloyloxyethyltrimethylammonium chloride copolymer (20/80 by weight) in the form of a dispersion containing 50% by weight of said copolymer in mineral oil. This dispersion is marketed under the name "SALCARE SC 92" by the company ALLIED COLLOIDS. It is also possible to use a crosslinked homopolymer of methacryloyloxyethyltrimethylammonium chloride containing about 50% by weight of the homopolymer in mineral oil or in a liquid ester. These dispersions are sold under the names "SALCARE &commat; SC 95" and "SALCARE SC 96" by the company ALLIED COLLOIDS.

Other cationic polymers that may be used in the context of the invention are polyalkyleneimines, in particular polyethyleneimines, polymers containing vinylpyridine or vinylpyridinium units, condensates of polyamines and of epichlorohydrin, quaternary polyureylenes and chitin derivatives.

Among all the cationic polymers that may be used in the context of the present invention, it is preferred to use the polymers of families (1), (9), (10)

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et notamment ceux dont le poids moléculaire, déterminé par chromatographie par perméation de gel, est compris entre 9500 et 9900 ;

et notamment ceux dont le poids moléculaire, déterminé par chromatographie par perméation de gel, est d'environ 1200 La concentration en polymère cationique dans la composition selon la présente invention peut varier de 0,01 à 10% en poids par rapport au poids total de la composition, de préférence de 0,05 à 5% et plus préférentiellement encore de 0,1 à 3%. (11) and (14) and even more preferentially the polymers with repeating units of the following formulas M) and (U):

and in particular those whose molecular weight, determined by gel permeation chromatography, is between 9500 and 9900;

and in particular those whose molecular weight, determined by gel permeation chromatography, is about 1200. The concentration of cationic polymer in the composition according to the present invention may vary from 0.01 to 10% by weight relative to the total weight of the composition, preferably from 0.05 to 5% and more preferably from 0.1 to 3%.

Amphoteric Polymers The amphoteric polymers that may be used in accordance with the present invention may be chosen from polymers comprising K and M units statistically distributed in the polymer chain, where K denotes a unit derived from a monomer comprising at least one basic nitrogen atom and M denotes a unit derived from an acidic monomer comprising one or more carboxylic or sulphonic groups, or K and M may denote groups derived from zwitterionic monomers of carboxybetams or of sulphobetaines; K and M may also denote a cationic polymer chain comprising primary, secondary, tertiary or quaternary amine groups, in which at least one of the amine groups carries a carboxylic or sulphonic group connected via a hydrocarbon radical, or K and M are part of a chain of an α, β-dicarboxylic ethylene-based polymer having one of the carboxylic groups having

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 reacted with a polyamine having one or more primary or secondary amine groups.

The amphoteric polymers corresponding to the definition given above, which are more particularly preferred, are chosen from the following polymers: (1) The polymers resulting from the copolymerization of a monomer derived from a vinyl compound carrying a carboxylic group such as, more particularly, the acrylic acid, methacrylic acid, maleic acid, alpha-chloro acrylic acid, and a basic monomer derived from a substituted vinyl compound containing at least one basic atom such as, more particularly, dialkylaminoalkyl methacrylate and acrylate, dialkylaminoalkylmethacrylamide and acrylamide. Such compounds are described in U.S. Patent No. 3,836,537
Mention may also be made of the sodium acrylate / acrylamidopropyltrimethylammonium chloride copolymer sold under the name Polyquart
KE 3033 by the company HENKEL.

The vinyl compound may also be a dialkyldiallylammonium salt such as dimethylidallylammonium chloride. Copolymers of acrylic acid and of the latter monomer are available under the names MERQUAT 280,
MERQUAT 295 and MERQUAT PLUS 3330 by the company CALGON.

 (2) polymers comprising units derived from: a) at least one monomer chosen from acrylamides or methacrylamides substituted on the nitrogen with an alkyl radical, b) with at least one acidic comonomer containing one or more carboxylic groups reagents, and c) at least one basic comonomer such as primary, secondary, tertiary and quaternary amine substituent esters of acrylic and methacrylic acids and the quaternization product of dimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

The N-substituted acrylamides or methacrylamides which are more particularly preferred according to the invention are the groups in which the alkyl radicals contain from 2 to 12 carbon atoms and more particularly N-ethylacrylamide, N-tert-butyl-acrylamide and N-tert-octyl-acrylamide. N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide and the corresponding methacrylamides.

The acidic comonomers are chosen more particularly from acrylic, methacrylic, crotonic, itaconic, maleic, fumaric and monoesteric acids.

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 alkyl having 1 to 4 carbon atoms of maleic or fumaric acids or anhydrides.

Preferred basic comonomers are aminoethyl, butylaminoethyl, N, N'-dimethylaminoethyl, and N-tert-butylaminoethyl methacrylates.

The copolymers whose CTFA (4th Ed., 1991) name is octylacrylamide / acrylates / butylaminoethylmethacrylate copolymer, such as the products sold under the name AMPHOMER or LOVOCRYL 47 by the company National Starch, are particularly used.

dérivant de polyaminoamide de formule générale :

- CO-R-CO-Z-- (X)

dans laquelle R19 représente un radical divalent dérivé d'un acide dicarboxylique saturé, d'un acide aliphatique mono ou dicarboxylique à double liaison éthylénique, d'un ester d'un alcanol inférieur ayant 1 à 6 atomes de carbone de ces acides ou d'un radical dérivant de l'addition de l'un quelconque desdits acides avec une amine bis primaire ou bis secondaire, et Z désigne un radical d'une poiyalkylène-polyamine bis-primaire, mono

ou bis-secondaire et de préférence représente : a) dans les proportions de 60 à 100 moles %, le radical

--H--CH) -N-- (XI) H x H - Jp H H p où x=2 et p=2 ou 3, ou bien x=3 et p=2 ce radical dérivant de la diéthylène triamine, de la triéthylène tétraamine ou de la du propylene triamine ; b) dans les proportions de 0 à 40 moles % le radical (XI) ci-dessus, dans lequel x=2 et p=1 et qui dérive de l'éthylènediamine, ou le radical dérivant de la pipérazlne :

c) dans les proportions de 0 à 20 moles % le radical -NH-(CH2)6-NH- dérivant de l'hexaméthylènediamine, ces polyaminoamines étant réticulées par addition d'un agent réticulant bifonctionnel choisi parmi les épihalohydrines, les diépoxydes, les dianhydrides, les dérivés bis insaturés, au moyen de 0,025 à 0,35 mole d'agent réticulant par (3) The crosslinked polyaminoamides and alkylated partially or totally

derived from polyaminoamide of the general formula:

