FR2945739A1 - Composition useful for dyeing keratin fibers comprises in a medium, specific secondary paraphenylenediamine oxidation base or its addition salt with acid, and heterocyclic oxidation base e.g. pyrazolopyridine compounds with acid/base - Google Patents

Abstract

A composition comprises: in a medium suitable for dyeing keratin fibers: at least one oxidation base selected from 2-[[2-(4-amino-phenylamino)-ethyl]-(2-hydroxy-ethyl)-amino]-ethanol or its addition salt with an acid, and at least one heterocyclic oxidation base selected from pyrazolopyridine compounds; diamino-N,N-dihydropyrazolone compound; 4,5-diaminopyrazole compound or their addition salts with an acid or a base. A composition comprises: in a medium suitable for dyeing keratin fibers: at least one oxidation base selected from 2-[[2-(4-amino-phenylamino)-ethyl]-(2-hydroxy-ethyl)-amino]-ethanol (I) or its addition salt with an acid, and at least one heterocyclic oxidation base selected from pyrazolopyridine compound of formula (II) or (III); diamino-N,N-dihydropyrazolone compound of formula (IV); 4,5-diaminopyrazole compound of formula (V) or their addition salts with an acid or a base. R 1-R 5H or halo, -NHSO 3H, OH, 1-4C alkyl, 1-4C alkoxy, 1-4c alkylthio, mono (1-4C)alkylamino, di(1-4C)alkylamino (in which the two alkyl groups can, jointly with the nitrogen atom to which they are bonded, form a ring which can be interrupted by at least one N, O or S), heterocycle, nitro, phenyl, carbonyl, (1-4C) alkoxycarbonyl, carboxamido, cyano, amino, sulfonyl, -CO 2H, -SO 3H, -PO 3H 2, -PO 4H 2, or group of formula -Q 1-C(=R 1a)-Y 1(i); R 1aO or N; Q 1O or NH or NH (1-4C) alkyl group; Y 1OH, amino, 1-4C alkyl, (1-4C) alkoxy, (1-4C) alkylamino or di(1-4C)alkylamino; Z 1,Z 2simple covalent bond or divalent radical selected from -S-, -SO- or -SO 2-, -O(CH 2) p- or -NR 6'(CH 2) q(C 6H 4) t-; R 6' : H or 1-6C alkyl (optionally substituted by OH); p,q : 0-6; t : 0 or 1; R 1',R 2' : H, 1-10C alky (optionally substituted and optionally interrupted by heteroatom selected from O, N, Si, S, SO or SO 2), halo, SO 3H, optionally saturated or aromatic and optionally substituted 5- to 8-membered ring (optionally comprising at least one heteroatom selected from N, O, S, SO 2or -CO-, it being possible for the ring to be cationic and/or substituted with a cationic radical), -N +>R 17R 18R 19or T 1; T 1optionally substituted 1-6C alkylcarbonyl, -O-CO-R, -CO-O-R, NR-CO-R' or -CO-NRR'; R,R' : H or optionally substituted 1-6C alkyl; R 17-R 19linear or branched 1-5C alkyl (optionally substituted by OH); R 3',R 4',R 5' : H, OH, 1-6C alkoxy, 1-6C alkylthio, amino, monoalkylamino, 1-6C dialkylamino (in which the alkyl radical can form, with the nitrogen atom to which they are attached, optionally saturated and optionally aromatic 5- to 8-membered heterocycle which can include at least one heteroatom selected from N, O, S, SO 2or CO, it being possible for the heterocycle to be cationic and/or substituted with a cationic radical), 1-6C alkyl-carbonyl (optionally substituted), -O-CO-R, -CO-O-R, NR-CO-R' or -CO-NRR', halo, -NHSO 3H, 1-4C alkyl (optionally substituted) or optionally saturated or optionally aromatic and optionally substituted carbon ring;or R 3'+R 4'+R 5' : ring (optionally saturated); X : ion or group of ions which makes it possible to provide the electronegativity of derivative of formula (III); R a',R b' : T 2; R c',R d' : H or T 2; T 2linear or branched, 1-10C (preferably 1-6C) alkyl (optionally substituted by OR 15a, NR 16aR 17a, carboxyl, sulfonic, CONR 16aR 17acarboxamido, SO 2NR 16R 17sulfonamido, heteroaryl or aryl (all optionally substituted by t 1)), aryl (optionally substituted by t 1); or 5- or 6-membered heteroaryl (optionally substituted by 1-4C alkyl or 1-2C alkoxy); t 1(1-4C) alkyl, OH, 1-2C alkoxy, amino or (di)(1-2C)alkylamino; R 15aT 3; R 16a,R 17aT 3or T 4; T 3H, linear or branched 1-4C alkyl (optionally substituted by OH, 1-2C alkoxy, CONR 18R 19carboxamido, SO 2R 18sulfonyl or aryl (optionally substituted by t 1)) or aryl (optionally substituted by t 1); T 4CONR 18R 19carboxamido or SO 2R 18sulfonyl; R 18,R 19H, linear or branched 1-4C alkyl (optionally substituted by OH or 1-2C alkoxy);or NR a',R b' : T 5;or NR c'R d' : T 5or T 6; T 5optionally saturated 5- to 7-membered heterocycle (optionally substituted by halo, amino, (di)(1-4C) alkylamino, OH, carboxyl, carboxamido or (1-2C) alkoxy or 1-4C alkyl (optionally substituted by OH, amino, (di) alkylamino, alkoxy, carboxyl or sulfonyl); T 65- or 7-membered heterocycle (where the carbon atom is replaced with optionally substituted O or N atom); R 21-R 26H or 1-6C alkyl (optionally substituted by