FR2945740A1 - Composition, useful for dyeing keratin fibers, preferably human hair, comprises oxidation bases comprising 2-((2-(4-amino-phenylamino)-ethyl)-(2-hydroxy-ethyl)-amino)-ethanol and 4,5-diaminopyrazole compound in a medium - Google Patents

Abstract

Composition comprises: one or more oxidation bases comprising 2-[[2-(4-amino-phenylamino)- ethyl]-(2-hydroxy-ethyl)-amino]-ethanol (I) or its addition salts with an acid; and one or more 4,5-diaminopyrazole compound (II) or their acid or base addition salts in a medium. Composition comprises: one or more oxidation bases comprising 2-[[2-(4-amino-phenylamino)-ethyl]-(2-hydroxy-ethyl)-amino]-ethanol (I) or its addition salts with an acid; and one or more 4,5-diaminopyrazole compound of formula (II) or their acid or base addition salts in a medium. Either R 1>-R 6>H, 1-6C alkyl (optionally substituted by at least one substituent comprising OR, NHR, NRR1a, SR, SOR, SO 2R, COR, COOH, CONH 2, CONHR, CONRR1a, PO(OH) 2, SH, SO 3X, a non-cationic heterocycle, Cl, Br or I), 2-4C hydroxyalkyl, 2-4C aminoalkyl, phenyl (optionally substituted by halo, 1-4C alkyl, nitro, CF 3, amino or 1-4C alkylamino), benzyl (optionally substituted by halo, 1-4C alkyl, amino or methylenedioxy), or group of formula (-(CH 2) m-X 1>-(CH-Y 1>) n-Z); or R 5>together with the nitrogen atom of NR 3>R 4>group in position 5 : at least 4-membered heterocycle; X : H, Na, K or NH 4; R, R1a : 1-4C alkyl or 1-4C alkenyl; m, n : 0-3; X 1>O or NH; Y 1>H or 1-4C alkyl; Z : methyl (when n is 0) or 1-4C alkyl or NR2aR3a (when n is >= 1); and R2a, R3a : H or 1-4C alkyl. Provided that at least one of R 1>-R 4>is H. Independent claims are included for: (1) dyeing keratin fibers, comprising applying the composition on the keratin fibers in the presence of one or more oxidizing agents during a sufficient time to develop the desired color; and (2) multi-compartment device comprising first compartment containing (I) and a second compartment containing one or more oxidizing agents. [Image].

Description

The invention relates to a dye composition comprising at least one particular secondary para-phenylenediamine oxidation base and a diaminopyrazole oxidation base, and to a diberal-containing dimerization composition. that the dyeing process using this composition. It is known to dye keratinous fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho or para-phenylenediamines, ortho or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as than indolic compounds. The variety of molecules involved in oxidation bases and couplers, allows to obtain a rich palette of colors. The so-called "permanent" coloration obtained with these oxidation dyes must also meet a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity and to have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and friction. The dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say, to obtain the lowest possible color differences throughout the same keratin fiber, which is in general differently sensitized (ie damaged) between its point and its root.

It is already known to use oxidation bases of the para-phenylene diamine secondary type of formula (I) below for dyeing keratinous fibers, especially the hair. In particular, such a base is disclosed in EP1580184 and EP0055386. This base has the drawbacks of leading to insufficiently intense or chromatic and / or too selective staining. Furthermore, it is known to use, in the field of dyeing keratin fibers, dyeing compositions using a diaminopyrazole base.

The object of the present invention is to obtain a composition for hair dyeing which has improved dyeing properties in terms of intensity or chromaticity, and / or selectivity and / or resistance to external agents such as shampoos, sweat and permanent deformities and light.