- CO-R-CO-Z-- (X)

wherein R19 represents a divalent radical derived from a saturated dicarboxylic acid, an ethylenically double bonded mono or dicarboxylic aliphatic acid, an ester of a lower alkanol having 1 to 6 carbon atoms of these acids or a radical derived from the addition of any one of said acids with a primary bis or secondary bis amine, and Z denotes a radical of a bis-primary polyalkylene polyamine, mono

or bis-secondary and preferably represents: a) in the proportions of 60 to 100 mol%, the radical

Where X = 2 and p = 2 or 3, or else x = 3 and p = 2, this radical derived from diethylene triamine, triethylene tetraamine or propylene triamine; b) in the proportions of 0 to 40 mol%, the radical (XI) above, in which x = 2 and p = 1 and which is derived from ethylenediamine, or the radical derived from piperazine:

c) in the proportions of 0 to 20 mole%, the radical -NH- (CH 2) 6 -NH- derived from hexamethylenediamine, these polyaminoamines being crosslinked by addition of a bifunctional crosslinking agent chosen from epihalohydrins, diepoxides, dianhydrides, bis unsaturated derivatives, by means of 0.025 to 0.35 moles of crosslinking agent

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 amino group of the polyaminoamide and alkylated by the action of acrylic acid, chloroacetic acid or an alkane sultone or their salts.

The saturated carboxylic acids are preferably chosen from acids having 6 to 10 carbon atoms, such as adipic acid, trimethyl-2, 2, 4-adipic acid and trimethyl-2,4,4-adipic acid, terephthalic acid, ethylenic double bond such as acrylic acid, methacrylic acid, itaconic acid.

The alkanesultones used in the alkylation are preferably propane or butane sultone, the salts of the alkylating agents are preferably the sodium or potassium salts.

dans laquelle R20 désigne un groupement insaturé polymérisable tel qu'un groupement acrylate, méthacrylate, acrylamide ou méthacrylamide, y et z représentent un nombre entier de 1 à 3, R21 et R22 représentent un atome d'hydrogène, méthyle, éthyle ou propyl, R23 et R24 représentent un atome d'hydrogène ou un radical alkyle de telle façon que la somme des atomes de carbone dans R23 et R24 ne dépasse pas 10. (4) polymers having zwitterionic units of formula:

in which R 20 denotes a polymerizable unsaturated group such as an acrylate, methacrylate, acrylamide or methacrylamide group, y and z represent an integer of 1 to 3, R 21 and R 22 represent a hydrogen, methyl, ethyl or propyl atom, R 23 and R24 represents a hydrogen atom or an alkyl radical such that the sum of the carbon atoms in R23 and R24 does not exceed 10.

Polymers comprising such units may also comprise units derived from non-zwitterionic monomers such as dimethyl or diethylaminoethyl acrylate or methacrylate or alkyl acrylates or methacrylates, acrylamides or methacrylamides or vinyl acetate.

By way of example, mention may be made of the copolymer of methyl methacrylate / methyl dimethylcarboxymethylammonioethylmethacrylate, such as the product sold under the name DIAFORMER Z301 by the company SANDOZ.

 (5) polymers derived from chitosan having monomeric units corresponding to the following formulas (XIII), (XIV), (XV):

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le motif (XIII) étant présent dans des proportions comprises entre 0 et 30%, le motif (XIV) dans des proportions comprises entre 5 et 50% et le motif F dans des proportions comprises entre 30 et 90%, étant entendu que dans ce motif (XV), R25 représente un radical de formule :

dans laquelle si q=O, R26, R27 et R28'identiques ou différents, représentent chacun un atome d'hydrogène, un reste méthyle, hydroxyle, acétoxy ou amino, un reste monoa ! coy ! armne ou un reste dialcoylamine éventuellement interrompus par un ou plusieurs atomes d'azote et/ou éventuellement substitués par un ou plusieurs groupes amine, hydroxyle, carboxyle, alcoylthio, sulfonique, un reste alcoylthio dont le groupe alcoyle porte un reste amino, l'un au moins des radicaux R26, R27 et R28 étant dans ce cas un atome d'hydrogène ; ou si q=1, R26, R27 et R28 représentent chacun un atome d'hydrogène, ainsi que les sels formés par ces composés avec des bases ou des acides.

the unit (XIII) being present in proportions of between 0 and 30%, the unit (XIV) in proportions of between 5 and 50% and the unit F in proportions of between 30 and 90%, it being understood that in this R25 represents a radical of formula

wherein if q = O, R26, R27 and R28 'are the same or different, each represents a hydrogen atom, a methyl, hydroxyl, acetoxy or amino residue, a monovalent residue; coy! armne or a dialkylamine residue optionally interrupted by one or more nitrogen atoms and / or optionally substituted with one or more amine, hydroxyl, carboxyl, alkylthio, sulphonic groups, an alkylthio radical whose alkyl group carries an amino residue, one at least radicals R26, R27 and R28 being in this case a hydrogen atom; or if q = 1, R26, R27 and R28 each represents a hydrogen atom, as well as the salts formed by these compounds with bases or acids.

 (6) The polymers derived from the N-carboxyalkylation of chitosan, such as N-carboxymethylchitosan or N-carboxybutylchitosan sold under the name "Evalsan" by the company Jan Dekker.