OR e', NHR e', NR e'R f', SR e', SOR e', SO 2R e', COR e', COOH, CONH 2, CONHR e', CONR e'R f', PO(OH) 2, SH, SO 3X 1, non cationic heterocycle, Cl, Br or I); X 1H, Na, K, or NH 4; R e',R f' : 2-4C alkyl or 2-4C alkenyl; 2-4C aminoalkyl; phenyl (optionally substituted by halo or 1-4C alkoxy), 1-4C alkyl, nitro, trifluoromethyl, amino or 1-4C alkylamino; benzyl radical (optionally substituted by halo or 1-4C alkyl), 1-4C alkoxy, methylenedioxy or amino; -(CH 2) m-X 2-(CH) n(Y 2)-Z 1(ii); m,n : 0 or 3; X 2O or NH; Y 2H or 1-4C alkyl; Z 1methyl, OR g' or NR h'R i'; R g',R h',R i' : H or 1-4C alkyl;or NR 5NR 3R 4in position 5 heterocyclic group having at least 4 members. Provided that Z 1is divalent radical -S-, -SO- or -SO 2-, when R 1' is a methyl radical; when Z 1and Z 2, represents a covalent bond, then R 1' and R 2' can also represent T 1; at least one of the groups R 1' and R 2' represents a cationic radical; when n is 0, then Z 1is 1-4C alkyl; when n is >= 1, then Z 1is OR g' or NR h'R i'; at least one of R 21, R 22, R 23and R 24is H. Independent claims are included for the following: (1) dyeing keratin fibers involving: applying the composition to the keratin fibers in the presence of at least one oxidizing agent for a time sufficient to develop the desired coloring; and (2) multicompartment device comprises a first compartment containing the dyeing composition and a second compartment containing at least one oxidizing agent. [Image].

Description

The invention relates to a dye composition comprising at least one particular para-phenylenediamine secondary oxidation base and a pyrazolopyridine oxidation base, as well as to a dyeing composition comprising at least one secondary para-phenylenediamine oxidation base and a pyrazolopyridine oxidation base, and also to a pyrazolopyridine oxidation base. 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 keratinous fibers, dyeing compositions using a pyrazolopyridine 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. 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, H HO and one or more pyrazolopyridine oxidation bases chosen from the bases of formula (II) or (III) or their addition salts with an acid or with a base 1 ~ NNR R4 7 R5 in which: R 1, R 2, R 3, R 4 and R 5, which may be identical or different, represent a hydrogen or halogen atom; a radical -NHSO3H; a hydroxyl radical; a (C 1 -C 4) alkyl radical; a (C 1 -C 4) alkoxy radical; a (C 1 -C 4) alkylthio radical; mono (C 1 -C 4) alkylamino; a di (C 1 -C 4) alkylamino radical in which the two alkyl groups can, together with the nitrogen atom to which they are bonded, form a ring which can be interrupted by one or more nitrogen, oxygen or sulfur; a heterocycle; a nitro radical; a phenyl radical; a carbonyl radical; a (C 1 -C 4) alkoxycarbonyl radical; a carboxamido radical; a cyano radical; an amino radical; a sulfonyl radical; a radical -CO2H, a radical -SO3H; a radical -PO3H2; a radical -PO4H2; or a group: R "'QY in which R"' represents an oxygen or nitrogen atom, Q represents an oxygen atom, an NH or NH (C 1 -C 4) alkyl group, and Y represents a radical hydroxyl, amino, C 1 -C 4 alkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) alkylamino, or di (C 1 -C 4) alkylamino. Wherein Z1 and Z2 independently represent a single covalent bond, a divalent radical selected from a -O (CH2) p radical, where p denotes an integer ranging from 0 to 6; a radical --NR'6 (CH2) q (C6H4) t0, q denoting an integer ranging from 0 to 6 and t denoting 0 or 1. R'6 represents a hydrogen atom, an optionally substituted C1-C6 alkyl radical; substituted with one or more hydroxy groups. Z1 can also represent a divalent radical ûS-, -SO-, -SO2- when R ', is a methyl radical, • R'1 and R'2 represent independently: - a hydrogen - a C1-C10 alkyl radical optionally substituted and optionally interrupted by a heteroatom or a group selected from O, N, Si, S, SO, SO 2, a halogen, an SO 3 H radical, a 5 to 8-membered ring, substituted or unsubstituted, saturated, unsaturated or aromatic, optionally containing one or more heteroatoms or groups selected from N, O, S, SO2, -CO-, the ring being cationic and / or substituted with a cationic radical, - a moiety ùN + R17R18R19, R17, R19 and R19 being linear or branched C 1 -C 5 alkyl optionally substituted with one or more hydroxy groups. When Z1 and Z2 respectively represent a covalent bond, then R'1 respectively R'2 may also represent a radical: C1-C6alkylcarbonyl optionally substituted with -0-00-R, -CO-OR, NR-CO-R 'or in which R and R 'independently represent a hydrogen atom or an optionally substituted C1-C6 alkyl radical; R'3, R'4 and R'5, which may be identical or different, represent