FR2989585A1 - Dyeing keratinous fibers such as hair, involves applying dye composition with oxidation dye precursor and oxidizing composition with chemical oxidizing agent to fibers, where compositions comprise an associative thickening polymer - Google Patents

Abstract

Dyeing keratinous fibers, comprises applying a mixture obtained from a dye composition comprising at least an oxidation dye precursor and an oxidizing composition comprising at least one chemical oxidizing agent to fibers, where the compositions are delivered from pressurized containers and the mixture of the compositions comprises an associative thickening polymer. An independent claim is included for a device for dyeing keratinous fibers comprising a first pressurized container containing the dye composition, a second pressurized container containing the oxidizing composition, and a unit to deliver the compositions.

Description

The present invention relates to a hair dyeing method using a mixture comprising at least one associative thickening polymer. The invention relates to a method for dyeing hair using a mixture comprising at least one associative thickening polymer. said mixture being obtained from two compositions, at least one of which is packaged in a pressurized container, and a device suitable for carrying out this process. Among the methods for staining human keratinous fibers, such as the hair, mention may be made of oxidation or permanent staining. More particularly, this mode of staining uses one or more oxidation dyes, usually one or more oxidation bases possibly associated with one or more couplers. In general, the oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or para-aminophenols as well as heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, combined with oxidizing products, allow access to colored species. Very often, the shades obtained with these oxidation bases are varied by combining them with one or more couplers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds.

The variety of molecules involved in the oxidation bases and couplers allows a rich palette of colors to be obtained. The permanent coloring processes therefore consist in using with the dyeing composition an aqueous composition comprising at least one oxidizing agent such as hydrogen peroxide, under alkaline pH conditions in the vast majority of cases. The alkaline agent conventionally used is ammonia or other alkaline agents, such as alkanolamines. The coloring compositions may be in various forms such as lotions, gels, emulsions, creams or foams. These compositions, in particular the compositions comprising oxidation dyes, are obviously sensitive to oxidation and contain this makes reducing agents or antioxidants. This protective action against oxidation is further enhanced by the inert atmosphere that is sometimes used in the packaging of these compositions.

The difficulty encountered with this type of compositions results precisely from their sensitivity to oxidation. Indeed, during their use, they are placed in contact with the oxygen of the air and this then requires that they be used quickly. Otherwise, the compositions become unusable after storage and are lost. There are in the field of hair dyeing, compositions which are packaged in pressurized containers and which make it possible to prevent the composition from coming into contact with the air during their use, as is described, for example, in the documents US 2010/0236570 or FR 2 048 629.

However, the coverage of the hair, in particular white hair, remains to be improved as well as the galenic quality of the product from the pressurized container. There is a constant need to develop oxidation dyeing compositions in foam form which are easy to prepare and apply, which remain sufficiently stable over time and while retaining effective dyeing properties, especially in terms of hair coverage, more particularly white, but also intensity, homogeneity and chromaticity of the coloring obtained.

This and other objects are achieved by the present invention which relates to a process for dyeing keratinous fibers in which a mixture obtained from: - a dyeing composition comprising at least one dye precursor is applied to said fibers; oxidation, and - an oxidizing composition comprising at least one chemical oxidizing agent, - at least one of the compositions being delivered from a pressurized device, - the mixture of the two compositions comprising at least one associative thickening polymer . It also relates to an appropriate device for carrying out the method according to the invention, including: a first container containing a coloring composition comprising at least one oxidation dye precursor, and a second container containing an oxidizing composition comprising at least one chemical oxidizing agent, - at least one of the two containers being pressurized, preferably both containers being pressurized; means for delivering the compositions; the mixture of the two compositions comprising at least one associative thickening polymer. Preferably, the composition used in the process according to the invention is in the form of a foam which is particularly pleasant to apply. It has a light and airy texture, which makes it particularly pleasant to use. The qualities of the foam are sufficiently persistent over time to allow application of the product of homogeneous color and without sagging. The composition of the invention makes it possible to retain dyeing properties such as the power of color, resistance to external agents (shampoos, perspiration, light) and selectivity, and especially the coverage of white hair. Other characteristics and advantages of the invention will emerge more clearly on reading the description and examples which follow. In what follows, and unless otherwise indicated, the boundaries of a domain of values are included in this field. The term "at least one" associated with an ingredient in the composition means "one or more". The terms oxyalkylenated, oxyethylenated, oxypropylenated, glycerol, respectively cover mono- or polyoxyalkylenated compounds, oxyethylenated, oxypropylenated, glycerolated unless otherwise specified.

Unless otherwise indicated, the contents of the ingredients present in the compositions are indicated without taking into account the propellant content (s). The human keratinous fibers treated by the process according to the invention are preferably the hair. Associative thickening polymer As indicated above, the mixture used in the context of the invention comprises at least one associative thickening polymer, which are well known to those skilled in the art and in particular of nonionic, anionic, cationic or amphoteric nature.

It is recalled that the associative polymers are hydrophilic polymers capable, in an aqueous medium, to associate reversibly with each other or with other molecules. Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone. Hydrophobic group is understood to mean a radical or polymer with a hydrocarbon chain, saturated or unsaturated, linear or branched, comprising at least 6 carbon atoms, preferably 8 carbon atoms, preferably 10 to 30 carbon atoms, in particular 12 to 30 carbon atoms and more preferably 18 to 30 carbon atoms. Preferably, the hydrocarbon group comes from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene. These associative polymers use at least one other repeating unit in their structure than an alkylene oxide or glycidol unit and, in this sense, are different from the surfactants. Preferably, the mixture used in the invention comprises at least one associative polymer chosen from associative polyurethanes, more particularly cationic or nonionic, associative cellulose derivatives, more particularly cationic or nonionic, associative vinyllactams, polyacids associative unsaturates, associative aminoplast-ethers, associative polymers or copolymers comprising at least one ethylenically unsaturated monomer containing a sulfonic group, alone or in mixtures.

Among the associative thickening polymers, mention may be made of associative polyurethane derivatives, such as those obtained by polymerization: approximately 20% to 70% by weight of a carboxylic acid with α, 3 -monoethylenic unsaturation, approximately 20 to 80% by weight a non-surfactant α, β-monoethylenic unsaturated monomer different from the foregoing; -about 0.5 to 60% by weight of a nonionic mono-urethane which is the reaction product of a monohydroxy surfactant with a monoisocyanate monoethylenically unsaturated. Such are described in particular in EP173109 and more particularly in Example 3. More precisely, this polymer is a methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate terpolymer of ethoxylated behenyl alcohol (400E) in a 25% aqueous dispersion. This product is proposed under the reference VISCOPHOBE DB1000 by the company AMERCHOL.

The cationic associative polyurethanes whose family has been described in application FR 0009609 are also suitable. It can be represented more particularly by the following general formula (A): RX- (P) n- [L- (Y) m] r- Wherein - R and R ', which may be identical or different, represent a hydrophobic group or a hydrogen atom; X and X ', which may be identical or different, represent a group comprising an amine functional group which may or may not carry a hydrophobic group, or alternatively the L "group; L, L' and L", which may be identical or different, represent a group derived from a diisocyanate; ; P and P ', which may be identical or different, represent a group comprising an amine functional group which may or may not carry a hydrophobic group; Y represents a hydrophilic group; r is an integer from 1 to 100, preferably from 1 to 50 and in particular from 1 to 25; n, m, and p are each independently from 0 to 1000; the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group. In a very advantageous embodiment, the only hydrophobic groups of these polyurethanes are the groups R and R 'located at the chain ends. According to a first preferred embodiment, the associative polyurethane corresponds to the formula (A) in which R and R 'both independently represent a hydrophobic group; X, X 'each represents a group L "; n and p are between 1 and 1000 and L, L', L", P, P ', Y and m have the meaning indicated in formula (A). According to another preferred embodiment of the invention, the associative polyurethane corresponds to the formula (A) in which R and R 'both represent independently a hydrophobic group, X, X' each represent a group L ", n and p is 0, and L, L ', L ", Y and m have the meaning as in formula (A) indicated above. The fact that n and p are 0 means that these polymers do not comprise units derived from an amine-functional monomer incorporated in the polymer during the polycondensation. The protonated amine functions of these polyurethanes result from the hydrolysis of isocyanate functions, in excess, at the end of the chain, followed by the alkylation of the primary amine functions formed by alkylation agents with a hydrophobic group, that is to say ie compounds of the type RQ or R'Q, in which R and R 'are as defined above and Q is a leaving group such as a halide, a sulfate, etc. According to another preferred embodiment of the invention, the associative polyurethane corresponds to the formula (A) in which R and R 'both independently represent a hydrophobic group; X and X 'are each independently a group having a quaternary amine; n and p are zero, and L, L ', Y and m have the meaning indicated in formula (A).

The number average molecular weight of the cationic associative polyurethanes is usually between 400 and 500,000, in particular between 1000 and 400000 and ideally between 1000 and 300000 g / mol. When X and / or X 'denote a group comprising a tertiary or quaternary amine, X and / or X' may represent one of the following formulas: R3 -N -R2- -N + - or -R2 - ± I for X R1 Wherein R 1 represents R 1, R 1, R 2, R 2, R 2, R 2, R 2, R 2, R 2, R 2, R 2, R 2, R 2, R 2, R 2, R 2, R 1 and R 2; an alkylene radical having 1 to 20 carbon atoms, linear or branched, with or without a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms may be replaced by a heteroatom selected from N, S, O , P; R1 and R3, which may be identical or different, denote a linear or branched C1-C30 alkyl or alkenyl radical, an aryl radical, at least one of the carbon atoms may be replaced by a heteroatom chosen from N, S; , O, P; A- is a physiologically acceptable counterion.

The groups L, L 'and L "represent a group of formula: -Z -C -NH-R4-NH-C-Z-II-II wherein: Z represents -O-, -S- or -NH-; and R4 represents an alkylene radical having 1 to 20 carbon atoms, linear or branched, with or without a saturated or unsaturated ring, an arylene radical, one or more of the carbon atoms may be replaced by a heteroatom selected from N, S , O and P.

The groups P and P ', comprising an amine function, may represent at least one of the following formulas: RO °-R5 -N-R7-or -R5-N--R R R R-R R-R6 \-R5 - CH-R7- OR -R5-CH-R7 -R6 -N- + R9 to R8 R6, R8 -R5-CH-R7 -N OR Ru) R10 or -R5-CH-R7-1+ R6 -N -R9 AI R8 wherein: R5 and R7 have the same meanings as R2 defined above; R6, R8 and R9 have the same meanings as R1 and R3 defined above; R10 represents an alkylene group, linear or branched, optionally unsaturated and may contain one or more heteroatoms selected from N, O, S and P; A- is a cosmetically acceptable counterion. As regards the meaning of Y, the term "hydrophilic group" means a water-soluble polymeric group or not. By way of example, non-polymers include ethylene glycol, diethylene glycol and propylene glycol. When it comes, according to a preferred embodiment, a hydrophilic polymer, there may be mentioned by way of example polyethers, sulfonated polyesters, sulfonated polyamides, or a mixture of these polymers. Preferably, the hydrophilic compound is a polyether and in particular a poly (ethylene oxide) or poly (propylene oxide). The associative polyurethanes of formula (A) are formed from diisocyanates and various compounds having functions with a labile hydrogen. The functions with a labile hydrogen can be alcohol, primary or secondary amine or thiol functions giving, after reaction with the diisocyanate functions, respectively polyurethanes, polyureas and polythioureas. The term "polyurethanes" of the present invention includes these three types of polymers namely polyurethanes themselves, polyureas and polythioureas as well as copolymers thereof. A first type of compound used in the preparation of the polyurethane of formula (A) is a compound comprising at least one amine-functional unit. This compound can be multifunctional, but preferentially the compound is difunctional, that is to say that according to a preferred embodiment, this compound comprises two labile hydrogen atoms carried for example by a hydroxyl function, primary amine, secondary amine or thiol. It is also possible to use a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low. As indicated above, this compound may comprise more than one amine-functional unit. It is then a polymer bearing a repetition of the amine functional unit. This type of compounds can be represented by one of the following formulas: HZ- (P), - ZH, or HZ- (P ') p-ZH in which Z, P, P', n and p are as defined upper.