 (7) The polymers corresponding to the general formula (XI) such as those described for example in the French patent 1,400,366:

<Desc / Clms Page number 27>

dans laquelle R29 représente un atome d'hydrogène, un radical CH30, CH3CH20, phényle, R30 désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R31 désigne l'hydrogène ou un radical alkyle inférieur tel que méthyle, éthyle, R32 désigne un radical alkyle inférieur tel que méthyle, éthyle ou un radical répondant à la formule :-R33-N (R31) 2, R33 représentant un groupement-CH2-CH2-,-CH2-CH2-CH2- ,-CH2-CH (CH3)-, R31 ayant les significations mentionnées ci-dessus, ainsi que les homologues supérieurs de ces radicaux et contenant jusqu'à 6 atomes de carbone, r est tel que le poids moléculaire est compris entre 500 et 6000000 et de préférence entre 1000 et 1000000.

in which R29 represents a hydrogen atom, a radical CH30, CH3CH20, phenyl, R30 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R31 denotes hydrogen or a lower alkyl radical such as methyl, ethyl, R32 denotes a lower alkyl radical such as methyl, ethyl or a radical corresponding to the formula: -R33-N (R31) 2, R33 representing a group -CH2-CH2-, -CH2-CH2-CH2-, -CH2-CH (CH 3) -, R 31 having the meanings mentioned above, as well as the higher homologues of these radicals and containing up to 6 carbon atoms, r is such that the molecular weight is between 500 and 6000000 and preferably between 1000 and and 1000000.

et X désigne le symbole E ou E', E ou E'identiques ou différents désignent un radical bivalent qui est un radical alkylène à chaîne droite ou ramifiée comportant jusqu'à 7 atomes de carbone dans la chaîne principale non substituée ou substituée par des groupements hydroxyle et pouvant comporter en outre des atomes d'oxygène, d'azote, (8) Amphoteric polymers of the -DXDX-type chosen from: a) the polymers obtained by the action of chloroacetic acid or sodium chloroacetate on compounds comprising at least one unit of formula: -DXDXD- (XVI 1) where D denotes a radical

and X denotes the symbol E or E ', E or E' the same or different denotes a divalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the unsubstituted or group-substituted main chain hydroxyl and may further comprise oxygen, nitrogen,

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de soufre, 1 à 3 cycles aromatiques et/ou hétérocycliques ; les atomes d'oxygène, d'azote et de soufre étant présents sous forme de groupements éther, thioéther, sutfoxyde, sulfone, sulfonium, alkylamine, alkénylamine, des groupements hydroxyle, benzylamine, oxyde d'amine, ammonium quaternaire, amide, imide, alcool, ester et/ou uréthanne ; b) les polymères de formule : -D-X-D-X- (XVIII) où D désigne un radical

et X désigne le symbole E ou E'et au moins une fois E' ; E ayant la signification indiquée ci-dessus et E'est un radical bivalent qui est un radical alkylène à chaîne droite ou ramifiée ayant jusqu'à 7 atomes de carbone dans la chaîne principale, substitué ou non par un ou plusieurs radicaux hydroxyle et comportant un ou plusieurs atomes d'azote, l'atome d'azote étant substitué par une chaîne alkyle interrompue éventuellement par un atome d'oxygène et comportant obligatoirement une ou plusieurs fonctions carboxyle ou une ou plusieurs fonctions hydroxyle et bétaïnisées par réaction avec l'acide chloracétique ou du chloracétate de soude.

sulfur, 1 to 3 aromatic and / or heterocyclic rings; the oxygen, nitrogen and sulfur atoms being present in the form of ether, thioether, sulphoxide, sulphone, sulphonium, alkylamine, alkenylamine, hydroxyl groups, benzylamine, amine oxide, quaternary ammonium, amide, imide groups, alcohol, ester and / or urethane; b) polymers of formula: -DXDX- (XVIII) where D denotes a radical

and X denotes the symbol E or E 'and at least once E'; E having the meaning indicated above and E is a divalent radical which is a straight or branched chain alkylene radical having up to 7 carbon atoms in the main chain, substituted or unsubstituted by one or more hydroxyl radicals and having a or a plurality of nitrogen atoms, the nitrogen atom being substituted by an optionally interrupted alkyl chain by an oxygen atom and necessarily comprising one or more carboxyl functions or one or more hydroxyl functions and betaineized by reaction with chloroacetic acid or chloroacetate of soda.

 (9) (C1-C5) alkyl vinyl ether / maleic anhydride copolymers partially modified by semiamidation with an N, N-dialkylaminoalkylamine such as N, N-dimethylaminopropylamine or by semi-esterification with an N, N-dialkanolamine These copolymers may also comprise other vinylic comonomers such as vinylcaprolactam.

The amphoteric polymers that are particularly preferred according to the invention are those of the family (1).

According to the invention, the amphoteric polymer (s) may represent from 0.01% to 10% by weight, preferably from 0.05% to 5% by weight, and still more preferably from 0.1% to 3% by weight. , the total weight of the composition.

The compositions of the invention preferably comprise one or more surfactants.

The surfactant or surfactants can be indifferently chosen, alone or in mixtures, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants.

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d'aminoalcools ou sels de magnésium) des composés suivants : les alkylsulfates, les alkyléthersulfates, alkylamidoéthersulfates, alkylarylpolyéthersulfates, monoglycéndes sulfates ; les alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, a-oléfine-sulfonates, paraffine-sulfonates ; les alkyl (C6-C24) sulfosuccinates, les alkyl (C6C24) éthersulfosuccinates, les alkyl (C6-C24) amidesulfosuccinates ; les alkyl (Ce-C2') sulfoacétates ; les acyl (C6-C24) sarcosinates et les acyl (C6-C24) glutamates. On peut également utiliser les esters d'alkyl (C6-C24) polyglycosides carboxyliques tels que les alkylglucoside citrates, les alkylpolyglycoside tartrate et les alkylpolyglycoside sulfosuccinates., les alkylsulfosuccinamates ; les acyliséthionates et les N-acyltaurates, le radical alkyle ou acyle de tous ces différents composés comportant de préférence de 12 à 20 atomes de carbone, et le radical aryl désignant de préférence un groupement phényle ou benzyl. Parmi les tensioactifs anioniques encore utilisables, on peut également citer les sels d'acides gras tels que les sels des acides oléique, ricinoléique, palmitique, stéarique, les acides d'huile de coprah ou d'huile de coprah hydrogénée, les acyl-lactylates dont le radical acyle comporte 8 à 20 atomes de carbone. On peut également utiliser les acides d'alkyl D galactoside uroniques et leurs sels, les acides alkyl (C6-C24) éther carboxyliques polyoxyalkylénés, les acides alkyl (C6-C24) aryl éther carboxyliques polyoxyalkylénés, les acides alkyl (C6-C24) amido éther carboxyliques polyoxyalkylénés et leurs sels, en particulier ceux comportant de 2 à 50 groupements oxyde d'alkylène en particulier d'éthylène, et leurs mélanges. The surfactants that are suitable for carrying out the present invention are, in particular: (i) Anionic surfactant (s): As an example of anionic surfactants that can be used, alone or as mixtures, in the context of the According to the present invention, mention may be made especially of (non-limiting list) salts (in particular alkaline salts, in particular sodium salts, ammonium salts, amine salts, salts,