an atom hydrogen, - a hydroxyl radical, - a C1-C6 alkoxy radical, - a C1-C6 alkylthio radical, - an amino radical, - a monoalkylamino radical, - a C1-C6 dialkylamino radical in which the alkyl radicals. can form with the nitrogen atom to which they are attached a 5-8 membered heterocycle, saturated, unsaturated, aromatic or not, which may contain one or more heteroatoms or groups selected from N, O, S, SO2, CO, l heterocycle which may be cationic, and / or substituted with a cationic radical, an alkylcarbo radical C1-C6 nyl, optionally substituted ,. a radical -O-O-R, CO-OR, NR-CO-R 'or CO-NRR' with R and R 'as defined previously, a halogen, a radical -NHSO3H, an optionally substituted C1-C4 alkyl radical ,. a saturated, unsaturated or aromatic carbon ring, optionally substituted. R'3, R'4 and R'5 may form, two by two, a partially saturated or non-saturated ring; X represents an ion or group of ions making it possible to ensure the electronegativity of the derivative of formula (II), with the proviso that at least one of the groups R ', and R'2 represents a cationic radical. 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 pyrazolopyridine oxidation bases. chosen from oxidation bases of formula (II) or (III) or their addition salts with an acid or with 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. to the various attacks that hair can undergo such as shampoos, sweat, permanent deformations and light .. It should be noted that in what follows, and unless otherwise indicated, the limits of a domain of values are included in this area. The compounds of formula (I) (II) or (III) may be in the form of addition salts chosen in particular from acid addition salts such as hydrochlorides, hydrobromides, sulphates, citrates, succins , tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The compounds of formula (I) (II) or (III) 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%. In the compounds of formula (II) to (III) above, and unless otherwise indicated, the alkyl expression used for the alkyl radicals as well as for the groups comprising an alkyl part, signifies a linear or branched carbon chain comprising 1 to 4 carbon atoms, substituted or unsubstituted by one or more heterocycles, or by one or more phenyl groups or by one or more groups selected from halogen atoms such as chlorine, bromine, iodine and fluorine ; hydroxyl, alkoxy, amino, carbonyl, carboxamido, sulphonyl, -CO2H, -SO3H, -PO3H2, -PO4H2, -NHSO3H, sulphonamide, (C1-C4) alkylamino, trialkyl (C1-C4) ammonium radicals, or by a dialkyl radical (C1-C4) amino in which the two alkyl groups can form, together with the nitrogen atom of said dialkyl (C 1 -C 4) amino group to which they are attached, a ring which can be interrupted by a or several atoms of nitrogen, oxygen or sulfur. Similarly, according to the invention, the alkoxy expression used for the alkoxy radicals as well as for the groups comprising an alkoxy part, signifies a linear or branched O-carbon chain containing from 1 to 4 carbon, substituted or unsubstituted by one or more groups selected from heterocycles; halogen atoms such as chlorine, bromine, iodine and fluorine; hydroxyl, amino, carbonyl, carboxamido, sulphonyl, -CO2H, -SO3H, -PO3H2, -PO4H2, -NHSO3H, sulphonamide, (C1-C4) alkylamino, trialkyl (C1-C4) ammonium radicals, or else by a (C 1 -C 4) dialkylamino radical in which the two alkyl groups can form, together with the nitrogen atom of said dialkyl (C 1 -C 4) amino group to which they are attached, a ring which can be interrupted by one or several atoms of nitrogen, oxygen or sulfur. According to the invention, the term "heterocycle" means an aromatic or non-aromatic ring containing 5, 6, 7 or 8 vertices, and from 1 to 3 heteroatoms chosen from nitrogen, sulfur and oxygen atoms. These heterocycles may be fused to other heterocycles or to a phenyl group. They may be substituted by a halogen atom; a (C 1 -C 4) alkyl radical; a (C 1 -C 4) alkoxy radical; a hydroxyl radical; an amino radical; a (C 1 -C 4) alkylamino radical; di (C 1 -C 4) alkylamino wherein the two alkyl groups together with the nitrogen atom to which they are attached form a ring which can be interrupted by one or more nitrogen, oxygen or sulfur atoms. These heterocycles may, in addition, be quaternized with a (C 1 -C 4) alkyl radical. Among these optionally fused heterocycles, there may be mentioned by way of example the rings: thiadiazole, triazole, isoxazole, oxazole, azaphosphole, thiazole, isothiazole, imidazole, pyrazole, triazine, thiazine, pyrazine, pyridazine, pyrimidine, pyridine, diazepine, oxazepine, benzotriazole, benzoxazole, benzimidazole, benzothiazole, morpholine, piperidine, piperazine, azetidine, pyrrolidine, aziridine, 