As examples of an amine-functional compound, there may be mentioned N-methyldiethanolamine, N-tert-butyl diethanolamine and N-sulfoethyldiethanolamine. The second compound used in the preparation of the polyurethane of formula (A) is a diisocyanate corresponding to the formula O = C = N-R 4 -N = C = O, in which R 4 is defined above.

Mention may in particular be made of methylenediphenyl diisocyanate, methylene cyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate. A third compound used in the preparation of the polyurethane of formula (A) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (A). This compound consists of a hydrophobic group and a function with labile hydrogen, for example a hydroxyl function, primary or secondary amine, or thiol. By way of example, this compound may be a fatty alcohol, such as in particular stearyl alcohol, dodecyl alcohol or decyl alcohol. When this compound comprises a polymer chain, it may be for example hydrogenated polybutadiene a-hydroxyl.

The hydrophobic group of the polyurethane of formula (A) can also result from the quaternization reaction of the tertiary amine of the compound having at least one tertiary amine unit. Thus, the hydrophobic group is introduced by the quaternizing agent. This quaternizing agent is a compound of the type RQ or R'Q, in which R and R 'are as defined above and Q denotes a leaving group such as a halide, a sulphate, etc. The cationic associative polyurethane may further comprise a hydrophilic block. This sequence is provided by a fourth type of compound used in the preparation of the polymer. This compound can be multifunctional. It is preferably difunctional. One can also have a mixture where the percentage of multifunctional compound is low. The functions with a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends by one of these functions with labile hydrogen.

By way of examples, non-polymers include ethylene glycol, diethylene glycol and propylene glycol. When it is a hydrophilic polymer, mention may be made by way of example of polyethers, sulphonated polyesters, sulphonated polyamides, or a mixture of these polymers.

Preferably, the hydrophilic compound is a polyether and in particular a poly (ethylene oxide) or poly (propylene oxide). The hydrophilic group Y in formula (A) is optional. Indeed, the quaternary or protonated amine functional units may be sufficient to provide the solubility or hydrodispersibility necessary for this type of polymer in an aqueous solution. Although the presence of a hydrophilic Y group is optional, cationic associative polyurethanes having such a group are preferred. The associative polyurethane derivatives of the invention may also be nonionic polyether polyurethanes. More particularly, said polymers contain in their chain both hydrophilic sequences of a most often polyoxyethylenated nature and hydrophobic sequences which may be aliphatic chains alone and / or cycloaliphatic and / or aromatic chains.

Preferably, these polyurethane polyethers comprise at least two hydrocarbon-based (hydrophobic) lipophilic chains, more particularly having from 8 to 30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains possibly being pendant chains or hydrophilic end-chain chains. . In particular, it is possible that one or more pendant chains are provided. In addition, the polymer may comprise a hydrocarbon chain at one end or at both ends of a hydrophilic block. The polyether polyurethanes may be multiblocked, in particular in the form of a triblock. The hydrophobic sequences may be at each end of the chain (for example: hydrophilic central block triblock copolymer) or distributed at both the ends and in the chain (multiblock copolymer for example). These same polymers may also be graft or star. The hydrophobic chain nonionic polyurethane polyethers may be triblock copolymers whose hydrophilic sequence is a polyoxyethylenated chain containing from 50 to 1000 oxyethylenated groups. Nonionic polyurethane polyethers have a urethane bond between the hydrophilic blocks, hence the origin of the name. By extension are also included among the hydrophobic chain nonionic polyurethane polyethers, those whose hydrophilic blocks are linked to the hydrophobic blocks by other chemical bonds. By way of examples of nonionic polyurethane polyethers with a hydrophobic chain which can be used in the invention, it is also possible to use the urea-functional Rheolate 205® sold by Rheox or the Rheolates® 208, 204 or 212, the Rheolate FX1100 as well as the Acrysol RM 184®. Mention may also be made of the product ELFACOS T210® with a C12-C14 alkyl chain and the product ELFACOS T212® with a C18 alkyl chain from AKZO. The product DW 1206B® from ROHM & HAAS with a C20 alkyl chain and a urethane bond, proposed at 20% solids content in water, can also be used. It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of examples, such polymers include, for example, Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by Rheox. It is also possible to use the product DW 1206F and the DW 1206J proposed by the company Rohm & Haas. The usable polyurethane polyethers described above may also be selected from those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271, 380, 389 (1993). Even more particularly, according to the invention, it is preferred to use a polyether polyurethane obtainable by polycondensation of at least three compounds comprising (i) at least one polyethylene glycol comprising from 150 to 180 moles of ethylene oxide, (ii) stearyl alcohol or decyl alcohol and (iii) at least one diisocyanate.

Such polyether polyurethanes are sold in particular by the company ROHM & HAAS under the names Aculyn 46® and Aculyn 44®, ACULYN 46® is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, stearyl alcohol and methylenebis (4-cyclohexylisocyanate) (SMDI) at 15% by weight in a matrix of maltodextrin (4%) and water (81%); ACULYN 44® is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylene bis (4-cyclohexylisocyanate) (SMDI), at 35% by weight in a propylene glycol mixture ( 39%) and water (26%)].

The mixture may likewise comprise polymers derived from associative celluloses such as: quaternized cationic celluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof; quaternized cationic hydroxyethylcelluloses modified with groups having at least one hydrophobic chain, such as alkyl, arylalkyl, alkylaryl groups having at least 8 carbon atoms, or mixtures thereof. The alkyl radicals carried by the celluloses or hydroxyethylcelluloses quaternized above preferably comprise from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups. Examples of quaternized alkylhydroxyethylcelluloses with C8-C30 hydrophobic chain are QUATRISOFT LM 200®, QUATRISOFT LM-X 529-18-A®, QUATRISOFT LM-X 529-18B® (C12 alkyl) and QUATRISOFT products. LM-X 529-8® (018 alkyl), SOFTCAT SL100 marketed by the company AMERCHOL and the products CRODACEL QM®, CRODACEL QL® (C12 alkyl) and CRODACEL QS® (C18 alkyl) marketed by the company CRODA . nonionic cellulose derivatives such as hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C 8 -C 22, such as the product NATROSOL PLUS GRADE 330 CS® (alkyls in 016) sold by the company AQUALON, or the BERMOCOLL EHM 100® product sold by the company BEROL NOBEL, the cellulose derivatives modified with polyalkylene glycol ether alkyl phenol groups, such as the product AMERCELL POLYMER HM-1500® sold by the company AMERCHOL.

As regards the associative polyvinyllactams, mention may be made, for example, of the polymers especially described in FR 0101106. Said polymers are more particularly cationic polymers and comprise: -a) at least one monomer of vinyl lactam or alkylvinyllactam type; -b) at least one monomer with the following structures (a) or (b): CH 2 = C (R 1) -O 2 -X- (Y) (CH 2 -CH 2 -O), (CH 2 -CH (R 2) -O) (Y1) q (a) + CH2 = C (R1) -CO-X- (1) r (CH2-CH2-O), (CH2-CH (R2) -O), -O114 (b) y-R4 Wherein: X denotes an oxygen atom or a radical NR6, R1 and R6 denote, independently of one another, a hydrogen atom or a linear or branched C1-C5 alkyl radical; , R2 denotes a linear or branched C1-C4 alkyl radical, R3, R4 and R5 denote, independently of one another, a hydrogen atom, a linear or branched C1-C30 alkyl radical or a radical of formula (IV): (Y2) (CH2-CH (R7) -O)) R8 (C) Y, Y1 and Y2 denote, independently of one another, a linear or branched alkylene radical of 02-016, R7 denotes a hydrogen atom, or a linear or branched alkyl radical in 0104 or a linear or branched C1-C4 hydroxyalkyl radical, R8 denotes a hydrogen atom or a linear or branched C1-C30 alkyl radical, p, q and rd denote, independently of each other, either the value zero or the value 1, m and n denote, independently of one another, an integer ranging from 0 to 100, x denotes an integer ranging between from 1 to 100, Z denotes an organic or inorganic acid anion, provided that: - at least one of the substituents R3, R4, R5 or R8 denotes a linear or branched C9-C30 alkyl radical, - Si m where n is different from zero, then q is 1, - if m or n are zero, then p or q is 0.

The poly (vinyllactam) polymers may be crosslinked or uncrosslinked and may also be block polymers. Preferably, the Z-counterion of the monomers of formula (b) is chosen from halide ions, phosphate ions, methosulphate ion and tosylate ion.

Preferably R3, R4 and R5 denote, independently of one another, a hydrogen atom or a linear or branched C1-C30 alkyl radical. More preferably, the monomer b) is a monomer of formula (b) for which, even more preferably, m and n are equal to zero. The vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (d): CH (R 9) = C (R 10) (d) (CH 2) s in which: s denotes an integer ranging from 3 to 6, R 9 denotes an atom of hydrogen or a C 1 -C 5 alkyl radical, R 10 denotes a hydrogen atom or a C 1 -C 5 alkyl radical, with the proviso that at least one of the radicals R 9 and R 10 denotes a hydrogen atom. Even more preferentially, the monomer (d) is vinylpyrrolidone. Poly (vinyllactam) polymers may also contain one or more additional monomers, preferably cationic or nonionic. As more particularly preferred compounds according to the invention, mention may be made of the following terpolymers comprising at least: a) a monomer of formula (d), b) -a monomer of formula (a) in which p = 1, q = 0, R3 and R4 denote, independently of one another, a hydrogen atom or a C1-C5 alkyl radical and R5 denotes a C9-O24 alkyl radical and c) -a monomer of formula (b) ) in which R3 and R4 denote, independently of one another, a hydrogen atom or a C1-C5 alkyl radical. Even more preferentially, terpolymers comprising, by weight, 40 to 95% of monomer (d), 0.1 to 55% of monomer (b) and 0.25 to 50% of monomer (b) are used. Such polymers are described in particular in patent application WO 00/68282, the content of which forms an integral part of the invention. As poly (vinyllactam), one uses in particular 35 terpolymers vinylpyrrolidone / dimethylaminopropylmethacrylamide / dodecyl tosylate diméthylméthacrylamidopropylammonium, vinylpyrrolidone / dimethyl aminopropylmethacrylamide / tosylate cocoyldiméthylméthacrylamido propyl ammonium, vinylpyrrolidone / dimethylaminopropylmethacrylamide tosylate or chloride lauryldiméthylméthacrylamidopropylammonium. The vinylpyrrolidone / dimethylaminopropyl methacrylamide / lauryl dimethylmethacrylamidopropylammonium terpolymer is proposed in 20% water by ISP under the name STYLEZE W20. The associative polyvinyllactam derivatives of the invention may also be nonionic copolymers of vinylpyrrolidone and hydrophobic chain hydrophobic monomers which may be mentioned by way of example: the ANTARON V216® or GANEX V216® products (vinylpyrrolidone / hexadecene copolymer) ) sold by ISP products ANTARON V220® or GANEX V220® (vinylpyrrolidone / eicosene copolymer) sold by the company I.S.P.

Among the associative unsaturated polyacid derivatives, mention may be made of those comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit of the non-ethoxylated (C 10 -C 30) alkyl ester of unsaturated carboxylic acid type. These polymers are especially chosen from those whose hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (e) below: ## STR2 ## in which R 1 denotes H or CH 3 or C 2 H 5, that is to say, acrylic acid, methacrylic acid or ethacrylic acid units, and whose hydrophobic unit of alkyl ester (C 10 -C 30) unsaturated carboxylic acid type corresponds to the monomer of formula (f) below: CH C- Wherein R2 is H or CH3 or C2H5 (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH3 (methacrylate units). R 3 denotes a C 10 -C 30 alkyl radical, and preferably a C 12 -C 02 alkyl radical. C 10 -C 30 alkyl esters of unsaturated carboxylic acids include, for example, lauryl acrylate and stearyl acrylate. decyl acrylate, isodecyl acrylate, dodecyl acrylate and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

Anionic polymers of this type are for example described and prepared according to US Pat. Nos. 3,915,921 and 4,509,949. In this type of anionic associative polymers, polymers formed from a monomer mixture comprising : essentially acrylic acid, an ester of formula (f) described above and wherein R 2 denotes H or OH 3, R 3 denoting an alkyl radical having from 12 to 22 carbon atoms, and a crosslinking agent, which is a copolymerizable polyethylenically unsaturated monomer, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylenebisacrylamide. Among this type of anionic associative polymers, those consisting of 95 to 60% by weight of acrylic acid (hydrophilic unit), of 4 to 40% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit), are preferred. and 0 to 6% by weight of polymerizable crosslinking monomer, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of alkyl acrylate in 010-030 (Hydrophobic unit), and from 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above.