aminoalcohols or magnesium salts) of the following compounds: alkyl sulphates, alkyl ether sulphates, alkyl amido ether sulphates, alkyl aryl polyether sulphates, monoglyceres sulphates; alkylsulfonates, alkylphosphates, alkylamidesulfonates, alkylarylsulfonates, α-olefin-sulfonates, paraffin-sulfonates; (C6-C24) alkylsulphosuccinates, (C6C24) alkylsulfosuccinates, (C6-C24) alkylamidesulfosuccinates; alkyl (Ce-C2 ') sulphoacetates; acyl (C6-C24) sarcosinates and acyl (C6-C24) glutamates. It is also possible to use (C6-C24) alkyl polyglycoside carboxylic esters such as alkylglucoside citrates, alkylpolyglycoside tartrate and alkylpolyglycoside sulfosuccinates, alkylsulfosuccinamates; acylisethionates and N-acyltaurates, the alkyl or acyl radical of all these different compounds preferably comprising from 12 to 20 carbon atoms, and the aryl radical preferably denoting a phenyl or benzyl group. Among the anionic surfactants that can still be used, mention may also be made of fatty acid salts such as the salts of oleic, ricinoleic, palmitic and stearic acids, coconut oil acids or hydrogenated coconut oil acids, acyl lactylates. wherein the acyl radical has 8 to 20 carbon atoms. It is also possible to use alkyl D galactoside uronic acids and their salts, polyoxyalkylenated (C6-C24) alkyl carboxylic ether acids, polyoxyalkylenated (C6-C24) aryl ether carboxylic acids, (C6-C24) alkyl amido acids. polyoxyalkylenated carboxylic ether and their salts, in particular those containing from 2 to 50 alkylene oxide groups, in particular ethylene, and mixtures thereof.

 (ii) Nonionic surfactants (sl: Nonionic surfactants are also well-known compounds per se (see in particular in this connection "Handbook of Surfactants" by MR PORTER, Blackie & Son editions (Glasgow and London), 1991, pp 116-178) and their nature is not critical in the context of the present invention, so they can be

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notamment choisis parmi (liste non limitative) les alcools, les alpha-diols, les alkylphénols polyéthoxylés, polypropoxylés, ayant une chaîne grasse comportant par exemple 8 à 18 atomes de carbone, le nombre de groupements oxyde d'éthylène ou oxyde de propylène pouvant aller notamment de 2 à 50. On peut également citer les copolymères d'oxyde d'éthylène et de propylène, les condensats d'oxyde d'éthylène et de propylène sur des alcools gras ; les amides gras polyéthoxylés ayant de préférence de 2 à 30 moles d'oxyde d'éthylène, les amides gras polyglycérolés comportant en moyenne 1 à 5 groupements glycérol et en particulier 1,5 à 4 ; les amines grasses polyéthoxylées ayant de préférence 2 à 30 moles d'oxyde d'éthylène ; les esters d'acides gras du sorbitan oxyéthylénés ayant de 2 à 30 moles d'oxyde d'éthylène ; les esters d'acides gras du sucrose, les esters d'acides gras du polyéthylèneglycol, les alkylpolyglycosides, les dérivés de N-alkyl glucamin, les oxydes d'amines tels que les oxydes d'alkyl (C0-C14) amines ou les oxydes de N-acylaminopropylmorpholine. On notera que les alkylpolyglycosides constituent des tensio-actifs non-ioniques rentrant particulièrement bien dans le cadre de la présente invention.

in particular chosen from (non-limiting list) polyethoxylated, polypropoxylated alcohols, alpha-diols, alkylphenols, having a fatty chain comprising, for example, 8 to 18 carbon atoms, the number of ethylene oxide or propylene oxide groups being in particular from 2 to 50. Mention may also be made of copolymers of ethylene oxide and propylene oxide, condensates of ethylene oxide and of propylene oxide on fatty alcohols; polyethoxylated fatty amides preferably having from 2 to 30 moles of ethylene oxide, polyglycerolated fatty amides comprising on average 1 to 5 glycerol groups and in particular 1.5 to 4; polyethoxylated fatty amines preferably having 2 to 30 moles of ethylene oxide; oxyethylenated sorbitan fatty acid esters having from 2 to 30 moles of ethylene oxide; sucrose fatty acid esters, polyethylene glycol fatty acid esters, alkylpolyglycosides, N-alkyl glucamin derivatives, amine oxides such as (C0-C14) alkyl oxides or oxides N-acylaminopropylmorpholine. It will be noted that the alkylpolyglycosides constitute nonionic surfactants that fall particularly well within the scope of the present invention.

 (iii) amphoteric (s) or zwitterionic (s) surfactant (s): Amphoteric or zwitterionic surfactants, the nature of which does not fall within the scope of the present invention of a critical nature, may especially be (non-limiting list) derivatives of aliphatic secondary or tertiary amines, in which the aliphatic radical is a linear or branched chain containing 8 to 18 carbon atoms and containing at least one water-soluble anionic group (for example carboxylate, sulphonate, sulphate, phosphate or phosphonate); mention may also be made of (C8-C20) alkyl betaines, sulphobetaines, (C8-C20) alkylamido (C1-C6) alkyl betaines or (C8-C20) alkylamido (C1-C6) alkyl sulphobetaines.