3- (2-hydroxyethyl) benzothiazol-3-ium, and 1- (2-hydroxyethyl) pyridinium. According to the invention, phenyl is understood to mean a phenyl radical which is unsubstituted or substituted with one or more cyano, carbonyl, carboxamido, sulphonyl, -CO 2 H, -SO 3 H, -PO 3 H 2, -PO 4 H 2, hydroxyl, amino or monoalkyl (C -C4) amino, or dialkyl (C1-C4) amino wherein the two alkyl groups can form, together with the nitrogen atom of said dialkyl (C 1 -C 4) amino group to which they are attached, a ring which can be interrupted by one or more atoms of nitrogen, oxygen or sulfur. Among the QY groups, there may be mentioned the acetamide, dimethylurea, 0-methylcarbamate, methylcarbonate, N-dimethylcarbamate and the esters groups. Among the compounds of formula (II) above, 3-amino pyrazolo is preferred. - [1,5-a] pyridines corresponding to the following sub-formula, and their addition salts with an acid or with a base: in which: R 1, R 2, R 3, which may be identical or different, represent an atom of hydrogen, halogen, a hydroxyl radical, a (C 1 -C 4) alkyl radical, a (C 1 -C 4) alkylthio radical, a (C 1 -C 4) alkoxy radical, a -NHSO 3 H radical or an amino radical; a (C 1 -C 4) alkylamino radical; a di (C 1 -C 4) alkylamino radical in which the two alkyl groups may together with the nitrogen atom to which they are attached form a ring which may be interrupted by one or more nitrogen, oxygen or sulfur atoms, a heterocycle as defined above, a sulphonamide radical, a carbonyl radical, a radical alkoxy (C 1 -C 4) carbonyl, a carboxamido radical, or a group of formula: R "QY in which R" 'represents an oxygen or nitrogen atom, Q represents an oxygen atom, a grouping NH or NH (C 1 -C 4) alkyl, and Y represents a hydroxyl, amino, C 1 -C 4 alkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) alkylamino, or di (C 1 -C 4) radical; alkylamino. Among the 3-amino pyrazolo [1,5-a] pyridines of formula (II), which may be used as oxidation bases in the dyeing compositions in accordance with the invention, mention may be made especially 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-Amino-pyrazolo [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-diamino-pyrazolo [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] pyridine-7-ol; 2-methoxy-6,7-dimethylpyrazolo [1,5-a] pyridin-3-amine; 2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethanol; 4-ethyl-2-methoxy-7-methylpyrazolo [1,5-a] pyridin-3-amine hydrochloride; 1- (3-aminopyrazolo [1,5-a] pyridin-2-yl) pyrrolidin-3-ol; 2,2 '- [(3-aminopyrazolo [1,5-a] pyridin-2-yl) imino] diethanol; 2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) amino] ethanol; N2- (2-pyridin-3-ylethyl) pyrazolo [1,5-a] pyridine-2,3-diamine; and their addition with an acid or with a base. For the most part, the 3-amino pyrazolo [1,5-a] pyridines of formula (II) are compounds known in the pharmaceutical field, and are described in particular in US Patent 5,457,200. These compounds can be prepared according to synthetic methods well known in the literature and as described, for example, in US Pat. No. 5,457,200. By ring or cationic heterocycle is meant a ring containing one or more quaternary ammonium groups. By way of example of radicals of the -N + R17R18R19 type, mention may be made of the trimethylammonium, triethylammonium, dimethylethylammonium, diethylmethylammonium, diisopropylmethylammonium, diethylpropylammonium, betahydroxyethyl diethylammonium, di (betahydroxyethyl) methylammonium, tri (betahydroxyethyl) ammonium. As an example of cationic heterocycle, there may be mentioned imidazolium heterocycles, pyridiniums, piperaziniums, pyrrolidiniums, morpholiniums, pyrimidiniums, thiazoliums, benzimidazoliums, benzothiazoliums, oxazoliums, benzotriazoliums, pyrazoliums, triazoliums, benzoxazoliums. By way of example of cationic heterocycle, mention may be made of imidazoliums, pyridiniums, piperaziniums, pyrrolidiniums, morpholiniums, pyrimidiniums, thiazoliums, benzimidazoliums, benzothiazoliums, oxazoliums, benzotriazoliums, pyrazoliums, triazoliums, benzoxazoliums. The compounds of formula (III) may optionally be salified with strong mineral acids such as, for example, HCl, HBr, HI, H 2 SO 4, H 3 PO 4, or organic acids such as, for example, acetic, lactic, tartaric or citric acid. or succinic, benzenesulfonic, para-toluenesulfonic, formic, methanesulfonic. If they have anionic groups such as the groups -CO2H, -SO3H, -PO3H2, -PO4H2, the compounds of formulas (II) or (III) may be salified with hydroxides of alkali or alkaline earth metals such as sodium hydroxide or potash, by ammonia, by organic amines. 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.