Among said polymers above, the products sold by the company Goodrich under the trade names Pemulen TR1®, Pemulen TR2®, Carbopol 1382®, and even more preferentially Pemulen TR1®, and the product sold by the company, are particularly preferred. SEPPIC under the name COATEX SX®.

The anionic associative polymers may also be copolymers comprising among their monomers an α, β-ethylenically unsaturated carboxylic acid and an α, β-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol.

Preferably, these compounds also comprise, as monomer, an α, β-monoethylenically unsaturated carboxylic acid ester and an alcoholic acid ester. As an example of this type of compound, mention may be made of Aculyn 22® sold by the company Rohm and HAAS, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer.

As regards the thickening polymers of the aminoplast-ether type, there is meant any product resulting from the condensation of an aldehyde with an amine or an amide, as well as any structural unit formed of an aminoplast residue and a hydrocarbon residue. divalent bound to the aminoplast residue by an ether linkage.

The polymers having an aminoplast-ether backbone are preferably chosen from those containing at least one unit of structure (g) below: (ROLp AMP R01 in which: -AMP is an aminoplast residue with alkylene units (or divalent alkyl), -R denotes a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 acyl radical, -R01 is a divalent alkylene-oxy residue, -p denotes a positive integer, where the OR groups are linked to the alkylene units; AMP residue.

Preferably, the polymers having an aminoplast-ether backbone are chosen from those containing at least one unit of the following structure (h): RO.1 (R02) q AMP R01 (h) in which: -AMP, R, RO1 and p have the same meaning as above, - RO2 is a different group of RO linked to AMP by means of a heteroatom and comprising at least two carbon atoms, and, -q is a positive integer. More preferably, the polymers correspond to the following formulas (III) and (III) bis: embedded image in which: AMP, R, R01, R02, p and q have the same meaning as above, R 2 or R 3, which may be identical or different, represent a terminal group which may designate a hydrogen atom, a group RO 1 H, a group RO 2 H or a (g) (RC). v (R02) q R2 AMP R01 R3 AMP (OR) group p or any monofunctional group such as alkyl, cycloalkyl, aryl, aralkyl, alkylaryl, alkyloxyalkyl, aryloxyalkyl, cycloalkoxyalkyl, -a being a number greater than 1 and preferably greater than 1. 2. The aminoplast residues carrying their OR groups integrated in the polymers may be chosen in a non-limiting manner from the following structures (1) to (12): OR OR O (3) (1) OR OR O RONNOR (2) 0 RO OR RO NNN OR N OR OR O RO NOR ROOR (5) O (7) RO '° N RO OR jr (0 (9) H, N OR RO (OR (6) 0 RONOR R1 R1 (8) O OH Where: O (NOR OR 0 (12) H OR NOR (11) H OR NOR -R has the same meaning as above, -R1 denotes C1-04 alkyl, -y is a number at least equal to at 2, -x is 0 or 1.

Preferably, the aminoplast residue (s) carrying their OR groups are chosen from those of structure (13) below: ## STR1 ## in which R, p and x have the same meanings as previously.

The divalent alkylene-oxy residues are preferably those corresponding to the diols of the following general formula (14): ## STR2 ## Z- (ZO) y- (Z 1 (Z 2 O) w) t- (Z'O) y'-Z 3 OH (14) ), y and y 'being numbers ranging from 0 to 1000, and w being numbers ranging from 0 to 10, -Z, Z', Z2 and Z3 are C2-C4 alkylene radicals and preferably radicals -CH2-CH (Z4) - and -CH2-CH (Z4) -CH2-, -Z1 being a linear or cyclic radical, branched or unbranched, aromatic or otherwise, with or without one or more heteroatoms and having from 1 to 40 carbon atoms, -Z4 denoting a hydrogen atom or a C1-C4 alkyl radical or a C1-C3 acyl radical, it being understood that at least one of the radicals Z4 of the radicals Z, Z ', Z2 and Z3 is different from an acyl radical. Preferably Z4 denotes a hydrogen atom or a methyl radical. Even more preferably, t = 0 and Z, Z 'and Z3 denote -CH2CH2-, and at least one of y or y' is different from 0. The compounds of formula (14) are then polyethylene glycols. The aminoplast ether polymers of formula (g) contain at least one linear or cyclic chain comprising at least 8 carbon atoms, saturated or unsaturated, and are in particular described in US Pat. No. 5,914,373 to which reference may be made for details. . Aminoplast-ether backbone polymers of formula (g) include, in particular, Pure-Thix® L products [PEG-180 / Octoxyno1-40 / TMMG Copolymer (INCI name)], Pure-Thix M® [PEG- 180 / Laureth-50 / TMMG Copolymer (INCI name)], (13) Pure-Thix® HH [Polyether-1 (INCI name)]; Pure Thix TX-1442® [PEG-18 / dodoxynol-5 copolymer / PEG-25 tristyrylphenol / tetramethoxy methyl glycolurile] proposed by the company Süd-Chemie.

The thickening polymers used as ingredients in the mixture according to the invention may also be chosen from associative 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.

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

These associative polymers may or may not be crosslinked, and preferably are crosslinked polymers. In this case, the crosslinking agents from at least one monomer having at least two ethylenic unsaturations (carbon-carbon double bond). The crosslinking monomers having at least two ethylenic unsaturations are chosen for example from diallyl ether, triallyl cyanurate, diallyl maleate, allyl (meth) acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyl oxethanoyl, tetra- or diethylene glycol di (meth) acrylate, triallylamine, tetraallylethylenediamine, trimethylolpropane diallyl ether, trimethylolpropane triacrylate, methylene bis (meth) acrylamide or divinylbenzene, allyl ethers of alcohols of the series of sugars, or other allyl- or vinyl-ethers of polyfunctional alcohols, as well as the allyl esters of phosphoric and / or vinylphosphonic acid derivatives, or mixtures thereof. of these compounds. Methylenebisacrylamide, allyl methacrylate or trimethylol propane triacrylate are more particularly used. The degree of crosslinking generally varies from 0.01 to 10 mol%, relative to the polymer. The ethylenically unsaturated monomers containing sulphonic groups are chosen in particular from vinylsulphonic acid, styrenesulphonic acid, (meth) acrylamido (C1-C22) alkylsulphonic acids and N- (C1-C22) alkyl- (meth) acids. acrylamido (C1-C22) alkylsulphonic acids such as undecyl-acrylamidomethanesulfonic acid and their partially or totally neutralized forms. More particularly, it is possible to use (meth) acrylamido (C1-C22) alkylsulphonic acids such as, for example, acrylamido-methanesulfonic acid, acrylamido-ethanesulfonic acid, acrylamido-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid , 2-methacrylamido-dodecylsulphonic acid, 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid and their partially or completely neutralized forms. 2-Acrylamido-2-methylpropanesulfonic acid (AMPS) is preferably used as well as its partially or completely neutralized forms. The amphiphilic polymers present in the dispersion (A) according to the invention may also be chosen from AMPS random amphiphilic polymers modified by reaction with a n-monoalkylamine or a C6-C22 di-n-alkylamine, and such as those described in application W000 / 31154. The hydrophobic monomers that constitute the hydrophobic part of the polymer are preferably chosen from the acrylates or acrylamides of formula (k) below: ## STR1 ## wherein R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y is O or NH; R2 denotes a hydrophobic hydrocarbon radical as defined previously; x denotes a number of moles of alkylene oxide and ranges from 0 to 100. The radical R2 is advantageously chosen from linear C6-C18 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), branched or cyclic (for example cyclododecane (C12) or adamantane (C10)); perfluorinated C 6 -C 18 alkyl radicals (for example the group of formula - (CH 2) 2- (CF 2) 9-CF 3); the cholesteryl radical (C27) or a cholesteryl ester residue such as the cholesteryl oxyhexanoate group; polycyclic aromatic groups such as naphthalene or pyrene. Among these radicals, linear alkyl radicals and more particularly the n-dodecyl radical are more particularly preferred. According to one particular form of the invention, the monomer of formula (k) comprises at least one alkylene oxide unit (x and preferably a polyoxyalkylene chain) .The polyoxyalkylene chain, preferably, consists of ethylene oxide units. and / or of propylene oxide units and even more particularly of 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 7 to 25. The copolymers may also contain other hydrophilic ethylenically unsaturated monomers chosen, for example, from (meth) acrylic acids, their 13-substituted alkyl derivatives or their esters obtained with monoalcohols or mono- or polyalkylene glycols, (meth) acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid or mixtures thereof.

These copolymers are described in particular in the documents EP750899, US 5089578, the following Yotaro Morishima 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, No. 10 - 3694-3704 "; Solution properties of miscellence formed by non-ionic moieties covalently bound to a polyelectrolyte: known effects on rheumatic behavior (Langmuir, 2000, Vol.16, No. 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 distribution of the monomers in the copolymer can be statistical or block. Among these polymers of this type, mention may be made more specifically 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 units (O-C16) ) alkyl (meth) 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 Pat. No. 5,098,578; copolymers of fully neutralized AMPS and dodecyl methacrylate, as well as copolymers of uncrosslinked, crosslinked AMPS and n-dodecylmethacrylamide, such as those described in the Morishima articles cited above. above.

Mention may be made more particularly of copolymers consisting of AMPS units of formula (XXX) below: ## STR2 ## in which X + has the same definition as above, and of following formula (XXXI): 1:11 -CH 2 -c -O = c o -CH 2 -CH 2 -O 1 -R 4 x (XXXI) wherein x is an integer ranging from 3 to 100, preferably from 5 to 80 and more preferably from 7 to 25; R1 has the same meaning as that indicated above in formula (j) and R4 denotes a linear or branched C6-C22 alkyl, especially C8-C22, and more preferably 010-C22. Particularly preferred polymers are those where x = 25, R1 is methyl and R4 is n-dodecyl; they are described in the articles of Morishima mentioned above. The polymers for which X + denotes sodium or ammonium are more particularly preferred.

As such associative polymers with a sulfonic group, mention may be made of the product sold under the name ARISTOFLEX HMS by the company CLARIANT. The associative polymers of the invention are preferably anionic or cationic.

In a preferred variant, these associative polymers are celluloses or polyurethanes, preferably celluloses. According to a preferred embodiment of the invention, the content of associative polymer (s) represents 0.001 and 20% by weight, preferably 0.1 and 2% by weight, relative to the weight of the mixture. The non-associative polymer (s) present in the mixture used in the invention may be in the dye composition, in the oxidizing composition, or in both compositions simultaneously.

Coloring composition Dyes The dye composition used in the process according to the invention comprises at least one oxidation dye precursor.

As oxidation dye precursors, oxidation bases and couplers may be used. By way of example, the oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.

Among the para-phenylenediamines, there may be mentioned, for example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N-bis- ((3-hydroxyethyl) paraphenylenediamine, 4-N, N-bis - ((3-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis - ((3-hydroxyethyl) amino-2-chloroaniline, 2 (3-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N - ((3-hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N N- (ethyl, 3-hydroxyethyl) paraphenylenediamine, N- (13, γ-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2 (3-hydroxyethyloxy) paraphenylenediamine, 213-acetylaminoethyloxy para-phenylenediamine, N - ((3-methoxyethyl) paraphenylenediamine, 4- aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, hydroxyethylamino 5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid. Among the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2 (3-hydroxyethyl paraphenylenediamine, 2 (3-hydroxyethyloxy) paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis - ((3-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-13-acetylaminoethyloxy-para-phenylenediamine, and their addition salts with a Particularly preferred among the bis-phenylalkylenediamines are N, N'-bis - ((3-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1, 3-diamino propanol, N, N'-bis- (phydroxyethyl) N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N bis (p-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetram thylenediamine, N, N'-bis- (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3 , 6-dioxaoctane, and their addition salts. Examples of para-aminophenols include para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-chlorophenol, 4- amino 3-hydroxymethyl phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2 - ( 3-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid.

Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their addition salts. Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 3,4-diamino pyridine, and their addition salts. Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-a] pyridines oxidation bases or their addition salts described for example in the patent application FR 2801308. By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-aminopyrazolo [1,5-a] pyridin-5-yl) ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diaminopyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol; as well as their addition salts. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and tautomeric forms, when tautomeric equilibrium exists. Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 1-methyl pyrazole, 4,5-diamino 1 - ((3-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole, 4, 5-diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino pyrazole, 1-benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4 5-diamino-1 - ((3-hydroxyethyl) 3-methylpyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3- me 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino 4 - ((3-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts. 4-5-Diamino-1 - ((3-methoxyethyl) pyrazole may also be used, preferably a 4,5-diaminopyrazole and even more preferably 4,5-diamino-1 - ((3-hydroxyethyl) and pyrazole derivatives, mention may also be made of diamino N, Ndihydropyrazolopyrazolones and in particular those described in Application FR-A-2,886,136, such as the following compounds and their salts; addition: 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H, 5H pyrazolo [1,2-a] pyrazol-1-one, 2-aminomo-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2- amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1, 2-Dihydro-pyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one, 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one , 2-amino-3 1-methylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino [ 1,2-a] pyrazol-1-one, 4-amino-1,2-diethyl-5- (pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one, 4-amino-5- (3-Dimethylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H- pyrazolo [1,2-a] pyrazol-1-one. It is preferred to use 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and / or a salt thereof.

As heterocyclic bases, 4,5-diamino-1 - ((3-hydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] are preferably used. ] pyrazol-1-one and / or a salt thereof Among the couplers that can be used in the composition used in the process according to the invention, there may be mentioned in particular meta-phenylenediamines, meta-aminophenols, meta-diphenols , naphthalenic couplers, heterocyclic couplers such as, for example, indole derivatives, indoline derivatives, sesamol and its derivatives, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles , 1,3-benzodioxoles, quinolines, and the addition salts of these compounds with an acid, these couplers are more particularly chosen from 2,4-diamino-1- (phydroxyethyloxy) -benzene, 2-methyl 5-amino-phenol, 5-N - ((3-hydroxyethyl) amine 2-methylphenol, 3-amino-phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2-amino-4 - ((3-hydroxyethylamino) -1-methoxy-benzene, 1,3-diamino-benzene, 1,3-bis (2,4-diaminophenoxy) -propane, sesamol, amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methyl-pyridine, 1-H-3-methyl-pyrazol-5-one, 1-phenyl-3-methyl-pyrazol-5-one, 2-amino-3- hydroxypyridine, 3,6-dimethyl-pyrazolo [3,2-c] -1,2,4-triazole, 2,6-dimethyl-pyrazolo [1,5-13] -1,2,4- triazole, their acid addition salts, and mixtures thereof. The addition salts of the oxidation bases and the couplers are in particular chosen from acid addition salts such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates and tosylates. , benzenesulfonates, phosphates and acetates. The oxidation base (s) are generally present each in an amount of between 0.0001% and 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition. coloring composition. The coupler (s) are each in general from 0.0001 to 10% by weight relative to the total weight of the composition, and preferably from 0.005 to 5% by weight relative to the total weight of the dye composition. The dye composition used in the process according to the invention may contain synthetic or natural direct dyes, cationic or nonionic. By way of example of particularly suitable direct dyes, mention may be made of the nitro dyes of the benzene series; azo direct dyes; azomethines; methinic; azacarbocyanines such as tetraazacarbocyanines (tetraazapentamethines); quinone direct dyes and in particular anthraquinone, naphthoquinone or benzoquinone dyes; direct azine dyes; xanthenics; triarylmethanics; indoamines; indigoids; phthalocyanines, porphyrins and natural direct dyes, alone or in mixtures. In particular, mention may be made of azo direct dyes; methinic; carbonyls; azinic; nitro (hetero) aryl; tri- (hetero) aryl methanes; porphyrins; phthalocyanines and natural direct dyes, alone or in mixtures. When present, the direct dye (s) more particularly represent from 0.0001 to 10% by weight of the total weight of the dyeing composition, and preferably from 0.005 to 5% by weight. Alkaline agent According to a preferred variant of the invention, the dye composition comprises at least one alkaline agent. This agent may be chosen from inorganic or organic or hybrid alkaline agents or mixtures thereof. The inorganic alkaline agent (s) is (are) preferably chosen from ammonia, alkali carbonates or bicarbonates, such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium or potassium hydroxides, or mixtures thereof. The organic alkaline agent (s) is (are) preferably chosen from organic amines whose pKb at 25 ° C. is less than 12, and preferably less than 10, and even more advantageously less than 6. It should be noted that this is pKb corresponding to the highest basicity function. As hybrid compounds, mention may be made of the salts of the amines mentioned above with acids such as carbonic acid and hydrochloric acid. The organic alkaline agent (s) are, for example, chosen from alkanolamines, ethoxylated and / or oxypropylenated ethylenediamines, amino acids and compounds of the following formula: ## STR1 ## wherein W is a C 1 -C 4 alkylene radical; C6 optionally substituted by a hydroxyl group or a C1-C6 alkyl radical; Rx, Ry, Rz and Rt, identical or different, represent a hydrogen atom, a C1-C6 alkyl or C1-C6 hydroxyalkyl, C1-C6 aminoalkyl radical.

Examples of such amines include 1,3-diaminopropane, 1,3-diaminopropanol, spermine and spermidine. By alkanolamine is meant an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C 1 -C 8 alkyl groups carrying one or more hydroxyl radicals. Alkanolamines such as mono-, di- or trialkanolamines comprising one to three identical or different C 1 -C 4 hydroxyalkyl radicals are particularly suitable for carrying out the invention. Among compounds of this type, mention may be made of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N-dimethylaminoethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino -2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris-hydroxymethylamino-methane. More particularly, the amino acids that can be used are of natural or synthetic origin, in their L, D, or racemic form, and comprise at least one acid function chosen more particularly from the carboxylic, sulphonic, phosphonic or phosphoric acid functions. Amino acids can be in neutral or ionic form. As amino acids that may be used in the present invention, mention may in particular be made of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine and cysteine. , glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine. Advantageously, the amino acids are basic amino acids comprising an additional amine function optionally included in a ring or in a ureido function. Such basic amino acids are preferably chosen from those corresponding to the following formula: ## STR2 ## where R denotes a group chosen from: - (CH 2) 3NI-12 - (CH 2) 2NHCONH 2 - (C1 The compounds corresponding to the above formula are histidine, lysine, arginine, ornithine, citrulline. The organic amine may also be chosen from heterocyclic organic amines. In addition to the histidine already mentioned in the amino acids, mention may in particular be made of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole. . The organic amine may also be selected from amino acid dipeptides. As amino acid dipeptides that may be used in the present invention, carnosine, anserin and balenine may be mentioned in particular. The organic amine is chosen from compounds containing a guanidine function. As amino amines of this type which can be used in the present invention, mention may in addition be made of arginine already mentioned as amino acid, creatine, creatinine, 1,1-dimethylguanidine, 1,1 diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2- gamino (imino) methyl] amino) ethane-1-sulfonic acid . As hybrid compounds, mention may in particular be made of guanidine carbonate or monoethanolamine hydrochloride. More particularly, the coloring composition used in the process of the invention contains, as alkaline agent, ammonia and / or at least one alkanolamine and / or at least one basic amino acid, more preferably ammonia and / or at least one alkanolamine. Preferably, the alkaline agent is chosen from ammonia, monoethanolamine, or their mixture. Advantageously, the dyeing composition has an alkaline agent (s) content ranging from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight and better still from 1% to 10% by weight. weight relative to the weight of said coloring composition. Note that this content is expressed in NH3 in the case where the alkaline agent is ammonia.

Surfactants The coloring composition may further comprise one or more surfactants. In particular, the surfactant or surfactants are chosen from anionic, amphoteric, zwitterionic, cationic or nonionic surfactants, and preferably nonionic surfactants. The term "anionic surfactant" is understood to mean a surfactant comprising as ionic or ionizable groups only anionic groups. These anionic groups are preferably chosen from -C (O) OH, -C (O) O-, -SO3H, -S (O) 20-, -O (O) 20H, -OS (O) 20- , -P (O) OH2, -P (O) 20-, -P (O) O2, -P (OH) 2, = P (O) OH, -P (OH) O-, = P (O) 0-, = POH, = PO-, the anionic parts comprising a cationic counterion such as an alkali metal, an alkaline earth metal, or an ammonium.

As examples of anionic surfactants that can be used in the dyeing composition according to the invention, mention may be made of alkyl sulphates, alkyl ether sulphates, alkylamido ether sulphates, alkylaryl polyether sulphates, monoglyceride sulphates, alkyl sulphonates, alkyl amide sulphonates, alkylarylsulfonates, alpha-olefin-sulfonates, paraffin-sulfonates, alkylsulfosuccinates, alkylethersulfosuccinates, alkylamide-sulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N-acyltaurates, salts of alkyl monoesters and polyglycoside-polycarboxylic acids, acyllactylates, D-galactoside-uronic acid salts, alkyl ether-carboxylic acid salts, alkyl aryl ether carboxylic acid salts, salts of alkyl amidoether carboxylic acids, and the corresponding non-salified forms of all these compounds, the alkyl groups and acyl of all these compounds having from 6 to 40 carbon atoms and the aryl group denoting a phenyl group. These compounds may be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units. The salts of C 6 -C 24 alkyl monoesters and polyglycoside polycarboxylic acids may be selected from C 60 -C 24 alkyl polyglycoside citrates, C 6 -C 24 alkyl polyglycoside tartrates and C 6 -C 24 alkyl polyglycoside sulfosuccinates. 024.

When the agent or the anionic surfactants are in the salt form, they may be chosen from alkali metal salts such as the sodium or potassium salt and preferably sodium salt, ammonium salts, amine salts and in particular aminoalcohols or alkaline earth metal salts such as magnesium salts.