This object is achieved with the present invention which relates to a keratinous fiber coloring composition comprising, in a suitable dyeing medium, one or more oxidation bases selected from the compound of formula (I) or its salts. addition with an acid, OH HO and one or more 4,5-diaminopyrazole oxidation bases of formula (II) or their addition salts with an acid or a base, R6 NRIR2 (3) (4) (II) in which: R 1, R 2, R 3, R 4, R 5 and R 6, which are identical or different, represent a hydrogen atom; a C1-C6 alkyl radical which is unsubstituted or substituted with at least one substituent selected from OR, NHR, NRR ', SR, SOR, SO2R, COR, COOH, CONH2, CONHR, CONRR', PO (OH) 2, SH, SO3X, a non-cationic heterocycle, Cl, Br or I wherein X is hydrogen, Na, K, or NH4, and R and R ', which may be identical or different, represent a C1-C4 alkyl or alkenyl; a C2-C4 hydroxyalkyl radical; a C2-C4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted by a halogen atom or a C1-C4 alkyl, C1-C4 alkoxy, nitro, trifluoromethyl, amino or C1-C4 alkylamino radical; a benzyl radical; a benzyl radical substituted by a halogen atom or by a C1-C4 alkyl, C1-C4 alkoxy, methylenedioxy or amino radical; a radical - (CH2) m - X- (H) - Z IY in which m and n are integers, identical or different, between 0 and 3 inclusively, X represents an oxygen atom or the grouping NH, Y represents a hydrogen atom or a C1-C4 alkyl radical, and Z represents a methyl radical when n is 0, or Z represents a C1-C4 alkyl radical, a group OR or NR "R when n is greater than or equal to 1, R "and R" ', which may be identical or different, denoting a hydrogen atom or a C1-C4 alkyl radical; or R9 forms with the nitrogen atom of the NR group, R6 in the 5-position a heterocycle comprising at least 4 members, at least one of the radicals R 1, R 2, R 3 and R 4 represents a hydrogen atom. The invention also relates to a dyeing process using this composition.

Another subject of the invention is the use of the composition of the present invention for dyeing keratinous fibers, in particular human keratinous fibers such as the hair. The invention also relates to multi-compartment devices comprising compositions using one or more oxidation bases chosen from the compound of formula (I) or its addition salts with an acid and one or more oxidation bases. 5-diaminopyrazole of formula (II) or one of its addition salts with an acid or a base. The composition of the present invention makes it possible in particular to obtain a keratinous fiber coloring composition which is suitable for use in oxidation dyeing and makes it possible to obtain a coloring with various shades, intense or chromatic, aesthetic, not very selective and resistant. well to the various aggressions that can undergo the hair such as the shampoos, the sweat and the permanent deformations ..

It should be noted that in what follows, and unless otherwise indicated, the boundaries of a domain of values are included in this area. The compounds of formula (I) or (II) may be in the form of addition salts chosen especially from acid addition salts such as hydrochlorides, hydrobromides, sulphates, citrates, succinates and tartrates. lactates, tosylates, benzenesulfonates, phosphates and acetates. The compounds of formula (II) carrying an acid substituent may be in the form of addition salts with a base such as sodium, potassium, ammonium or alkanolamine salts. They may also be in the form of solvates, for example a hydrate, or a linear or branched alcohol solvate, such as ethanol or isopropanol. By way of examples of derivatives of formula (II) that can be used according to the invention, mention may be made of the compounds described in DE-A-38 43 892, DE-A-41 33 957 and patent applications WO 94/08969. , WO 94/08970, FR-A-2733749 and DE-A-195 43 988, such as 4,5-diamino-1-methylpyrazole, 4,5-diamino-1- (2-hydroxyethyl) pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) -pyrazole, 4,5-diamino-1,3-dimethyl-pyrazole, 4,5-diamino-3-methyl-1-phenyl-pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4, 5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4,5-diamino-1- (13-hydroxyethyl) -3- methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxy-phenyl) -pyrazole, 4,5-diamino-1- ethyl-3-hydroxy-methyl-pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl-pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl-pyrazo 4,5-Diamino-3-methyl-1-isopropylpyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl-pyrazole, and their addition salts. According to a particular embodiment, the dicmainopyrazole of formula (II) is such that R6 is hydrogen. According to this variant, R 1, R 2, R 3 and R 4 represent a hydrogen atom or a C 1 -C 4 alkyl radical and R 5 is an alkyl, hydroxyalkyl or alkoxyalkyl radical.