In the context of the invention, the term "derivative of formula (III)" means any mesomeric or isomeric forms. By way of examples of derivatives of formula (III), mention may be made of the following compounds in which X- is as defined previously: NH 2 NH / NON X salt of [2- (3-Amino-pyrazolo [1.5- a] pyridin-2-ylamino) -ethyl] -trimethylammonium 3- (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -1-methyl-3H-imidazol-1-ium salt NH 2 N- [N- [N-] + X] NH 2 [2- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] -ethyl-dimethyl-ammonium salt NH / NON X- + [2- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] - (2-hydroxy-ethyl) -dimethyl-ammonium NH 2 -NH 2 OH NH 2 N-N- [N- [3- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -propyl] -trimethyl-ammonium NH 2 / NO N-N-. [4- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -butyl] -trimethyl-ammonium NH 2 / NO N-1 salt. [5- (3-Amino) pyrazolo [1,5-a] pyridin-2-ylamino) -pentyl] -trimethylammonium NH 2 NH 2 NXN 3- [2- (3-Amino-pyrazolo [1,5-a] pyridine -2-ylamino) -ethyl] -1-methyl-3H-imidazol-1-ium NH 2 \ NN-N- [3- (3-Ami) salt N-pyrazolo [1,5-a] pyridin-2-ylamino) -propyl] -1-methyl-3H-imidazol-1-ium NH 2 3- [3- (3-Amino-pyrazolo) salt a] pyridin-2-ylamino) -propyl] -1- (2-hydroxy-ethyl) -3H-imidazol-1-ium / NH / NON / N / NX 3- [2- (3-Amino) salt pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -1- (2-hydroxy-ethyl) -3H-imidazol-1-ium NH 2 / ~ OH X NH 2 / NO ~ N ~ Salt of 1 - {2 - [(3-Aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} -1-methylpyrrolidinium NH 2 + / NO N / X 1- {2 - [(3-Aminopyrazolo [1- [2 - [(3-aminopyrazolo 1,5-a] pyridin-2-yl) oxy] ethyl} -1-methylpiperidinium NH2 / NO / \ OX- 4- {2 - [(3-aminopyrazolo [1,5-a] pyridin-2- salt yl) oxy] ethyl} -4-methylmorpholin-4-ium NH2 / NO N + / X {2 - [(3-Aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} trimethyl- ammonium NH2 / NO ~ N + / \ X {2 - [(3-Aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} -diisopropyl-methyl-ammonium salt NH2 XN NN S el 1- (1- (3-Aminopyrazolo [1,5-a] pyridin-2-yl) -1-methylpyrrolidinium yl) -pyrrolidin-3-yl] -timethyl-ammonium NH2 / X / NO 1- [3- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -propyl] -1-methylpiperidinium NH 2 / ù 1 + XN N- 4- Salt salt (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -1,1-dimethyl-piperazin-1-ium NN ~ / NH₂ / X / NH \ / NO N / - / / + NN 4- [2- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] -1,1-dimethyl-piperazin-1-ium NH 2 / X / NH 4 salt / NO N / - \ NN / \ _ / 4- [2- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] -1-methyl-1-propyl- 4- (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -1- (2-hydroxy-ethyl) piperazin 4- (3-amino-pyrazolo [1,5-a] pyridin-2-yl) -1-piperazin-1-ium NH 2 X NN -1-ium NH2 / NO NH N + • / \ X [4- (3-Amino-pyrazolo [1,5-a] pyridin-2-ylamino) -phenyl] -trimethyl-ammonium salt NH2 O \\ NO ~, ~ N / ~ N x- 3- [3- (3-Amino-pyrazolo [1,5-a] pyridin-2-yloxy) -propyl] -1-methyl-3H-imidazol-1-ium salt NH2 / N + / NO 4- (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -1,1-dimethyl- [1,4] diazepan-1-ium NH 2 NH + ~ N- [2- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] -trimethylammonium NH 2 - / / + X Se salt 4- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yl) -1,1-dimethyl-piperazin-1-ium NN / N-NH 2 N / - 4- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yl) -1- (2-hydroxy-ethyl) -1-methyl-piperazin salt -1-ium NH 2 N + X N + N% [1- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yl) -pyrrolidin-3-yl salt ] -trimethylammonium NH2 N NJ X 1- (3-amino-6,7-dimethylpyrazolo [1,5-a] pyridin-2-yl) -1-methylpyrrolidinium salt [1- (3-Amino) 6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yl) -pyrrolidin-3-yl] - (2-hydroxyethyl) -dimethylammonium NH 2 N -N + X OH [2- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -pyrrolidin-3-yl} -trimethylammonium ~ / NO NH 2 / N -NH 2 X 1- {2 - [(3-Amino-6,7-dimethylpyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} -1-methylpyrrolidinium salt NH 2 / ~ / NO * Salt 1- {2 - [(3-Amino-6,7-dimethylpyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} -1-methylpiperidinium NH 2 - / NO 4 - 4- [(3-amino-6,7-dimethylpyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} -4-methylmorphol in-4- ium ~ / NON-NH 2 ù X {2 - [(3-amino-6,7-dimethylpyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} trimethyl ammonium NH 2 / salt O ~ / NO Salt of {2 - [(3-amino-6,7-dimethylpyrazolo [1,5-a] pyridin-2-yl) oxy] ethyl} -diisopropyl-methyl-ammonium NH 2 / ~ / NO NH N + x- [3- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-ylamino) -propyl] -trimethyl-ammonium salt NH 2 O N + x- (3-Amino-6,7-dimethyl-pyrazolo [1,5-a] pyridin-2-yloxy) -propyl] -trimethyl-ammonium NH 2 NO 2 + X [3- (3-Amino-7) salt, 8-Dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yloxy) -propyl] trimethylammonium NH 2 H + N + N + 1 x Salt of {2 - [( 3-Amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] ethyl] trimethylammonium / NH 2 H + NO N ~~ i x {3 - [(3-Amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] propyl} -trimethylammonium NH 2 salt salt ## STR5 ## N, NN of N, N + N, N, N- {2 - [(3-amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2 - yl) amino] ethyl-3-methyl-1H-imidazol-3-ium Salt NH2 N ~ / N, / ~ IN + ~ NON x 1- {3 - [(3-amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] propyl} -3-methyl-1H-imidazol-3-ium salt NH2H NO x NN {1- {2 - [(3-amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1] 5-a] pyridin-2-yl) amino] ethyl-1-methylpyrrolidinium NH 2 H + N + N-N + 1- {2 - [(3-amino-7,8-dihydro-6H-cyclopenta) salt [e] pyrazolo [1,5-a] pyridin-2-yl) amino] ethyl} -1-methylpiperidinium NH 2 / i H NO NN X 4- {2 - [(3-amino-7,8-dihydro) salt 6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] ethyl} -4-methylmorpholin-4-ium NH 2 X / 1H NO N ~ N + N + 2 - [( 3-amino-7,8-dihydro-6H-cyclopenta [e] pyrazolo [1,5-a] pyridin-2-yl) amino] ethyl} -diisopropyl-methyl-ammonium NH 2 NN \N + X-Salt of [3] - (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-ylamino) -propyl] -trimethyl-ammonium NH 2 NH / NON ~ N - - [2- (3-Amino-4) salt dimethylamino-pyrazolo [1,5-a] pyridin-2-ylamino) -ethyl] -trimethylammonium NH 2 N + N N N / N 4- (3-Amino-4-dimethylamino-pyrazolo) salt 1,5-a] pyridin-2-yl) -1-methyl -piperazin-1-ium NH2 + [1- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yl) -pyrrolidin-3-yl] -trimethylammonium-ammonium salt N1N X NH2 / N NO + N ~ + X ~ N ù 3- [2- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -1-methyl-3H-imidazole salt -1-ium NH2 / NON _ X [2- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -trimethyl-ammonium salt NH2 OX- / NO N-1- {1- [2- (3-Amino-4-dimethylamino-pyrazolo [1,5-a] pyridin-2-yloxy) -ethyl] -pyrrolidin-3-yl} -trimethylammonium salt X-NH2 / NON Sp (3-Amino-2-methanesulfonyl-pyrazolo [1,5-a] pyridin-4-yl) -trimethylammonium-x-NH2 salt (3-Amino-2-methoxy-pyrazolo salt) [1,5-a] pyridin-4-yl) -trimethylammonium / NO The nature of the counterion is not critical on the dye power of the compounds of formula (III). When R '1 or R' 2 denotes a heterocycle, this heterocycle is preferably a cationic heterocycle or a heterocycle substituted with a cationic radical. By way of example, mention may be made of imidazoles substituted with a quaternary ammonium radical or imidazoliums, piperazines substituted with a quaternary ammonium radical or piperaziniums, pyrrolidines substituted with a quaternary ammonium radical or pyrrolidiniums, diazepanes substituted with a quaternary ammonium radical or diazepaniums. According to a different embodiment, R'1 or R'2 represent a group -N + R17R18R19, R17, R19 and R19 being linear or branched C1-C5 alkyls optionally substituted with one or more hydroxyl groups, such as trialkylammonium, tri (hydroxyalkyl) ammonium, hydroxyalkyl-dialkylammonium or di (hydroxyalkyl) alkylammonium. The radicals R'3, R'4 and R'5 independently may be a hydrogen atom, a C1-C4 alkyl radical may be substituted. By way of example, mention may be made of methyl, ethyl, hydroxyethyl, aminoethyl, propyl and butyl radicals. According to a particular embodiment, R'3, R'4 and R'5 independently represent a hydrogen atom or a C1-C4 alkyl radical. According to a particular embodiment, R'4 and R'5 together form a partially saturated or unsaturated 5- or 8-membered ring, in particular an optionally substituted cyclopentene or cyclohexene. According to a particular embodiment, the compound of formula (III) corresponds to the following formula (III '): XZ \ 1 R'1 R'5 in which Z1, R'1, R'3, R'4 and R 5 are as previously defined. According to a particular embodiment of this formula, Z1 represents a covalent bond, a radical NRR6 (CH2) q or a radical O (CH2) p and R'1 is a cationic radical. By these compounds, 2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) oxy] ethanol hydrochloride, 4 - [(3-aminopyrazolo [1,5-a] chloride) is preferred. ] pyridin-2-yl-1,1-dimethylpiperazin-1-ium hydrochloride, 1- {2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) amino] ethyl chloride - 3-methyl-1H-imidazol-3-iumhydrochloride, 2 - [(3-aminopyrazolo [1,5-a] pyridin-2-yl) oxy] -N, N, N-trimethylethanaminium hydrochloride chloride Composition The dyeing agent according to the invention may contain and preferably contains one or more couplers conventionally used for dyeing keratinous fibers, Among these couplers, mention may be made in particular of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, Heterocyclic couplers and their addition salts By way of example of a coupler, mention may be made of 2-methyl-5-aminophenol, 5-N- (13-hydroxyethyl) amino-2-methylphenol and 6-chloro-2. -methyl-5-aminophenol, 3-amino phen ol, 2,4-dichloro-3-aminophenol, 5-amino-4-chloro-o-cresol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 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-methylindole, 2-amino-3-hydroxy-pyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 2,6-dihydroxy-3-4-dimethylpyridine, 3-amino-2-methylamino 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), (II) and (III) or of their salts.