By way of example of aminoalcohol salts, mention may be made in particular of the salts of mono-, di- and triethanolamine, the salts of mono-, di- or triisopropanolamine and the salts of 2-amino-2-methyl-1-one. propanol, 2-amino-2-methyl-1,3-propanediol and tris (hydroxymethyl) amino methane. The alkali metal or alkaline earth metal salts and in particular the sodium or magnesium salts are preferably used. Among the anionic surfactants mentioned, it is preferred to use (C 6 -C 24) alkyl sulphates, alkyl (C 6 -C 24) ether sulphates comprising from 2 to 50 ethylene oxide units, in particular in the form of alkali metal or ammonium salts. , aminoalcohols, and alkaline earth metals, or a mixture of these compounds. In particular, it is preferred to use (C 12 -C 20) alkyl sulphates, C 12 -C 20 alkyl ether sulphates comprising from 2 to 20 ethylene oxide units, in particular in the form of alkali metal salts, ammonium salts, aminoalcohol , and alkaline earth metals, or a mixture of these compounds. More preferably, it is preferred to use sodium lauryl ether sulfate with 2.2 moles of ethylene oxide. The amphoteric or zwitterionic surfactant (s), preferably non-silicone surfactants, which may be used in the present invention may be in particular derivatives of secondary or tertiary aliphatic amines, optionally quaternized, in which the aliphatic group is a linear or branched chain containing from 8 to 8 carbon atoms. at 22 carbon atoms, said amine derivatives containing at least one anionic group such as, for example, a carboxylate group, sulfonate, sulfate, phosphate or phosphonate. Mention may in particular be made of (C 8 -C 20) alkyl betaines, sulfobetaines, (C 8 -C 20) alkylamido (C 3 -C 8) alkyl betaines and (C 8 -C 20) alkylamid (C 6 -C 8) alkyl sulfobetaines. Among the derivatives of secondary or tertiary aliphatic amines, optionally quaternized, which may be used, as defined above, there may also be mentioned the compounds of the following respective structures (B1) and (B2): Ra-C (O) -NH-CH2 -CH2-N + (Rb) (R1) -CH2C (O) O-, M +, X- (B1) Formula wherein: Ra represents a C1-C30 alkyl or alkenyl group derived from an acid RaCOOH, preferably present in hydrolyzed coconut oil, heptyl, nonyl or undecyl; Rb represents a beta-hydroxyethyl group; and - R, represents a carboxymethyl group; M + represents a cationic counterion derived from an alkali metal, alkaline earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine, and X represents an organic or inorganic anionic counterion, such as chosen from halides, acetates, phosphates, nitrates, (C 1 -C 4) alkyl sulphates, (C 1 -C 4) alkyl or (C 1 -C 4) alkylarylsulfonates, in particular methylsulphate and ethylsulphate; or else W and X- are absent; Ra-C (O) -NH-CH 2 -CH 2 -N (B) (131) (B2) Formula wherein: B is -CH 2 -CH 2 -O-X '; - B 'represents the group - (CH2), Y, with z = 1 or 2; X 'represents the group -CH2-C (O) OH, -CH2-C (O) OZ', -CH2-CH2-C (O) OH, -CH2-CH2-C (O) OZ ', or hydrogen atom; Y 'represents the group -C (O) OH, -C (O) OZ', -CH2-CH (OH) -SO3H or the group -CH2-CH (OH) -SO3-Z '; Z 'represents a cationic counterion derived from an alkaline or alkaline earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine; Ra, represents a C10-C30 alkyl or alkenyl group of an acid Ra-C (O) OH, preferably present in coconut oil or in hydrolysed linseed oil, an alkyl group, especially in 017 and its iso form, an unsaturated 017 group. These compounds of formula (B1) or (B2) are classified in the CTFA dictionary, 5th edition, 1993, under the names cocoamphodiacétate disodium, lauroamphodiacétate disodium, capryloamphodiacétate disodium, lauroamphodipropionate disodium, capryloamphodipropionate disodium, cocoamphodipropionique. Disodium caprylamphodiacetate, disodium cocoamphodipropionate, disodium caprylamphodipropionate, lauroamphodipropionic acid, acid For example, mention may be made of cocoamphodiacetate marketed by Rhodia under the trade name MIRANOL® C2M concentrate. It is also possible to use compounds of formula (B'2); Ra-NH-CH (Y ") - (CH2) nC (O) -NH- (CH2) n -N (Rd) (Re) (B'2) Formula wherein: ^ Y" represents the group -C (O) OH, -C (O) OZ-, -CH2-CH (OH) -SO3H or -CH2-CH (OH) -SO3-Z-; Rd and Re, independently of one another, represent a C 1 -C 4 alkyl or hydroxyalkyl radical; represents a cationic counterion derived from an alkali metal or alkaline earth metal, such as sodium, an ammonium ion or an ion; from organic amine; Ra "represents a C10-C30 alkyl or alkenyl group of a Ra-C (O) OH acid preferably present in coconut oil or in hydrolysed linseed oil. and n ', independently of one another, denote an integer ranging from 1 to 3. Among the compounds of formula (B'2), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and marketed by CHIMEX under the name CHIMEXANE HB.

Among the amphoteric or zwitterionic surfactants mentioned above, use is preferably made of alkyl (C 8 -C 20) betaines such as cocobetaine, (C 8 -C 20) alkylamido (C 3 -C 8) alkylbetaines such as cocamidopropylbetaine, the compounds of formula (B'2) such as the sodium salt of diethylaminopropyl lauryl amino succinamate (INCI name: sodium diethylaminopropyl cocoaspartamide) and mixtures thereof. More preferably, the amphoteric or zwitterionic surfactant (s) is (are) chosen from cocamidopropylbetaine, cocobetaine and the sodium salt of diethylaminopropyl laurylamino succinamate, and mixtures thereof. The cationic surfactant (s) that can be used in the dyeing composition according to the invention comprise, for example, primary, secondary or tertiary fatty amine salts, optionally polyoxyalkylenated salts, quaternary ammonium salts, and mixtures thereof. As quaternary ammonium salts, mention may be made, for example: - those corresponding to the following general formula (B3): - + R8 \ Rio X / D 1.9 R (B3) Formula in which: - R8 to R11 , identical or different, represent a linear or branched aliphatic group containing from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, it being understood that at least one of the groups R8 to R11 contain from 8 to 30 carbon atoms, and preferably from 12 to 24 carbon atoms; and - X-, represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (C 1 -C 4) alkyl sulphates, (C 1 -C 4) alkyl or (C 1 -C 4) alkylaryl- sulfonates, in particular methylsulfate and ethylsulfate. The aliphatic groups of R8 to R11 may further comprise heteroatoms such as in particular oxygen, nitrogen, sulfur and halogens. The aliphatic groups of R8 to R11 are, for example, chosen from C1-C30alkyl, C1-C30alkoxy, polyoxyalkylene (C2-06), alkyl (C1-C22) alkylamido (C2-C6) alkyl, ( C12-C22) acetate, and hydroxy-C1-C30 alkyl, X- is an anionic counterion selected from halides, phosphates, acetates, lactates, alkyl (C1-C4) sulfates, alkyl (C1-C4) - or alkyl (Cl C4) arylsulphonates. Of the quaternary ammonium salts of the formula (B3), tetraalkylammonium chlorides, such as, for example, dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group has from about 12 to about 22 atoms, are preferred. carbon, in particular behenyltrimethylammonium, distearyl dimethylammonium, cetyltrimethylammonium, benzyldimethylstearylammonium chlorides, or distearoylethylhydroxyethylmethylammonium methosulphate, dipalmitoylethylhydroxyethylammonium methosulphate or distearoylethylhydroxyethylammonium methosulphate, or else, finally, palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl (myristyl acetate) ammonium chloride sold under the name CERAPHYL® 70 by VAN DYK; the quaternary ammonium salts of imidazoline, such as, for example, those of formula (B4) below: ## STR2 ## in which R 12 represents a alkenyl or alkyl group having from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow; R13 represents a hydrogen atom, a C1-C4 alkyl group or an alkenyl or alkyl group having from 8 to 30 carbon atoms; R14 represents a C1-C4 alkyl group; R15 represents a hydrogen atom, a C1-C4 alkyl group; X represents an organic or inorganic anionic counterion, such as that chosen from halides, phosphates, acetates, lactates, (C 1 -C 4) alkyl sulphates, (C 1 -C 4) alkyl or (C 1 -C 4) alkylaryl- sulfonates. Preferably, R12 and R13 denote a mixture of alkenyl or alkyl groups containing from 12 to 21 carbon atoms, for example fatty acid derivatives of tallow, R14 denotes a methyl group, R15 denotes a hydrogen atom. Such a product is for example marketed under the name REWOQUAT® W 75 by the company REVVO; the quaternary di- or triammonium salts, in particular of formula (B5) below: R17 R19 R16 N (CH2) 3 N R21 R18 R20 (B5) Formula in which: R16 denotes an alkyl group comprising from about 16 to 30 carbon atoms, optionally hydroxylated and / or interrupted by one or more oxygen atoms; R 17 is chosen from hydrogen, an alkyl group containing from 1 to 4 carbon atoms or a group - (CH 2) 3 -N + (R 16a) (R 17a) (R 1sa), X; R16a, R17a, R18a, R18, R19, R20 and R21, which are identical or different, are chosen from hydrogen and an alkyl group comprising from 1 to 4 carbon atoms; and - X-, which may be identical or different, represent an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, alkyl (Cl-C4) sulphates, alkyl (Cl-C4) - or alkyl ( C1-C4) aryl sulfonates, in particular methylsulfate and ethylsulfate. Such compounds are, for example, the Finquat CT-P proposed by Finetex (Quaternium 89), the Finquat CT proposed by Finetex (Quaternium 75); quaternary ammonium salts containing one or more ester functions, such as those of the following formula (B6): OX / (CsH2s) R24O-CrHr2 (OH), R ± N + C, 1-1.2 (OH) Wherein R 22 is selected from C 1 -C 6 alkyl groups and C 1 -C 6 hydroxyalkyl or dihydroxyalkyl groups, R 23 is selected from: 0 - R 26 C - the saturated or unsaturated linear or branched C1-C22 hydrocarbon-based R27 groups, - the hydrogen atom, R25 is chosen from: O R2-8 C - the 2+ group 2X- - the R29 hydrocarbon groups in C1 -C6, linear or branched, saturated or unsaturated, - the hydrogen atom, - R24, R26 and R28, identical or different, are selected from C7-021 hydrocarbon groups, linear or branched, saturated or unsaturated; r, s and t, which may be identical or different, are integers of from 2 to 6, r1 and t1 which are identical or different, equal to 0 or 1 with r2 + r1 = 2r and t1 + t2 = 2t - y is an integer from 1 to 10, - x and z, which may be identical or different, are integers ranging from 0 to 10, - X- represents an anionic counterion, organic or inorganic, provided that the sum x + y + z is from 1 to 15, that when x is 0 then R23 is R27 and when z is 0 then R25 is R29. The alkyl groups R22 may be linear or branched, and more particularly linear.

Preferably, R 22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group. Advantageously, the sum x + y + z is from 1 to 10. When R 23 is a hydrocarbon R 27 group, it may be long and have 12 to 22 carbon atoms, or short and have from 1 to 3 carbon atoms.

When R 25 is a hydrocarbon R 29 group, it preferably has 1 to 3 carbon atoms. Advantageously, R24, R26 and R28, which are identical or different, are chosen from linear or branched, saturated or unsaturated C11-C21 hydrocarbon-based groups, and more particularly from saturated linear or branched C11-C21 alkyl and alkenyl groups. or unsaturated. Preferably, x and z, which are identical or different, are equal to 0 or 1. Advantageously, y is equal to 1. Preferably, r, s and t, identical or different, are equal to 2 or 3, and even more particularly are equal to 2 .

The anionic counterion X- is preferably a halide, such as chloride, bromide or iodide; a (C1-C4) alkyl sulphate; (C1-C4) alkyl or (C1-C4) alkyl aryl sulfonate. However, it is possible to use methanesulphonate, phosphate, nitrate, tosylate, an anion derived from an organic acid such as acetate or lactate or any other anion compatible with ammonium with an ester function.

The anionic counterion X- is even more particularly chloride, methylsulfate or ethylsulfate. In the dye composition according to the invention, the ammonium salts of formula (B6) are used more particularly in which: R22 denotes a methyl or ethyl group, x and y are equal to 1, -z is equal to 0 or 1, - r, s and t are equal to 2, - R23 is chosen from: o - the group R26 C - - the methyl, ethyl or hydrocarbon groups at 014-022, - the hydrogen atom, - R25 is chosen from: O - the group R2-8C - - the hydrogen atom, - R24, R26 and R28, which are identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups. Advantageously, the hydrocarbon radicals are linear. Examples of compounds of formula (B6) include salts, especially diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium, monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof, especially diacyloxyethyldimethylammonium chloride or methylsulfate. The acyl groups preferably have from 14 to 18 carbon atoms and come more particularly from a vegetable oil such as palm oil or sunflower oil. When the compound contains more than one acyl group, the latter groups may be identical or different.

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, alkyldiethanolamine or alkyldisopropanolamine, optionally oxyalkylenated, with fatty acids or with mixtures of fatty acids of plant or animal origin, or with transesterification of their methyl esters. This esterification is followed by quaternization using an alkylating agent such as an alkyl halide, preferably methyl or ethyl, a dialkyl sulphate, preferably methyl or ethyl sulphate. methyl methanesulfonate, methyl para-toluenesulfonate, glycol or glycerol chlorohydrin. Such compounds are, for example, sold under the names DEHYQUART® by the company HENKEL, STEPANQUAT® by the company STEPAN, NOXAMIUM® by the company CECA, REWOQUAT® VVE 18 by the company REWOWITCO. The coloring composition according to the invention may contain, for example, a mixture of quaternary ammonium mono-, di- and triester salts with a majority by weight of diester salts. It is also possible to use the ammonium salts containing at least one ester function described in US-A-4874554 and US-A-4137180. The behenoylhydroxypropyltrimethylammonium chloride proposed by KAO can be used under the name Quatarmin BTC 131.