Even more particularly preferred is 4,5-diamino-1- (2-hydroxyethyl) -1H-pyrazole and its salts, such as 4,5-diamino-1- (2-hydroxyethyl) -1H-pyrazole sulfate. of the following formula: ## STR2 ## H2SO4 The compounds of formula (I) or (II) are generally present each in an amount of between 0.001 to 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%. The dye composition according to the invention may contain and preferably contains one or more couplers conventionally used for dyeing keratinous fibers. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. By way of example of a coupler, there may be mentioned 2-methyl-5-aminophenol, 5-N- (R-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol, 3 amino phenol, 2,4-dichloro-3-aminophenol, 5-amino-4-chloro-o-cresol, 1,3-dihydroxy benzene, 1,3-dihydroxy-2-methyl benzene, 4- chloro 1,3-dihydroxybenzene, 2,4-diamino 1- (13-hydroxyethyloxy) benzene, 2-amino-4- (R-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3 bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-13-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxy naphthalene, 2,7-naphthalenediol, 1-acetoxy-2-methylnaphthalene, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy-pyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3-4-dimethylpyridine, 3-amino-2 -me thylamino-6-methoxypyridine, 1-N- (R-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (R-hydroxyethylamino) toluene, 3-methyl-1-phenyl-5- pyrazolone and their addition salts with an acid. In the composition of the present invention, the coupler or couplers, if they are present, generally represent an amount of between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%. The dye composition of the invention may optionally comprise one or more additional oxidation bases conventionally used for dyeing keratinous fibers, different from the compounds of formula (I) or (II). By way of example, these additional oxidation bases are chosen from para-phenylenediamines different from the bases of formula (I), bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, bases heterocyclic oxidation bases of formula (II) and their addition salts. Among the para-phenylenediamines, there may be mentioned, for example, para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine and 2,6-dimethyl-para-phenylenediamine. , 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl para-phenylenediamine 4-amino N, N-diethyl-3-methylaniline, N, N-bis- (13-hydroxyethyl) para-phenylenediamine, 4-N, N-bis (13-hydroxyethyl) amino-2-methylaniline , 4-N, N-bis - ((3-hydroxyethyl) amino-2-chloroaniline, 2-13-hydroxyethyl-para-phenylenediamine, 2-fluoro para-phenylenediamine, 2-isopropyl para-phenylenediamine, N - (13-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, [3-hydroxyethyl) para-phenylenediamine, N - ( (N, N'-aminophenyl) para-phenylenediamine, N-phenyl-para-phenylenediamine, phenylenediamine, N- (13-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl para-phenylenediamine, 2- (3-hydroxyethylamino-5-amino-toluene, 3-hydroxy-1- (4'-hydroxyethyl) aminophenyl) pyrrolidine and their addition salts with an acid.

Among the para-phenylenediamines mentioned above, paraphenylenediamine, para-toluenediamine, 2-isopropyl para-phenylenediamine, 2-13-hydroxyethyl para-phenylenediamine, 2-13-hydroxyethyloxy paraphenylenediamine, 2,6 dimethyl para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (3-hydroxyethyl) para-phenylenediamine, 2-chloro-para-phenylenediamine 2-13-acetylaminoethyloxy para-phenylenediamine, and their acid addition salts are particularly preferred.

Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- ((3-hydroxyethyl) N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, the N, N'-bis - ([3-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis; - (13-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts with an acid. Among para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2 are exemplified. methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (13-hydroxyethylaminomethyl) phenol, 4-amino-2 -fluorine o phenol, 1-hydroxy-4-methylamino-benzene, 2-2'-methylenebis-4-amino 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 with an acid. 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, 2,3-diamino-6-methoxy pyridine, 2 - ((3-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.

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, 2,4 dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in the patent application FR-A-2750048 and among which mention may be made of pyrazolo [1,5- a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [ 1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-N, 7-N-7-tetramethyl-pyrazolo [1,5-a] -pyrimidine-3, 7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine and their acid addition salts and their tautomeric forms, when tautomeric equilibrium exists. There may also be mentioned diaminopyrazolinones described in patent application FR2886137 and in particular 2,3-diamino-6,7-dihydro-1H, 5H-pyrazol-1-one and its salts. In general, the addition salts of the additional oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides and sulphates. citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines . The dye composition in accordance with the invention may also contain one or more direct dyes that may be chosen in particular from nitro dyes of the benzene series, azo direct dyes and methine direct dyes. These direct dyes may be nonionic, anionic or cationic in nature. The medium suitable for dyeing, also known as a dyeing medium, generally comprises water or a mixture of water and one or more solvents such as, for example, lower C 1 -C 4 alkanols, such as ethanol and isopropanol. polyols such as propylene glycol, dipropylene glycol or glycerol, and polyol ethers such as dipropylene glycol monomethyl ether. The solvent or solvents are generally present in proportions which may be between 1 and 40% by weight approximately with respect to total weight of the dye composition, and even more preferably between 3 and 30% by weight approximately. The dyeing composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric or zwitterionic surfactants, or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents. 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 composition. Of course, one skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged. The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. Among the acidifying agents, mention may be made, by way of 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.

Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (III): ## STR2 ## wherein W is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 4 alkyl radical; Ra, Rb, Rd and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.

The composition according to the invention may comprise one or more oxidizing agents. The oxidizing agents are those conventionally used for the oxidation dyeing of keratin fibers, for example hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and the like. oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred. The composition with or without an oxidizing agent according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form that is suitable for dyeing keratinous fibers, and in particular hair humans. It can result from mixing at the time of use of several compositions. In a first particular variant it results from the mixture of at least two compositions, one comprising one or more oxidation bases selected from compounds of formula (I) or their addition salts with an acid, optionally one or more different additional oxidation bases of the compounds of formula (I) or of formula (II) or their salts, and optionally one or more couplers, a second composition comprising the oxidation base (s) of formula (II) or their salts and optionally a third composition comprising one or more oxidizing agents as described above. In a second particular variant it results from the mixture of two compositions, one comprising one or more oxidation bases chosen from the compound of formula (I) or its addition salts with an acid, the oxidation base (s). of formula (II) or their salts, optionally one or more additional oxidation bases different from the compounds of formula (I) or of formula (II) or their salts, and optionally one or more couplers, another composition comprising one or more oxidizing agents as described above. The composition of the invention is therefore applied to the hair for dyeing keratinous fibers either as such or in the presence of one or more oxidizing agents, for dyeing keratinous fibers. The process of the present invention is a process in which the non-oxidizing composition according to the present invention as defined above is applied to the fibers either alone or in the presence of an oxidizing agent for a time sufficient to develop the desired coloration. The color can be revealed at acidic, neutral or alkaline pH and the oxidizing agent can be added to the composition of the invention just at the time of use or it can be used from an oxidizing composition containing it applied simultaneously or sequentially to the composition of the invention. According to one particular embodiment, the composition without an oxidant according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, one or more oxidizing agents. The mixture obtained is then applied to the keratinous fibers. After a residence time of about 3 to 50 minutes, preferably about 5 to 30 minutes, the keratinous fibers are rinsed, washed with shampoo, rinsed again and then dried. The oxidizing agents are those indicated above.

The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing hair and as defined above. The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dyeing composition, the pH of the resulting composition applied to the keratinous fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 11. It can be adjusted to the desired value by means of acidifying or basifying agents usually used for dyeing keratinous fibers and as defined above.

The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains the oxidation-free dye composition of the present invention defined above comprising one or more oxidation bases chosen from the compound of formula (I) or its addition salts with an acid and one or more oxidation bases chosen from compounds of formula (II) or their addition salts with an acid or a base and a second compartment contains one or more oxidizing agents. A second device consists of a first compartment containing a composition comprising one or more oxidation bases chosen from the compound of formula (I) or its addition salts with an acid, optionally one or more additional oxidation bases other than those of formula (I) or (II) optionally one or more couplers and a second compartment containing a composition comprising one or more oxidation bases selected from compounds of formula (II) or their addition salts with an acid or a base and possibly one or more couplers.

A third device may optionally comprise the two compartments of the second device plus a third compartment containing a composition comprising one or more oxidizing agents. These devices may be equipped with means for delivering the desired mixture onto the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant. The examples which follow serve to illustrate the invention without, however, being limiting in nature. 13 EXAMPLES

EXAMPLES OF DYE EXAMPLE 1 The composition Cl comprises the following ingredients: Composition Cl 2 - [{2 - [(4-aminophenyl) amino] ethyl} (2- [0.0034 moles hydroxyethyl] amino] ethanol trichlorhydrate 4,5-diamino-1- ( [3-hydroxyethyl) pyrazole 0.01 moles sulfate 6-Chloro-2-methyl-5-aminophenol 0.00635 moles Meta aminophenol 0.0073 moles Oleic alcohol polyglycerol 2 moles 4 g MA glycerol Oleyl alcohol polyglycerol 4 moles 6 g MA glycerol (78 % MA) Oleic acid 3 g Oleic amine 2 EO marketed 7 g MA under the name ETHOMEEN 012 by the company AKZO Laurylamino succinamate of 3 g MA diethylaminopropyl, 55% sodium salt MA Oleic alcohol 5 g Monoethanolamide of alkyl acid 10 g MA (C13 / C15 70/30, 50% linear) carboxylic ether (2OE) Propylene glycol 9.5 g Ethyl alcohol 5 g Hexylene glycol 9.3 g Sodium metabisulfite in solution 0.455 g MA aqueous at 35% MA Ammonium acetate 0.8 g Antioxidant, sequestering qs Fragrance, preservative q.s Ammonia at 20% of NH3 10.2 g Demineralized water q.s.p 100 g 14 Method of application The composition Cl is diluted extemporaneously with 1 time its weight of hydrogen peroxide at 20 volumes and whose pH is 3.