By way of example, these additional oxidation bases are chosen from the para-phenylenediamines different from the compound of formula (I) or its salts, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho- aminophenols, the heterocyclic bases different from the oxidation bases of formula (II) and (III) 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, 13-hydroxyethyl) para-phenylenediamine, N- ((3-y-dihydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine, 2-hydroxy-2-hydroxyethyloxy-para-phenylenediamine, 2-yl-acetylaminoethyloxy para phenylenediamine, N- (13-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl para-phenylenediamine, 2- (3-hydroxyethylamino 5-amino toluene, 3-hydroxy-1- (4 ') 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 paraphenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (3-hydroxyethyl) para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-13-acetylaminoethyloxy para-phenylenediamine, and their addition salts with an acid are particularly preferred. Among the bis-phenylalkylenediamines, N, N'-bis ((3-hydroxyethyl) N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, for example, is 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- (3-hydroxyethylaminomethyl) phenol, 4-amino 2-fluoro 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.

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-methylpyrazole, 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- meth 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 with an acid. 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 (IV): ## 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 chosen.

among the compound of formula (I) or its addition salts with an acid, optionally one or more additional oxidation bases different from the compounds of formula (I) or formulas (II) or (III) or their salts, and optionally one or more couplers, a second composition comprising the oxidation base (s) of formula (II) or (III) 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 (III) or their salts, optionally one or more additional oxidation bases different from the compounds of formula (I) or of formula (II) or (III) 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. 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 subject of the invention is also a multi-compartment device or "kit" for 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 compounds of formula (I) or its addition salts with an acid and one or more oxidation bases chosen from compounds of formula (II) or (III) 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), (II) or (III) or their addition salts with an acid or a base optionally one or more couplers and a second compartment containing a composition comprising one or more oxidation bases chosen from the compounds of formula (II) or (III) or their addition salts with an acid or a base and optionally 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. 29 EXAMPLES

EXAMPLES OF DYEING EXAMPLE 1 Compositions C1 and C2 comprise the following ingredients Cl C2 2 - [{2 - [(4-Aminophenyl) amino] ethyl} (2- (0.01 mol) 0.0029 hydroxyethyl) amino] ethanol trichlorhydrate moles 4- (3- Aminopyrazolo [1,5-a] pyridin-2-yl) -1,1 -0,06-dimethylpiperazin-1-ium chloride dihydrochloride moles 2 - [(3-Aminopyrazolo [1,5-a] pyridin-2-yl) oxy ] ethanol - 0.0122 hydrochloride moles 2,4-Diaminophenoxyethanol dihydrochloride 0.001 - moles 6-Chloro-2-methyl-5-amino phenol 0.011 - moles 1-Methyl-2-hydroxy-4-amino-benzene - 0.0037 moles 2-Methyl 5- (2-hydroxyethyl) amino phenol 0.005 0.0114 moles moles Oleyl alcohol polyglycerolated with 2 moles of glycerol 4 g MA 4 g MA Oleic alcohol polyglycerolated with 4 moles of glycerol 6 g MA 6 g MA (78% MA) Oleic acid 3 g 3 g Oleic amine 2 EO sold under 7 g MA 7 g MA denomination ETHOMEEN 012 by the company AKZO Laurylamino diethylaminopropyl succinamate, 3 g MA 3 g MA sodium salt 55% MA Oleic alcohol 5 g 5 g Monoethanolamide of alkyl acid (C13 / C15 70/30, 50 10 g MA 10 g MA% linear) ether carboxylic (2OE) Propylene glycol 9.5 g 9.5 g Ethyl alcohol 5 g 5 g Héxylene glycol 9.3 g 9.3 g Sodium metabisulfite in 35% aqueous solution 0.455 g 0.455 g MAMA MA Ammonium acetate 0.8 g 0.8 g Antioxidant, sequestering Qs Qs Fragrance, preservative Qs Qs Ammonia at 20% NH3 10.2 g 10.2 g Demineralized water qs 100 g qs 100 g 10 30 Mode of application

Each composition is diluted extemporaneously with 1 time its weight of oxygenated water at 20 volumes and whose pH is 3.

Each of the extemporaneous mixtures 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 to room temperature, the hair was then rinsed, washed with standard shampoo and dried.