Preferably the ammonium salts containing at least one ester function contain two ester functions. Among the cationic surfactants that may be present in the dye composition according to the invention, it is more particularly preferred to choose the cetyltrimethylammonium, behenyltrimethylammonium, dipalmitoylethylhydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium, dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof. Examples of nonionic surfactants useful in the dye composition used according to the invention are described, for example, in "Handbook of Surfactants" by M. R. PORTER, Blackie & Son editions (Glasgow and London), 1991, pp. 116-178. They are chosen in particular from alcohols, alpha-diols and (C1-C20) alkyl phenols, these compounds being etherified with ethoxylated and / or propoxylated, glycerolated groups and having at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, the number of ethylene oxide groups and / or propylene oxide ranging in particular from 1 to 100, more particularly from 2 to 50, more particularly from 2 to 30, and the number of glycerol groups that can go in particular from 1 to 30. - Mention may also be made of copolymers of ethylene oxide and propylene oxide, esters of fatty acids and of sorbitan optionally oxyethylenated, esters of fatty acids and of sucrose, esters of acids oxyalkylenated fats, optionally oxyalkylenated alkylpolyglycosides, alkylglucoside esters, N-alkylglucamine and N-acylmethylglucamine derivatives, aldobionamides and amine oxides. The nonionic surfactants are more particularly chosen from oxyalkylenated, glycerolated nonionic surfactants. The oxyalkylenated units are more particularly oxyethylenated units, oxypropylene, or their combination, preferably oxyethylenated. As examples of oxyalkylenated or glycerolated nonionic surfactants, mention may be made of: oxyalkylenated (C 8 -C 24) alkyl phenols; saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated C 8 -C 30 alcohols; saturated or unsaturated, linear or branched, oxyalkylenated C 8 -C 30 amides; saturated or unsaturated, linear or branched, C 8 -C 30 acid esters of polyethylene glycols; saturated or unsaturated, linear or branched, C8-030 esters of oxyethylenated sorbitol; vegetable oils oxyethylenated, saturated or not; condensates of ethylene oxide and / or propylene oxide, among others, alone or in mixtures. Oxyethylenated and / or oxypropylenated silicones. The surfactants having a number of moles of ethylene oxide and / or propylene ranging from 1 to 100, preferably from 2 to 50, preferably from 2 to 30. Advantageously, the nonionic surfactants do not comprise any reasons. Oxypropylenes. According to a preferred embodiment of the invention, the oxyalkylenated nonionic surfactants are chosen from oxyethylenated C 8 -C 30 alcohols comprising from 1 to 100 moles of ethylene oxide, preferably from 2 to 50, more particularly from 2 to 30 moles of ethylene oxide; linear or branched, saturated or unsaturated C 8 -C 30 acid esters, and oxyethylenated sorbitol esters comprising from 1 to 100 moles of ethylene oxide. As an example of glycerolated nonionic surfactants, the C 8 -C 40 alcohols, glycerolated, are preferably used. By way of example of compounds of this type, mention may be made of lauryl alcohol with 4 mol of glycerol (INCI name: POLYGLYCERYL-4 LAURYL ETHER), lauric alcohol with 1.5 mol of glycerol, and oleic alcohol containing 4 moles of glycerol (INCI name: POLYGLYCERYL-4 OLEYL ETHER), oleic alcohol containing 2 moles of glycerol (INCI name: POLYGLYCERYL-2 OLEYL ETHER), cetearyl alcohol containing 2 moles of glycerol, cetearyl alcohol with 6 moles of glycerol, oleocetyl alcohol with 6 moles of glycerol, and octadecanol with 6 moles of glycerol. Among the glycerolated alcohols, it is more particularly preferred to use the alcohol C8 / 010 to one mole of glycerol, the C10 / 012 alcohol to 1 mole of glycerol and the alcohol in O12 to 1.5 moles of glycerol.

Preferably, the surfactant or surfactants are chosen from nonionic, anionic or amphoteric surfactants. More particularly, the additional surfactant (s) present in the composition are chosen from nonionic surfactants. Preferably, the surfactant (s), when (they) are (are) present, is (are) chosen from oxyalkylenated, especially oxyethylenated, oxypropylene nonionic surfactants, or their combination, more particularly oxyethylenated; glycerol, or mixtures thereof. Even more preferentially, the nonionic surfactants are chosen from oxyethylenated sorbitol esters, oxyethylenated fatty alcohols and glycerolated fatty alcohols, and mixtures thereof. In the dyeing composition, the amount of the surfactant (s), when present, is preferably from 0.1 to 50% by weight, more preferably from 0.5 to 20% by weight, relative to the weight of said composition Medium The medium of the dye composition according to the invention is advantageously an aqueous medium. It may further comprise one or more organic solvents. As organic solvent, there may be mentioned for example linear or branched, preferably saturated monoalcohols or diols, comprising 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2 methyl 2,4-pentanediol), neopentyl glycol and 3-methyl-1,5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as benzyl alcohol, phenylethyl alcohol; polyols with more than two hydroxyl functions such as glycerol; polyol ethers such as, for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers such as, for example, propylene glycol monomethyl ether; and the alkyl ethers of diethylene glycol, especially C1-C4, for example, monoethyl ether or monobutyl ether diethylene glycol, alone or in mixture. The organic solvents, when they are present, generally represent between 1 and 40% by weight relative to the total weight of the dye composition, and preferably between 5 and 30% by weight relative to the total weight of the dye composition. Preferably the coloring composition is aqueous. In this case it preferably comprises from 30 to 95% of water by weight, better still from 40 to 90% by weight of water, more preferably from 50 to 85% by weight relative to the total weight of the composition. coloring. The pH of the dye composition, if it is aqueous, is generally between 3 and 12, preferably between 5 and 11. Preferably between 7 and 11 inclusive. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratinous fibers and in particular the alkaline agents of the invention mentioned above.

Fatty Bodies The coloring composition may optionally comprise one or more fatty substances. By "fatty substance" is meant an organic compound which is insoluble in water at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg) (solubility of less than 5% and preferably of 1%, even more preferentially at 0.1%). They have in their structure at least one hydrocarbon chain containing at least 6 carbon atoms or a chain of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same conditions of temperature and pressure, such as, for example, chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran ( THF), petrolatum oil or decamethylcyclopentasiloxane. The fatty substances of the invention do not contain salified or unsaturated carboxylic acid groups (COOH or COO-). In particular, the fatty substances of the invention are neither (poly) oxyalkylenated nor (poly) glycerolated. By "oil" is meant a "fat" which is liquid at room temperature (25 ° C), and at atmospheric pressure (760 mm Hg).

The term "non-silicone oil" means an oil containing no silicon atom (Si) and a "silicone oil" an oil containing at least one silicon atom. More particularly, the fatty substances are chosen from C 6 hydrocarbons. C16, hydrocarbons having more than 16 carbon atoms, non-silicone oils of animal origin, vegetable oils of the triglyceride type, synthetic triglycerides, fluorinated oils, fatty alcohols, fatty acid esters and / or fatty alcohol different from triglycerides and vegetable waxes, non-silicone waxes, silicones, and mixtures thereof.

It is recalled that the alcohols, esters and fatty acids more particularly have at least one hydrocarbon group, linear or branched, saturated or unsaturated, comprising 6 to 30, more preferably 8 to 30 carbon atoms, optionally substituted, in particular by one or several hydroxyl groups (in particular 1 to 4). If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise. Regarding the C 6 -C 16 hydrocarbons, the latter are linear, branched, optionally cyclic and preferably alkanes. By way of example, mention may be made of hexane, dodecane and isoparaffins, such as isohexadecane and isodecane. As hydrocarbon oils of animal origin, mention may be made of perhydrosqualene. Triglyceride oils of vegetable or synthetic origin are preferably chosen from liquid triglycerides of fatty acids containing from 6 to 30 carbon atoms, for example triglycerides of heptanoic or octanoic acids or, for example, sunflower oil or corn oil. , soya, squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor oil, avocado, triglycerides of caprylic / capric acids such as those sold by Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil; The linear or branched hydrocarbons, of mineral or synthetic origin, of more than 16 carbon atoms, are preferably chosen from paraffin oils, petroleum jelly, liquid petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam® . As regards the C 6 -C 16 alkanes, the latter are linear, branched, and possibly cyclic. By way of example, mention may be made of hexane, dodecane and isoparaffins, such as isohexadecane and isodecane.

As oils of animal, vegetable, mineral or synthetic origin, which can be used in the composition of the invention, mention may be made, for example, of: the fluorinated oils may be chosen from perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, sold under the names "FLUTEC® PC1" and "FLUTEC® PC3" by BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names "PF 5050®" and "PF 5060®" by the company 3M, or bromoperfluorooctyl sold under the name "Foralkyl®" by the company Atochem; nonafluoro-methoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name "PF 5052®" by the company 3M. The fatty alcohols that are suitable for carrying out the invention are more particularly chosen from linear or branched saturated or unsaturated alcohols containing from 6 to 30 carbon atoms, preferably from 8 to 30 carbon atoms. For example, cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol or linoleic alcohol may be mentioned; .

With regard to fatty acid esters and / or fatty alcohols, advantageously different from the triglycerides mentioned previously; mention may in particular be made of linear or branched C 1 -C 26 saturated or unsaturated aliphatic mono or poly acid esters and linear or branched C 1 -C 26 saturated or unsaturated aliphatic mono or polyalcohols, the total number of carbon of the esters being greater or equal to 6, more preferably greater than or equal to 10. Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isoketyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso) stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl ricinoleate acetyl; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononanoate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl palmitates and isopropyl palmitate, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate; , styryl, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate. Still within the scope of this variant, it is also possible to use esters of C 4 -C 22 di or tricarboxylic acids and of C 1 -C 22 alcohols and esters of mono di or tricarboxylic acids and of di, tri, alcohols. tetra or pentahydroxy in 02-026. These include: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate, tridecyl erucate; triisopropyl citrate; triisotearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; and polyethylene glycol distearates. Among the esters mentioned above, it is preferred to use ethyl, isopropyl, myristyl, cetyl, stearyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, myristates of alkyls such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and isononyl isonononate, cetyl octanoate. The dye composition may also comprise, as fatty ester, esters and diesters of C 6 -C 30, preferably C 12 -C 22, fatty acid sugars. It is recalled that "sugar" is understood to mean oxygenated hydrocarbon compounds which have several alcohol functions, with or without an aldehyde or ketone function, and which contain at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides. Suitable sugars include, for example, sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and their derivatives. especially alkyls, such as methyl derivatives such as methylglucose. The esters of sugars and of fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated C 6 -C 30, preferably C 12 -C 22, fatty acids. or unsaturated. If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise. The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters and mixtures thereof.

These esters may be for example oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonates, or mixtures thereof, such as in particular the mixed oleo-palmitate, oleostearate and palmitostearate esters. More particularly, the mono- and di-esters are used, and especially the mono- or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, sucrose, glucose or methylglucose. By way of example, mention may be made of the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

Mention may also be made, by way of examples, of esters or mixtures of esters of fatty acid sugar: the products sold under the names F160, F140, F110, F90, F70, SL40 by the company Crodesta, respectively denoting sucrose palmito-stearates of 73% monoester and 27% di- and tri-ester, 61% monoester and 39% di-, tri- and tetraester, 52% monoester and 48% monoester; % di-, tri, and tetraester, 45% monoester and 55% di-, tri-, and tetraester, 39% monoester, and 61% di-, tri-, and tetra- ester, and sucrose mono-laurate; the products sold under the name Ryoto Sugar Esters, for example 10 referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% di-triester-polyester; the sucrose mono-dipalmito-stearate marketed by Goldschmidt under the name Tegosoft® PSE. The non-silicone wax or waxes are chosen in particular from Carnauba wax, Candelila wax, and Alfa wax, paraffin wax, ozokerite, vegetable waxes such as olive wax, wax of rice, hydrogenated jojoba wax or the absolute waxes of flowers such as the essential wax of blackcurrant sold by the company BERTIN (France), animal waxes such as beeswax, or modified beeswax (cerabellina) ); other waxes or waxy raw materials which can be used according to the invention are, for example, marine waxes such as that sold by SOPHIM under the reference M82, and polyethylene or polyolefin waxes in general. The silicones that can be used in the dyeing composition of the present invention are volatile or cyclic, linear or branched volatile or non-volatile silicones, organic or non-modified, having a viscosity of 5 × 10 -6 to 2.5 m 2 / s at 25 ° C. ° C and preferably 1.10-5 to 1m2 / s. The silicones that can be used in accordance with the invention can be in the form of oils, waxes, resins or gums. Preferably, the silicone is chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), and organomodified polysiloxanes comprising at least one functional group chosen from amino groups and alkoxy groups. Organopolysiloxanes are further defined in Walter Noll's "Chemistry and Technology of Silicones" (1968), Academie Press. They can be volatile or nonvolatile. When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60 ° C. and 260 ° C., and even more particularly from: (i) cyclic polydialkylsiloxanes containing from 3 to 7, preferably from 4 to 5 silicon atoms. It is, for example, octamethylcyclotetrasiloxane sold in particular under the name VOLATILE SILICONE® 7207 by UNION CARBIDE or SILBIONE® 70045 V2 by RHODIA, decamethylcyclopentasiloxane marketed under the name VOLATILE SILICONE® 7158 by UNION CARBIDE, and SILBIONE ® 70045 V5 by RHODIA, as well as their mixtures. Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the VOLATILE® SILICONE FZ 3109 marketed by UNION CARBIDE, of formula: ## STR5 ## D 'D' -1 with D ': It is also possible to mention cyclic polydialkylsiloxane mixtures with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50) and the octamethylcyclotetrasiloxane mixture. and oxy-1,1 '- (hexa-2,2,2', 2 ', 3,3'-trimethylsilyloxy) bis-neopentane (ii) linear volatile polydialkylsiloxanes having 2 to 9 silicon atoms and having a viscosity less than or equal to 5.10-6 m 2 / s at 25 ° C. It is, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200" by Toray Silicone, silicones falling into this class are also described. in L article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics". Non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the above organofunctional groups and mixtures thereof are preferably used. These silicones are more particularly chosen from polydialkylsiloxanes, among which may be mentioned mainly polydimethylsiloxanes with trimethylsilyl end groups. The viscosity of the silicones is measured at 25 ° C. according to ASTM 445 Appendix C.