Among the amine derivatives, mention may be made of the products sold under the name MIRANOL, as described in US Pat. Nos. 2,528,378 and 2,781,354 and classified in the CTFA dictionary, 3rd edition, 1982, under the names Amphocarboxyglycinates and Amphocarboxypropionates of respective structures: R2-CONHCH2CH2-N (R3) (R4) (CH2COO-) in which: R2 denotes an alkyl radical of an R2-COOH acid present in the hydrolysed coconut oil, a heptyl radical, nonyl or undecyl, R3 denotes a beta-hydroxyethyl group and R4 a carboxymethyl group;

<Desc / Clms Page number 31>

et R2'-CONHCH2CH2-N (B) (C) dans laquelle : B représente -CH2CH20X', C représente- (CH) -Y', avec z = 1 ou 2, X'désigne le groupement-CH2CH2-COOH ou un atome d'hydrogène Y'désigne-COOH ou) e radical-CHs-CHOH-SOsH Ri désigne un radical alkyle d'un acide RU-COSH présent dans l'huile de coprah ou dans l'huile de lin hydrolysée, un radical alkyle, notamment en C7, Cg, C11 ou C13, un radical alkyle en C17 et sa forme iso, un radical CH insaturé.

and R2'-CONHCH2CH2-N (B) (C) wherein: B represents -CH2CH2OX ', C represents - (CH) -Y', with z = 1 or 2, X'disigne the group -CH2CH2-COOH or a hydrogen atom Y'désigne-COOH or) radical-CHs-CHOH-SOsH Ri denotes an alkyl radical of an acid RU-COSH present in coconut oil or in hydrolysed linseed oil, an alkyl radical , especially C7, C8, C11 or C13, a C17 alkyl radical and its iso form, an unsaturated CH radical.

These compounds are classified in the CTFA dictionary, 5th edition, 1993, under the names Disodium Cocoamphodiacetate, Disodium Lauroamphodiacetate, Disodium Caprylamphodiacetate, Disodium Capryloamphodiacetate, Disodium Cocoamphodipropionate, Disodium Lauroamphodipropionate, Disodium Caprylamphodipropionate, Disodium Capryloamphodipropionate, Lauroamphodipropionic Acid, Cocoamphodipropionic Acid.

By way of example, mention may be made of cocoamphodiacetate sold under the trade name MIRANOL C2M concentrated by the company RHODIA CHIMIE (iv) Cationic surfactants: Among the cationic surfactants, mention may be made in particular (non-limiting list): the salts of fatty amines primary, secondary or tertiary, optionally polyoxyalkylenated; quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium or alkylpyridinium chlorides or bromides; imidazoline derivatives; or oxides of amines with a cationic character.

The amounts of surfactants present in the composition according to the invention may vary from 0.01 to 40% and preferably from 0.5 to 30% of the total weight of the composition.

The compositions according to the invention may also contain other rheology adjusting agents such as cellulosic thickeners.

<Desc / Clms Page number 32>

(hydroxyéthycellulose, hydroxypropylcellulose, carboxyméthytcettutose..),) a gomme de guar et ses dérivés (hydroxypropylguar..), les gommes d'origine microbienne (gomme de xanthane, gomme de scléroglucane..), les épaississants synthétiques tels que les homopolymères réticulés d'acide acrylique ou d'acide acrylamidopropanesulfonique et les polymères associatifs non ioniques, anioniques, cationiques ou amphotères, tels que les polymères commercialisés sous les appellations PEMULEN TR1 ou TR2 par la société GOODRICH, SALCARE SC90 par la société ALLIED COLLOIDS, ACULYN 22, 28, 33, 44, ou 46 par la société ROHM & HAAS et ELFACOS T210 et T212 par la société AKZO.

(hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylketutose ..),) guar gum and its derivatives (hydroxypropylguar ..), gums of microbial origin (xanthan gum, scleroglucan gum ..), synthetic thickeners such as crosslinked homopolymers acrylic acid or acrylamidopropanesulphonic acid and associative nonionic, anionic, cationic or amphoteric polymers, such as the polymers sold under the names Pemulen TR1 or TR2 by the company Goodrich, Salcare SC90 by the company Allied Colloids, Aculyn 22, 28, 33, 44, or 46 by the company ROHM & HAAS and ELFACOS T210 and T212 by the company AKZO.

These auxiliary thickeners may represent from 0.01 to 10% by weight of the total weight of the composition.

monoéthylique et monobutylique d'éthyléneglycol, le propylèneglycol ou ses éthers tels que, par exemple, le monométhyléther de propylèneglycol, le butylèneglycol, le dipropylèneglycol ainsi que les alkyléthers de diéthylèneglycol comme par exemple, le monoéthyléther ou le monobutyléther du diéthylèneglycol. Les solvants peuvent alors être présents dans des concentrations comprises entre environ 0,5 et 20% et, de préférence, entre environ 2 et 10% en poids par rapport au poids total de la composition. The medium of the composition suitable for dyeing is preferably an aqueous medium consisting of water and may advantageously contain cosmetically acceptable organic solvents, of which, more particularly, alcohols such as ethyl alcohol, alcohol, and the like. isopropyl alcohol, benzyl alcohol. and pheny alcohol! éthyiique. or polyols or polyol ethers such as, for example, monomethyl ethers,

monoethyl and monobutyl ethylene glycol, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether, butylene glycol, dipropylene glycol and diethylene glycol alkyl ethers such as diethylene glycol monoethyl ether or monobutyl ether. The solvents can then be present in concentrations of between approximately 0.5 and 20% and, preferably, between approximately 2 and 10% by weight relative to the total weight of the composition.

The dye composition may also contain an effective amount of other agents, also known previously in direct dyeing, such as various conventional adjuvants such as sequestering agents, preservatives, associative polymers other than those of the invention, and in particular polyurethanes. nonionic associative polyethers.

Of course, those skilled in the art will take care to choose the optional additional compounds or compounds mentioned above, so that the advantageous properties intrinsically attached to the dye composition according to the invention are not, or not substantially impaired by the addition or additions envisaged.

In the ready-to-use composition with an oxidizing agent (lightening dyeing composition), the oxidizing agent is preferably chosen from hydrogen peroxide,

<Desc / Clms Page number 33>

le peroxyde d'urée, les bromates ou ferricyanures de métaux alcalins, les persels tels que les perborates et les persulfates. L'utilisation du peroxyde d'hydrogène est particulièrement préférée. Cet agent oxydant est avantageusement constitué par une solution d'eau oxygénée dont le titre peut varier, plus particulièrement, d'environ 1 à 40 volumes, et encore plus préférentiellement d'environ 5 à 40.

urea peroxide, alkali metal bromates or ferricyanides, persalts such as perborates and persulfates. The use of hydrogen peroxide is particularly preferred. This oxidizing agent is advantageously constituted by a solution of hydrogen peroxide whose content may vary, more particularly, from about 1 to 40 volumes, and even more preferably from about 5 to 40.