The extemporaneous mixture thus produced was applied to gray hair with 90% of white hair at a rate of 10 g per 1 g of hair. After 30 minutes of exposure at 27 ° C., the hair was then rinsed, washed with standard shampoo and dried.

Results Capillary staining was evaluated visually. We obtain a brown hair color with red reflection.

Claims (10)

REVENDICATIONS1. Coloring composition for keratinous fibers comprising, in a medium which is suitable for dyeing keratinous fibers: one or more oxidation bases chosen from the compound of formula (I) or its addition salts with an acid, H HO and one or more 4,5-diaminopyrazole compounds of formula (II) or their addition salts with an acid or a base, in which: R 1, R 2, R 3, R 4 and R 5 and R6, which may be identical or different, represent a hydrogen atom; a C1-C6 alkyl radical which is unsubstituted or substituted with at least one substituent selected from OR, NHR, NRR ', SR, SOR, SO2R, COR, COOH, CONH2, CONHR, CONRR', PO (OH) 2, SH, S03X, a non-cationic heterocycle, Cl, Br or I, X denoting a hydrogen atom, Na, K, or NH4, and R and R ', which may be identical or different, representing a C1-C4 alkyl or alkenyl; a C2-C4 hydroxyalkyl radical; a C2-C4 aminoalkyl radical; a phenyl radical; a phenyl radical substituted by a halogen atom or a C1-C4 alkyl, C1-C4 alkoxy, nitro, trifluoromethyl, amino or C1-C4 alkylamino radical; a benzyl radical; a benzyl radical substituted with a halogen atom or with a C1-C4 alkyl, C1-C4 alkoxy, methylenedioxy or amino radical; a radical ## STR2 ## wherein m and n are integers, identical or different, between 0 and 3 inclusively, X represents an oxygen atom or the group NH, Y represents a hydrogen atom or a C1-C4 alkyl radical, and Z represents a methyl radical when n is 0, or Z represents a C1-C4 alkyl radical, a group OR or NR "R" 'when n is greater than or equal to 1, R "and R" ', which may be identical or different, denoting a hydrogen atom or a C1-C4 alkyl radical; or R5 forms with the nitrogen atom of the NR3R4 group at the 5-position a heterocycle comprising at least 4 members, at least one of R 1, R 2, R 3 and R 4 represents a hydrogen atom. 2. Composition according to claim 1 wherein the compound of formula (II) is such that R6 is hydrogen, R1, R2, R3, R4 represents a hydrogen atom or a C1-C4 alkyl radical and R5 is an alkyl, hydroxyalkyl or alkoxyalkyl radical and C1-C4. 3. Composition according to claims 1 or 2 wherein the compound of formula (II) is 4,5-diamino-1- (2-hydroxyethyl) -1H-pyrazole and its salts, such as the sulfate of 4,5 -diamino-1- (2-hydroxyethyl) -1H-pyrazole. 4. Composition according to the preceding claim, characterized in that the content of compound of formula (I) or (II) is each of between 0.001 to 10% by weight of the total weight of the dye composition. 5. Composition according to any one of the preceding claims, characterized in that it contains one or more couplers chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. 6. Composition according to the preceding claim, characterized in that the coupler or couplers generally represent an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%. 7. Composition according to any one of the preceding claims, characterized in that it contains one or more oxidizing agents. 8. Composition according to the preceding claim, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes and preferably the hydrogen peroxide. 9. A process for dyeing keratinous fibers, wherein the composition as defined in any one of claims 1 to 6 is applied to the keratinous fibers in the presence of one or more oxidizing agents for a time sufficient to develop the desired coloration. . 10. A multi-compartment device in which a first compartment contains a dye composition as defined in any one of claims 1 to 6 and a second compartment contains one or more oxidizing agents.