Among these polydialkylsiloxanes, mention may be made, without limitation, of the following commercial products: SILBIONE® oils of the 47 and 70 047 series or the MIRASIL® oils marketed by RHODIA, such as, for example, the 70 047 V 500 000 oil; the oils of the MIRASIL® series marketed by RHODIA; the oils of the 200 series of Dow Corning, such as DC200 having a viscosity of 60,000 mm 2 / s; - VISCASIL® oils from GENERAL ELECTRIC and some oils from SF series (SF 96, SF 18) from GENERAL ELECTRIC.

Mention may also be made of polydimethylsiloxanes with dimethylsilanol end groups known under the name of dimethiconol (CTFA), such as the oils of the 48 series from the company RHODIA. In this class of polydialkylsiloxanes, mention may also be made of the products sold under the names "ABIL WAX® 9800 and 9801" by GOLDSCHMIDT, which are polydialkyl (Cl-C20) siloxanes. The silicone gums that can be used in accordance with the invention are in particular polydialkylsiloxanes, preferably polydimethylsiloxanes having high average molecular weights of between 200,000 and 1,000,000 used alone or in a mixture in a solvent. This solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane or their mixtures. More particularly useful products according to the invention are mixtures such as: - mixtures formed from a hydroxyl end-of-the-chain polydimethylsiloxane, or dimethiconol (CTFA) and a cyclic polydimethylsiloxane also called cyclomethicone (CTFA) such as the product Q2 1401 marketed by Dow Corning; mixtures of a polydimethylsiloxane gum and a cyclic silicone such as the product SF 1214 Silicone Fluid from the company General Electric, this product is an SF 30 gum corresponding to a dimethicone, having a number average molecular weight of 500 000 solubilized in oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane; mixtures of two PDMSs of different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company General Electric. The product SF 1236 is the mixture of an SE 30 gum defined above having a viscosity of 20 m 2 / s and an SF 96 oil with a viscosity of 5 × 10 -6 m 2 / s. This product preferably comprises 15% of SE gum and 85% of an SF 96 oil. The organopolysiloxane resins used in accordance with the invention are crosslinked siloxane systems containing the units: R 2 SiO 2/2, R 3 SiO 1/2, RSiO3 / 2 and 5i0412 wherein R represents an alkyl having 1 to 16 carbon atoms. Among these products, those that are particularly preferred are those in which R denotes a C1-C4 lower alkyl group, more particularly methyl. Among these resins may be mentioned the product sold under the name "Dow Corning 593" or those sold under the names "Silicone Fluid SS 4230 and SS 4267" by the company General Electric and which are silicones of dimethyl / trimethyl siloxane structure. Mention may also be made of the trimethylsiloxysilicate type resins sold in particular under the names X22-4914, X21-5034 and X21-5037 by the company SHI N-ETSU. The organomodified silicones that may be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.

In addition to the silicones described above, the organomodified silicones may be polydiarylsiloxanes, in particular polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned above. The polyalkylarylsiloxanes are particularly chosen from polydimethyl / methylphenylsiloxanes, linear and / or branched polydimethyl / diphenylsiloxanes with a viscosity ranging from 1 × 10 -5 to 5 × 10 -2 m 2 / s at 25 ° C. Among these polyalkylarylsiloxanes include by way of example the products sold under the following names: SILBIONE® oils of the 70 641 series from RHODIA; 25. RHODORSIL® 70 633 and 763 RHODIA series of oils; . DOW CORNING 556 COSMETIC GRAD FLUID oil from DOW CORNING; . silicones of the PK series from BAYER, such as the product PK20; . silicones of the PN and PH series of BAYER, such as the PN1000 and PH1000 products; 30 . certain oils of the SF series of GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250, SF 1265. Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising: substituted or unsubstituted amino groups, such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company GENESEE or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amino groups are, in particular, C1-C4 aminoalkyl groups; alkoxylated groups, such as the product sold under the name "Silicone Copolymer F-755" by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by the company GOLDSCHMIDT. More particularly, the fatty substances are chosen from liquid or pasty compounds at room temperature (25 ° C.) and at atmospheric pressure. Preferably, the fatty substance is a liquid compound at a temperature of 25 ° C. and at atmospheric pressure. The fatty substances are advantageously chosen from C 6 -C 16 alkanes, non-silicone oils of vegetable, mineral or synthetic origin, fatty alcohols, fatty acid esters and / or fatty alcohol esters, or mixtures thereof. Preferably, the fatty substance is chosen from liquid petrolatum, C6-C16 alkanes, polydecenes, liquid esters of fatty acid and / or fatty alcohol, liquid fatty alcohols or mixtures thereof. In a first variant of the invention the total fat content is less than 20% by weight relative to the total weight of the composition. It then varies preferably from 0 to 19%, better still from 0 to 15%, more preferably from 0 to 10% by weight relative to the total weight of the composition (mixture of the dyeing and oxidizing compositions). In a second variant of the invention the total fat content is greater than or equal to 20% by weight relative to the total weight of the composition (mixture of dye and oxidizing compositions). It then varies preferably from 20 to 80%, more preferably from 30 to 75%, more preferably from 50 to 70% by weight relative to the total weight of the composition (mixture of the dyeing and oxidizing compositions).

Other additives The coloring composition may also contain various adjuvants different from the associative polymers of the invention and conventionally used in compositions for the dyeing of hair, such as, for example, anionic, cationic, nonionic, amphoteric or zwitterionic polymers, or mixtures thereof; thickening agents such as crosslinked acrylic acid homopolymers, cellulosic thickeners (with for example hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose), guar gum and its derivatives (for example hydroxypropylguar), microbial origin (especially xanthan gum, scleroglucan gum); mineral thickeners such as clays; ammonium salts such as ammonium chloride, ammonium acetate; antioxidants or reducing agents such as ascorbic acid, erythorbic acid, sulfite, bisulfite or ammonium metabisulfite, ammonium thiolactate; penetrating agents, sequestering agents such as ethylenediamine tetraacetic or its salts; perfumes ; titanium oxides; buffers; dispersants; and preservatives, or mixtures thereof. The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the dye composition. Oxidizing Composition Chemical Oxidizing Agent The second composition used in the process according to the invention also comprises at least one chemical oxidizing agent. It should be noted that the oxidizing agents present in the oxidizing composition are qualified as "chemical" to differentiate them from the oxygen in the air.

In particular, the chemical oxidizing agent (s) that are suitable for the present invention are, for example, chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as, for example, persulfates, perborates, peracids and their precursors and alkali or alkaline earth metal percarbonates.

Advantageously, the oxidizing agent is hydrogen peroxide. The content of oxidizing agent (s) is more particularly from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, relative to the weight of the oxidizing composition.

Surfactants The oxidizing composition may further comprise one or more surfactants. In particular, the surfactant or surfactants are chosen from anionic, amphoteric, zwitterionic, cationic or nonionic surfactants, and preferably nonionic surfactants. Reference can be made to the lists of compounds of this type given in the context of the description of the dye composition. Preferably, these surfactants, if they are present, are chosen from nonionic surfactants. Even more preferably, the oxyalkylenated nonionic surfactants are chosen from oxyethylenated C 8 -C 30 alcohols comprising from 1 to 100 moles of ethylene oxide, preferably from 2 to 50 and more preferably from 2 to 30; linear or branched, saturated or unsaturated C 8 -C 30 acid esters of oxyethylenated sorbitol comprising from 1 to 100 moles of ethylene oxide.

In the oxidizing composition, the amount of the surfactant (s), when present, is preferably from 0.1 to 50% by weight, more preferably from 0.5 to 20% by weight, relative to the weight of said composition.

Medium The oxidizing composition is advantageously an aqueous composition. It may also comprise one or more organic solvents chosen from those listed previously; the latter more particularly, when present, from 1 to 40% by weight relative to the weight of the oxidizing composition, and preferably from 5 to 30% by weight. The oxidizing composition also preferably comprises one or more acidifying agents. Among the acidifying agents, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid citric acid, lactic acid, sulphonic acids. Usually, the pH of the oxidizing composition, when aqueous, is less than 7.

Other additives The oxidizing composition may also contain various adjuvants conventionally used different from the aforementioned associative thickening polymers, such as, for example, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof; thickeners such as crosslinked acrylic acid homopolymers, thickeners such as, for example, cellulosic polymers such as, for example, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, guar gum and its derivatives (for example hydroxypropylguar) gums of microbial origin (especially xanthan gum, scleroglucan gum); sequestering agents such as ethylenediamine tetraacetic or its salts; perfumes ; and preservatives, or mixtures thereof. The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the oxidizing composition.

Propellant Gas As indicated above, at least one of the coloring and / or oxidizing compositions used in the process according to the invention is delivered from a pressurized container. In other words, the mixture used in the process according to the invention comprises (initially) one or more propellants. It should be noted that in the context of the invention, the propellant gas can be used to allow the expulsion of the composition or compositions, but also to facilitate or cause their expansion.

As indicated above, at least one of the compositions comprises at least one propellant, and preferably both compositions comprise at least one propellant. In other words, the gas or gases are mixed with the composition. As a propellant gas suitable for the implementation of the invention, mention may be made of the gases usually employed in the cosmetics field, in particular the volatile hydrocarbons, optionally halogenated, for example n-butane, propane isobutane, pentane and their halogenated derivatives; carbon dioxide, nitrous oxide, dimethyl ether, nitrogen, alone or in mixtures. Preferably, the propellant gas or gases are chosen from alkanes and in particular from n-butane, propane and isobutane, and mixtures thereof. The gases are under pressure, more particularly at least partially in the form of liquid. In the preferred case where each of the compositions comprises at least one propellant gas, these may be identical or different, from one composition to another, whether in kind of the gas or gases, and in their respective proportions. they are mixtures. Preferably, the content of propellant gas (s) represents a content ranging from 1 to 30% by weight relative to the weight of the composition, preferably from 2 to 15% by weight relative to the weight of the composition in which it ( s) is (are).

Device The mixture applied to the fibers is thus obtained from the mixture of the dyeing and oxidizing compositions described above.

The mixture can be obtained from a single pressurized container comprising either the oxidizing composition or the dye composition as previously described, said composition being mixed before use with a composition (coloring or oxidizing respectively) from a non-pressurized container such as a vial, a tube, the mixture of the two compositions comprising and at least one associative thickening polymer.

The mixture can also be obtained from a single pressurized container comprising the oxidizing composition and the coloring composition as previously described in two separate pockets, the mixture of the two compositions comprising at least one associative thickening polymer.

Preferably, said mixture used in the context of the invention obtained from a device comprising: a first container containing the dyeing composition described above, and a second container containing the oxidizing composition also described previously, at least one of the containers being pressurized, preferably both containers being pressurized; means for delivering the compositions; the mixture of the two compositions comprising at least one associative thickening polymer. Preferably, each container is surmounted by a means for delivering each composition.