It is also possible to use one or more oxidation-reduction enzymes such as laccases, peroxidases and 2-electron oxidoreductases (such as uricase) as oxidizing agent, if appropriate in the presence of their respective donor or cofactor.

The pH of the ready-to-use composition without oxidizing composition ready for use or composition resulting from the mixing of the dye composition and the oxidizing composition] is generally between 2 and 12. It is preferably between 3 and 11, and may be adjusted to the desired value by means of acidifying or alkalizing agents well known in the art for dyeing keratinous fibers.

More preferably, when the composition contains an oxidizing agent for lightening the fibers, the pH of the ready-to-use mixture is greater than 7 and even more preferably greater than 8.

dans laquelle R est un reste propylène éventuellement substitué par un groupement hydroxyle ou un radical alkyle en Ci-C4 ; R38, R39, R4o et R41, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle en Ci-C4 ou hydroxyalkyl en Ci-C4. Among the alkalinizing agents, mention may be made, for example, of ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, hydroxyalkylamines and ethylenediamines which are oxyethylenated and / or oxypropylenated, the hydroxides of sodium or potassium and the compounds of formula (XIX) below:

wherein R is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; R38, R39, R40 and R41, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

The acidifying agents are conventionally, for example, inorganic or organic acids such as hydrochloric acid, orthophosphoric acid,

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 carboxylic acids such as tartaric acid, citric acid, lactic acid, or sulfonic acids.

The dyeing process according to the invention consists, preferably, in applying the composition without oxidant ready for use, or the composition produced extemporaneously at the time of use from the dyeing and oxidizing compositions described above, on the dry or moist keratinous fibers, and to let it act for a rest period varying, preferably from 1 to 60 minutes, and more preferably from 10 to 45 minutes, to rinse the fibers, then optionally to wash them with shampoo then rinse them again, and dry them.

A variant of this process consists in taking a dye composition containing at least one direct dye but without an amphiphilic polymer according to the invention, another composition containing at least one amphiphilic polymer according to the present invention and to be mixed at the time of use. these two compositions with the oxidizing composition, then to apply and let the mixture act as before.

In a preferred method of the invention, in the case of direct dyeing (with a dye composition) or direct dyeing (with a dye composition and an oxidizing composition), the dye composition and the or the oxidizing composition contain at least one substantive cationic or amphoteric polymer and at least one surfactant.

A concrete example illustrating the invention is indicated below, without being limiting in nature.

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EXAMPLE: The following composition was prepared: (expressed in grams)

<Tb>
<tb> Copolymer <SEP> acid <SEP> acrytamido-2-methyl-2-propanesulfonic acid /
<tb> n-dodecylacrylamide <SEP> (3.5% / 96, <SEP> 5%) <SEP> neutralized <SEP> to <SEP> 100% <SEP> by
<tb> the <SEP> soda .......................................... ............ <SEP> 1
<tb> Alcohol <SEP> isostearyl <SEP> (TEGO <SEP> ALKANOL <SEP> 66 <SEP> sold <SEP> by <SEP>
<tb> company <SEP> GOLDSCHMIDT) <SEP> 12
<tb> Benzyl <SEP> alcohol <SEP> 4
<tb> Polyethylene glycol <SEP> to <SEP> 8 <SEP> moles <SEP> oxide <SEP> of ethylene <SEP> 6
<tb> 1-Hydroxy-4-p-hydroxyethylamino-3-nitrobenzene <SEP> 0.5
<tb> Agent <SEP> sequestering .......................................... ............ <SEP> qs
<tb> Buffer <SEP> phosphate <SEP> ..................... <SEP> qs <SEP> ........... pH. <SEP> .... <SEP> ...... <SEP> 7
<tb> Water <SEP> demineralized ............................... qsp .........
<Tb>

On a utilisé cette composition de teinture directe pour teindre des mèches de cheveux gris à 90% de blancs, par immersion, avec un rapport de bain de 10g de composition pour 1g de cheveux.

This direct dyeing composition was used to dye gray hair strands at 90% white, by immersion, with a bath ratio of 10g of composition to 1g of hair.

After 20 minutes of installation, the locks were rinsed and dried.

A uniform coppery red glow was obtained.

Similar results were obtained by replacing the above-neutralized acrylamido-2-methyl-2-propanesulfonic acid / n-dodecylacrylamide acid copolymer with the sodium hydroxide of the above example with a methylene-bis-acrylamide cross-linked copolymer consisting of 75% by weight of AMPS units neutralized with ammonia and 25% by weight of units of formula (III) in which R1 = H, R4 = C16-C18 and x = 25.

Claims (63)

1. Direct dyeing composition for keratinous fibers, in particular for human keratinous fibers and more particularly the hair, comprising in a medium suitable for dyeing, at least one direct dye, characterized in that it also contains at least one an amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulphonic group, in free or partially or totally neutralized form and in addition at least one hydrophobic part. 2. Composition according to Claim 1, characterized in that the hydrophobic part of the amphiphilic polymer comprises from 6 to 50 carbon atoms. 3. Composition according to claim 2, characterized in that the hydrophobic portion of the amphiphilic polymer has from 6 to 22 carbon atoms. 4. Composition according to claim 3, characterized in that the hydrophobic part of the amphiphilic polymer comprises from 6 to 18 carbon atoms. 5. Composition according to claim 4, characterized in that the hydrophobic portion of the amphiphilic polymer comprises from 12 to 18 carbon atoms. 6. Composition according to any one of claims 1 to 5, characterized in that the amphiphilic polymers are partially or completely neutralized with a mineral or organic base. 7. Composition according to any one of claims 1 to 6, characterized in that the amphiphilic polymers have a molecular weight by weight ranging from 20,000 to 10,000,000. 8. Composition according to claim 7, characterized in that the molecular weight ranges from 50,000 to 8,000,000. <Desc / Clms Page number 37>  9. Composition according to claim 8, characterized in that the molecular weight ranges from 100,000 to 7,000,000. Composition according to any one of Claims 1 to 9, characterized in that the amphiphilic polymers are crosslinked or non-crosslinked. 11. Composition according to claim 10, characterized in that the amphiphilic polymers are crosslinked. 12. Composition according to any one of claims 10 or 11, characterized in that the crosslinking agent (s) are chosen from the olefinically polyunsaturated compounds commonly used for the crosslinking of polymers obtained by radical polymerization. 13. Composition according to Claim 12, characterized in that the crosslinking agent (s) is (are) chosen from methylene-bis-acrylamide, allyl methacrylate or trimethylol propane triacrylate (TMPTA). 14. Composition according to any one of claims 11 to 13, characterized in that the degree of crosslinking preferably ranges from 0.01 to 10 mol% and more particularly from 0.2 to 2 mol% relative to the polymer. 15. Composition according to any one of the preceding claims, characterized in that the ethylenically unsaturated monomer containing sulfonic group is chosen from vinylsulfonic acid, styrene sulphonic acid, (meth) acrylamido (C 1 -C 22) acids. alkylsulphonic acids, N- (C1-C22) alkyl (meth) acrylamido (C1-C22) alkylsulphonic acids and their partially or completely neutralized forms. 16. Composition according to Claim 15, characterized in that the ethylenically unsaturated monomer containing a sulfonic group is chosen from acrylamido acid.

 methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2- acid <Desc / Clms Page number 38>  methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido 2,4,4-trimethylpentanesulfonic acid, 2-methacrylamido-dodecylsulfonic acid, 2acrylamido-2-acid , 6-dimethyl-3-heptanesulfonic acid, and their partially or completely neutralized forms. 17. Composition according to any one of claims 15 or 16, characterized in that the ethylenically unsaturated monomer containing sulfonic group is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and its forms partially or completely neutralized.

18. Composition according to Claim 17, characterized in that the amphiphilic polymers are chosen from the random polymers of AMPS modified by reaction with a n-mono (C6-C22) alkylamine or a di-n- (C6-C22) at ! kyiamine. 19. Composition according to any one of claims 17 or 18, characterized in that the AMPS amphiphilic polymers additionally contain at least one ethylenically unsaturated monomer having no fatty chain. 20. Composition according to Claim 19, characterized in that the ethylenically unsaturated monomer not comprising a fatty chain is chosen from (meth) acrylic acids and their p-substituted alkyl derivatives and their esters obtained with monoalcohols or alcohols. mono or polyalkylene glycols, or from (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures thereof. 21. Composition according to any one of claims 1 to 17, characterized in that the AMPS amphiphilic polymers are chosen from amphiphilic copolymers of AMPS and at least one hydrophobic monomer with ethylenic unsaturation comprising at least a part. hydrophobic having from 6 to 50 carbon atoms.  22. Composition according to Claim 21, characterized in that the hydrophobic part contains from 6 to 22 carbon atoms. 23. Composition according to Claim 22, characterized in that the hydrophobic part contains from 6 to 18 carbon atoms. <Desc / Clms Page number 39>  24. Composition according to Claim 23, characterized in that the hydrophobic part contains from 12 to 18 carbon atoms. 25. Composition according to any one of claims 21 to 24, characterized in that the hydrophobic monomer ethylenically unsaturated is chosen from acrylates or acrylamides of formula (1) below: in which R1 and R3, identical or different, denote a hydrogen atom or a linear or branched C 1 -C 6 alkyl radical (preferably methyl); Y denotes O or NH, R2 denotes a hydrophobic hydrocarbon radical containing at least 6 to 50 carbon atoms and more preferably 6 to 22 carbon atoms and even more preferably 6 to 18 carbon atoms and more particularly 12 to 18 carbon atoms. carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.

26. Composition according to Claim 25, characterized in that the hydrophobic radical R2 is chosen from linear, branched or cyclic C6-C, g alkyl radicals; perfluorinated alkyl radicals of Ce-C18; the cholesteryl radical or a cholesterol ester; polycyclic aromatic groups. 27. Composition according to any one of claims 25 or 26, characterized in that the monomer of formula (1) further comprises at least one alkylene oxide unit (x 1). <Desc / Clms Page number 40>  Composition according to any one of Claims 25 to 27, characterized in that the monomer of formula (1) additionally comprises at least one polyoxyalkylene chain.

29. Composition according to Claim 28, characterized in that the polyoxyalkylene chain is composed of ethylene oxide units and / or propylene oxide units. 30. Composition according to Claim 29, characterized in that the polyoxyalkylene chain consists solely of ethylene oxide units. 31 Composition according to any one of claims 25 to 30, characterized in that the number of oxyalkylenated units ranges from 3 to 100. 32. Composition according to claim 31, characterized in that the number of oxyalkylenated units ranges from 3 to 50. 33. Composition according to claim 32, characterized in that the number of oxyalkylenated units ranges from 8 to 25. 34 Composition according to any one of claims 21 to 26, characterized in that the amphiphilic polymer of AMPS is selected from: - crosslinked or non-crosslinked copolymers, neutralized or not, comprising from 15 to 60% by weight of units AMPS and from 40 to 85% by weight of (Ca-C16) alkyl (meth) acrylamide units or (Ca-C16) alkyl (meth) acrylate units, based on the polymer; terpolymers comprising from 10 to 90 mol% of acrylamide units, from 0.1 to 10 mol% of AMPS units and from 5 to 80 mol% of n- (C6-18) alkylacrylamide units, relative to the polymer . <Desc / Clms Page number 41>  35. Composition according to any one of claims 21 to 26, characterized in that the amphiphilic AMPS polymer is chosen from: - uncrosslinked copolymers of partially or completely neutralized AMPS and n-dodecyl methacrylate.  crosslinked or uncrosslinked copolymers of partially or totally neutralized AMPS and n-dodecylmethacrylamide. 36. Composition according to claims 21 to 33, characterized in that the AMPS amphiphilic polymer is chosen from copolymers consisting of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (II) below:

 in which X + is a proton, an alkali metal cation, an alkaline earth cation or the ammonium ion, and units of the following formula (here):

 in which x denotes an integer ranging from 3 to 100, preferably from 3 to 50 and more preferably from 8 to 25; R 1 has the same meaning as that indicated above in formula (1) and R 4 denotes a linear or branched C 6 -C 22 and more preferably C 12 -C 18 alkyl. <Desc / Clms Page number 42>  Composition according to Claim 36, characterized in that x = 25, Ri is methyl and R4 is n-dodecyl.