One or both containers may be rigid-walled and directly contain the composition. Alternatively, one or both containers may be rigid-walled and enclose a flexible-walled pouch that contains the composition. According to this embodiment, either the coloring composition is in a pocket or the oxidizing composition is in a pocket or both. According to this configuration, the composition in the pocket may not include propellant, the latter being in the volume defined between the rigid walls of the container and the bag. Preferably, the composition contained in the bag also comprises at least one propellant gas. According to another variant, the device comprises a first rigid-walled container which contains one or other of the dyeing or oxidizing compositions, the first rigid walls enclosing a flexible pouch which contains the other coloring or oxidizing compositions and which constitutes a second container. According to another preferred variant, the device comprises two containers with rigid walls, preferably without pocket, each containing a composition.

The device comprises means for delivering the compositions, the means comprising at least one dispensing valve which overcomes the container (s). Preferably, the means for delivering the compositions comprises two dispensing valves, each valve surmounting a container.

The at least one valve is in selective fluid communication with the interior of the at least one container via an inlet port of the valve, the communication being established in response to the actuation of an actuating means, such as a button. -poussoir. When the device comprises a first rigid-walled container which encloses a flexible pouch, a single valve is provided to deliver the two compositions. The valve is then provided with two inlet ports, one of the ports being able to communicate with the inside of the bag and the other with the volume defined between the bag and the rigid walls of the container. When the containers do not contain a pocket, they are provided with a dip tube for conveying the composition to the inlet port of the dispensing valve. When the containers enclose a pocket, the inlet port of the valve opens into the pocket. The device may comprise at least one diffuser that caps the valve or valves.

According to a first variant, the device comprises a single diffuser which covers the two valves. According to a second variant, the device comprises two diffusers, each independently styling a valve. The push button can be part of the diffuser. The diffuser may be provided with one or more distribution ducts provided for conveying the composition or compositions to one or more dispensing orifices. When the device comprises two diffusers, each of the diffusers is provided with a conduit for conveying the composition between the outlet orifice of the valve and a dispensing orifice. When the device comprises a single diffuser, it may be provided with two delivery conduits compositions, each conduit communicating with the outlet port of a valve. According to a first embodiment, the two ducts each end at a dispensing orifice (not communicating with each other before the dispensing orifice). According to this configuration, the mixture of the compositions is made only after being distributed (thus after the dispensing orifices). According to a second embodiment, the two ducts end in a mixing chamber, from which a single duct is directed towards a single dispensing orifice. According to this configuration, the mixture of the compositions is made just before its expulsion from the device. Preferably, the two ducts open directly to each one of a dispensing orifice.

When the device comprises two diffusers, namely that it comprises two containers each surmounted by a valve and a diffuser that are specific to it, the two containers may be free with respect to each other, it is ie not secured. Alternatively, the two containers may be secured, for example by means of an outer envelope covering partially containers (including thermoformed film, rigid metal or plasticized envelope), or even by means of notches made in the outer wall of each container allowing them to hang. When the device comprises a single diffuser which caps the two valves, it allows to secure the two containers. In this case, it is also possible to provide an outer envelope covering part of the containers. According to a particular embodiment of the invention, the device comprises two interconnected containers, the device for delivering the compositions concomitantly, via one or preferably two dispensing orifices. Preferably, according to this embodiment, the containers are rigid walls, a dispensing valve overlying each of the containers, a single diffuser covering the two valves, the two containers being secured.

Of course, the devices are designed in such a way that the dyeing and oxidizing compositions are brought into contact at the time of application of the mixture obtained.

Advantageously, the mixture of the dye composition and the oxidizing composition used in the process according to the invention, which is applied to the fibers, is in the form of a foam which is therefore produced just before its application. . More particularly, the dye composition that is delivered (obtained) from a pressurized container is in the form of a cream, a gel, a foam, preferably in the form of a foam. Furthermore, the oxidizing composition that is delivered (obtained) from a pressurized container is in the form of a cream, a gel, a foam, preferably in the form of a foam.

The pH of the mixture of the dyeing and oxidizing compositions is advantageously between 3 and 12, preferably between 5 and 11, preferably between 7 and 11 inclusive. It should be noted that the distribution valve (s), as well as the propellant (s) content, are adapted so as to allow the distribution of the compositions in respective appropriate proportions. In practice the weight ratio of coloring composition / oxidizing composition in the distributed mixture varies from 0.25 to 4 and preferably from 0.5 to 2. Even more preferentially, this ratio is 1.

The dyeing process according to the invention consists in applying the mixture thus obtained to human, dry or moist keratin fibers for a time sufficient to develop the desired coloration. According to the invention, the mixture obtained according to the process of the invention is applied to the keratin fibers, preferably in the form of a foam. The dyeing process is generally carried out at room temperature (between 15 to 25 ° C) and up to temperatures of up to 60 ° C to 80 ° C. After a pause of one minute to one hour, preferably from 5 minutes to 30 minutes, the keratin fibers are rinsed with water, optionally washed with a shampoo followed by rinsing with water. The following example serves to illustrate the invention without being limiting in nature.

EXAMPLE Dyeing composition (contents expressed in g% as they are): Ingredients Cocoyl betaine concentration in 30% aqueous solution (MIRATAINE BB / FLA 10 sold by the company Rhodia) Hydrogenated castor oil oxyhylenated (40%) (EUMULGIN 0.8 HRE 40) crystallized sorbitol (NEOSORB P 60 marketed by the company ROQUETTE) poly (di-methyl) di-allyl ammonium chloride in water at 40% at 2 perfume 0.4 erythorbic acid 0.5 ethylene diamine tetraacetic acid 0, 2 sodium metabisulfite 0.5 monoethanolamine 4,5 1-methyl-2,5-diamino-benzene 0.2 1-hydroxy-4-amino-benzene 1.25 1,3-dihydroxybenzene 0.75 1-hydroxy-3 amino-benzene 0.30 1-methyl-2-hydroxy-4-beta-hydroxyethylamino-benzene 0.15 2-methyl-1,3-dihydroxybenzene 0.65 ammonia (concentration 20% ammonia) 6 hydroxyethyl cellulose alkyl ( 014/16) (NATROSOL PLUS 330 0.3 marketed by ASHLAND) stearyl alcohol oxyethylenated (100 OE) (BRIJ S100-PA- (SG) 2 sold by the company CRODA) sucrose (SUCROSE ULTRA PURE GRADE marketed 1.33 by AMRESCO) deionized water 63.35 Oxidizing composition (contents expressed in g% in the state) chemical name Concentration mixture cetylstearyl alcohol / cetylstearyl alcohol 2.85 oxyethylene (33 0E) (SINNOWAX AO sold by the company COGNIS) alkyl acid monoethanolamide (C13 / 015 70/30 50% linear) carboxylic ether (20E) 0.85 glycerol 0.5 tetrasodium pyrophosphate, 10H 2 O , 02 disodium tin hexahydroxide disodium 0.04 diethylene triamine pentaacetic acid, pentasodium salt 0.15 40% aqueous solution hydrogen peroxide 50% solution 12 phosphoric acid Qs pH 2.2 deionized water QSP 100 Each of the compositions above is packaged in an aerosol container in the presence of the following propellants, in the weight ratio composition / propellant gas 94/6. - Coloring composition: 50% propane, 35% n-butane, 15% i-butane - Oxidizing composition: 25% propane, 40% n-butane, 35% i-butane The two aerosols are secured via a dispensing head incorporating the two distribution channels from the two pressurized containers, the mixture of the two compositions in a 1/1 weight ratio is effected only immediately after the outlet of the dispensing head. The resulting mixture is left on the fibers for 30 minutes at room temperature (25 ° C). A dark natural shade is obtained, covering the white hair well.

Claims (4)

REVENDICATIONS1. Process for dyeing keratinous fibers in Claims 1. A method for dyeing keratinous fibers in which a mixture obtained from: a coloring composition comprising at least one oxidation dye precursor and an oxidizing composition comprising at least one oxidizing agent is applied to said fibers; at least one of the compositions being delivered from a pressurized container, the mixture of the two compositions comprising at least one associative thickening polymer. 2. Method according to the preceding claim, characterized in that the associative thickening polymer or polymers are chosen from associative polyurethanes, more particularly cationic or nonionic, associative cellulose derivatives, more particularly cationic or nonionic, associative vinyllactams, associative unsaturated polyacids and more particularly those comprising at least one hydrophilic unit of the olefinic unsaturated carboxylic acid type, and at least one non-ethoxylated (C 10 -C 30) alkyl ester-type hydrophobic unit and the copolymers comprising, among their monomers, a carboxylic acid with α, β-monoethylenic unsaturation and α, β-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol, the associative aminoplast-ethers, the associative polymers or copolymers comprising at least one ethylenically unsaturated monomer containing a sulfonic group , alone or in mixtures 3. Method according to any one of claims 1 or 2, characterized in that the associative thickening polymer or polymers are nonionic or cationic 4. Method according to any one of claims 1 to 3, characterized in that the associative thickening polymer or polymers are chosen from associative polyurethanes, more particularly nonionic, associative cellulose derivatives cationic or nonionic. Process according to any one of the preceding claims, characterized in that the content of associative thickening polymer (s) represents from 0.1 to 40% by weight, preferably from 0.001 to 20% by weight, more particularly from 0.1 to 2% by weight relative to the weight of the mixture. . Process according to any one of the preceding claims, characterized in that the oxidation dye precursor (s) are chosen from oxidation bases and couplers. 7. Method according to any one of the preceding claims, characterized in that the pressurized container or containers comprise at least one propellant gas selected from volatile hydrocarbons, optionally halogenated, for example n-butane, propane, isobutane, pentane and their halogenated derivatives; carbon dioxide, nitrous oxide, dimethyl ether, nitrogen, compressed air, alone or in mixtures, preferably among alkanes, even more preferentially among n-butane, propane, isobutane and their mixtures . Process according to the preceding claim, characterized in that the propellant gas or gases represent a content ranging from 1 to 30% by weight relative to the weight of the composition, preferably from 2 to 15% by weight relative to the weight of the composition. in which he (they) is (are). . Process according to claim 7 or 8, characterized in that the coloring composition and the oxidizing composition each comprise at least one identical or different propellant gas. 10. Process according to any one of the preceding claims, characterized in that the chemical oxidizing agent (s) is (are) chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts and peracids and their precursors; and preferably hydrogen peroxide. 11. Method according to any one of the preceding claims, characterized in that the dye composition comprises at least one alkaline agent, more particularly chosen from ammonia, alkanolamines and amino acids, or mixtures thereof; preferably ammonia, alkanolamines and mixtures thereof. Process according to the preceding claim, characterized in that the alkaline agent (s) represent a content ranging from 0.01% to 30% by weight. preferably from 0.1 to 20% by weight, more preferably from 1 to 10% by weight, based on the weight of the dye composition. Process according to any one of the preceding claims, characterized in that the dye composition and / or the oxidizing composition comprises at least one surfactant chosen from cationic, amphoteric, nonionic and anionic surfactants. Process according to any one of the preceding claims, characterized in that the coloring composition and the oxidizing composition are each in a different container, constituting a single pressurized device, for delivering the two compositions. Process according to any one of Claims 1 to 14, characterized in that the dyeing composition and the oxidizing composition are each in a different pressurized container, the containers being optionally secured and making it possible to deliver the compositions concomitantly by the intermediate of one or two distribution ports. Process according to any one of the preceding claims, characterized in that the mixture of the dye composition and the oxidizing composition takes place after the dispensing orifices. Process according to any of the preceding claims, characterized in that the mixture of the coloring composition and the oxidizing composition, which is applied to the fibers, is in the form of a foam. Device suitable for carrying out the method according to any one of the preceding claims, characterized in that it comprises: - a first container containing a coloring composition comprising at least one oxidation dye precursor, and - a second container comprising an oxidizing composition comprising at least one chemical oxidizing agent, - at least one of the containers being pressurized, preferably both containers being pressurized - means for delivering the compositions - mixing the two compositions comprising at least one associative thickening polymer. 19. Device according to claim 18, wherein each container is surmounted by a means for delivering each composition. 20. Device according to one of claims 18 or 19, wherein the containers are secured, the device for delivering the compositions concomitantly, through one or preferably two dispensing orifices.