38. Composition according to claim 36 or 37, characterized in that the concentration of AMPS pattern varies from 70 to 99 mol% and the concentration of the unit of formula (here) varies from 1 to 30 mol% relative to the copolymer. . 39. A composition according to claim 38, characterized in that the AMPS pattern concentration varies from 70 to 90 mol% and the pattern concentration of formula (here) varies from 10 to 30 mol% relative to the copolymer. 40. Composition according to any one of the preceding claims, characterized in that the amphiphilic polymers are present in concentrations ranging from 0.01 to 30% by weight, more preferably from 0.1 to 10% by weight, and more preferably more preferably from 0.5 to 2% by weight relative to the total weight of the composition 41. The composition as claimed in any one of the preceding claims, characterized in that the direct dye is chosen from neutral, acidic or cationic nitro-benzene direct dyes, neutral azo, acidic or cationic direct dyes, quinone direct dyes, and particular neutral anthraquinone. acidic or cationic, direct azine dyes, triarylmethane direct dyes, indoamine direct dyes and natural direct dyes 42. Composition according to any one of the preceding claims, characterized in that the direct dye (s) are present in concentrations ranging from 0.001% to 20% and preferably from 0.005% to 10% by weight relative to the total weight. of the composition. 43. Composition according to any one of the preceding claims, characterized in that the ratio of active materials of the concentrations of the direct dye (s) to the amphiphilic polymers defined in any one of Claims 1 to 40 is between 0.01. and 1000 and preferably between 1 and 10. 44. Composition according to any one of the preceding claims, characterized in that it also contains at least one amphoteric or cationic polymer. <Desc / Clms Page number 43> 45. Composition according to claim 44, characterized in that the cationic polymer is a quaternary polyammonium consisting of repeating units corresponding to the following formula (W):

 46. Composition according to claim 44, characterized in that the cationic polymer is a quaternary polyammonium consisting of repeating units corresponding to the following formula (U):

 47. A composition according to claim 44, characterized in that the amphoteric polymer is a copolymer comprising at least as monomers of acrylic acid and a dimethyldiallylammonium salt. 48. Composition according to any one of Claims 44 to 47, characterized in that the cationic or amphoteric polymer or polymers represent from 0.01% to 10%, preferably from 0.05% to 5%, and even more preferably from 0.1% to 3% by weight, of the total weight of the composition. 49. Composition according to any one of the preceding claims, characterized in that it contains at least one surfactant chosen from anionic, cationic, nonionic or amphoteric surfactants. <Desc / Clms Page number 44> 50. Composition according to Claim 49, characterized in that the surfactants represent 0.01 to 40% and preferably 0.1 to 30% by weight of the total weight of the composition. 51. Composition according to any one of the preceding claims, characterized in that it has a pH ranging from 2 to 12. 52. Composition according to any one of the preceding claims, characterized in that it additionally contains an oxidizing agent. 53. Composition according to Claim 52, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, persalts, oxidation-reduction enzymes with, if appropriate, their respective donor or cofactor. 54. Composition according to Claim 53, characterized in that the oxidizing agent is hydrogen peroxide. 55. A composition according to claim 54, characterized in that it is a hydrogen peroxide solution whose title varies from 1 to 40 volumes. 56. Composition according to any one of claims 52 to 55, characterized in that it has a pH greater than 7 and preferably greater than 8. 57. Process for the direct dyeing of keratinous fibers, in particular human keratinous fibers, and more particularly the hair, characterized in that it consists in applying to the fibers a dyeing composition as defined in any one of Claims 1. at 51. 58. Process for the direct lightening dyeing of keratinous fibers, in particular human keratinous fibers and more particularly the hair, characterized in that it consists in applying to the fibers a composition resulting from the extemporaneous mixing of a dyeing composition containing, in a medium suitable for dyeing, at least one direct dye, and an oxidizing composition containing an oxidizing agent, the dye composition and / or the oxidizing composition containing at least one amphiphilic polymer comprising at least one ethylenically unsaturated monomer containing a sulfonic group , in free form or partially or totally neutralized and in <Desc / Clms Page number 45>  in addition to at least one hydrophobic part, as defined in any one of claims 1 to 40. 59. A method according to claims 57 or 58. characterized in that it consists in applying to the dry or wet keratinous fibers, direct dyeing composition or direct dyeing lightening, to let it act during a break time varying from 1 to about 60 minutes, and preferably 10 to 45 minutes, rinsing the fibers, then optionally washing them with shampoo, then rinsing them again, and drying them. Direct lightening process for the dyeing of keratinous fibers, in particular human keratinous fibers and more particularly the hair, characterized in that it consists in applying to the dry or moist keratinous fibers the composition produced extemporaneously at the time of use. from a dye composition comprising at least one direct dye, but without an amphiphilic polymer as defined in claims 1-40, another composition containing at least one amphiphilic polymer as defined in claims 1-40, and an oxidizing composition, let it work for a break of between 1 and 60 minutes. and preferably from 10 to 45 minutes, rinsing the fibers, then optionally washing them with shampoo, then rinsing them again, and drying them. 61. A dyeing process according to any one of claims 57-60, characterized in that the dye composition and / or the oxidizing composition contain at least one substantive cationic or amphoteric polymer and at least one surfactant. 62. A device with two compartments or "kit" for dyeing keratinous fibers, in particular human keratinous fibers and more particularly the hair, characterized in that a compartment contains a composition containing at least one direct dye, and another compartment contains a composition comprising at least one amphiphilic polymer as defined in any one of claims 1 to 40. 63. Devices with two compartments or "Kits" for the direct lightening dyeing of keratinous fibers, in particular human keratinous fibers and more particularly the hair, characterized in that a compartment contains a coloring composition containing, in a medium suitable for dyeing, at least one direct dye, and another compartment contains an oxidizing composition containing <Desc / Clms Page number 46>  an oxidizing agent, at least one amphiphilic polymer as defined in any one of claims 1 to 40 being present in the dye composition or in the oxidizing composition, or in each of the two compositions.