Results The capillary coloration obtained was evaluated visually. We obtain the following colorations Composition color Reflet Cl Brown Violine Cendré C2 Dark Blonde Red 20

Claims (10)

REVENDICATIONS1. Coloring composition of keratinous fibers comprising, in a medium 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 HON and one or more oxidation bases selected from compounds of formula (II) or (III) or their addition salts with an acid or a base R 2 NH 2 NN, L R 1 R 7 in which: R 1, R 2, R 3 R4 and R5, which may be identical or different, represent a hydrogen or halogen atom; a radical -NHSO3H; a hydroxyl radical; a (C 1 -C 4) alkyl radical; a (C 1 -C 4) alkoxy radical; a (C 1 -C 4) alkylthio radical; mono (C 1 -C 4) alkylamino; a di (C 1 -C 4) alkylamino radical in which the two alkyl groups can, together with the nitrogen atom to which they are bonded, form a ring which can be interrupted by one or more nitrogen, oxygen or sulfur; a heterocycle; a nitro radical; a phenyl radical; a carbonyl radical; a (C 1 -C 4) alkoxycarbonyl radical; a carboxamido radical; a cyano radical; an amino radical; a sulfonyl radical; a radical -CO2H, a radical -SO3H; a radical -PO3H2; a radical -PO4H2; or a group: R "'QY in which R" "represents an oxygen or nitrogen atom, Q represents an oxygen atom, an NH or NH (C 1 -C 4) alkyl group, and YR 6 4 represents a hydroxyl, amino, C1-C4alkyl, (C1-C4) alkoxy, (C1-C4) alkylamino, or di (C1-C4) alkylamino radicals. Wherein Z1 and Z2 independently represent - a single covalent bond, - a divalent radical selected from - a radical -O (CH2) p, where p denotes an integer ranging from 0 to 6 - a radical ùNR ' 6 (CH2) q (C614) where q denotes an integer ranging from 0 to 6 and t denotes 0 or 1. R'6 represents a hydrogen atom, a C1-C6 alkyl radical optionally substituted with one or more hydroxy groups. Z1 can also represent a divalent radical ùS-, -SO-, -SO2- when R'1 is a methyl radical, • R'1 and R'2 independently represent: - a hydrogen - a C1-C10 alkyl radical, optionally substituted and optionally interrupted by a heteroatom or a group selected from O, N, Si, S, SO, SO 2, - a halogen, - a SO 3 H radical, - a 5 to 8-membered ring, substituted or unsubstituted, saturated, unsaturated or aromatic, optionally containing one or more heteroatoms or groups selected from N, O, S, SO2, -CO-, the ring may be cationic and / or substituted with a cationic radical, a group -N + R17R18R19, R17, R19 and R19 are linear or branched C 1 -C 5 alkyl optionally substituted with one or more hydroxy groups. when Z1 respectively Z2 represents a covalent bond, then R'1 respectively R'2 may also represent a radical: - C, -C6 alkylcarbonyl optionally substituted - -O-00-R, CO-OR, NR-CO-R 'or in which R and R 'independently represent a hydrogen atom or an optionally substituted C1-C6 alkyl radical; R'3, R'4 and R'5, which may be identical or different, represent a hydrogen atom; hydrogen, - a hydroxyl radical, - a C1-C6 alkoxy radical, - a C1-C6 alkylthio radical, - an amino radical, - a monoalkylamino radical, - a C1-C6 dialkylamino radical in which the alkyl radicals can form, with the nitrogen atom to which they are attached, a 5- to 8-membered saturated or unsaturated heterocycle, aromatic or otherwise, which may contain one or more heteroatoms or groups chosen from N, O, S, SO 2, CO, and heterocycle which may be cationic, and / or substituted by a cationic radical, - an alkylcarbonyl radical in C1-C6, optionally substituted ,. a -O-00-R, -CO-OR, NR-CO-R 'or -CO-NRR' radical with R and R 'as defined previously, - a halogen, - a radical - NHSO3H, - a C1-alkyl radical -C4 optionally substituted ,. a saturated, unsaturated or aromatic carbon ring, optionally substituted. R'3, R'4 and R'5 may form, two by two, a partially saturated or non-saturated ring; X represents an ion or group of ions making it possible to ensure the electronegativity of the derivative of formula (II) with the proviso that at least one of R 'and R'2 is a cationic radical. 2. A composition according to claim 1 wherein the compound of formula (II) or its acid or base addition salts have the following formula: wherein R 1, R 2, R 3 are the same or different, represent a hydrogen or halogen atom; a hydroxyl radical; a (C 1 -C 4) alkyl radical; a (C 1 -C 4) alkylthio radical; a (C 1 -C 4) alkoxy radical; a radical -NHSO3H; an amino radical; a (C 1 -C 4) alkylamino radical; a di (C 1 -C 4) alkylamino radical in which the two alkyl groups can, together with the nitrogen atom to which they are bonded, form a ring which can be interrupted by one or more nitrogen, oxygen or sulfur; a heterocycle as defined above; a sulfonamide radical, a carbonyl radical, a (C 1 -C 4) alkoxycarbonyl radical, a carboxamido radical, or a group of formula: R "'QY in which R"' represents an oxygen or nitrogen atom, Q represents an oxygen atom, an NH or NH (C 1 -C 4) alkyl group, and Y represents a hydroxyl, amino, C 1 -C 4 alkyl or (C 1 -C 4) alkoxy (C 1 -C 4) radical; alkylamino, or di (C 1 -C 4) alkylamino. 3. Composition according to claim 1 wherein the compound of formula (III) or its addition salts with an acid or a base meet the NH2 x? Wherein R'3, R'4 and R'5 are as defined above, Z represents a covalent bond, a radical O (CH 2) p 20 and R ', is a cationic radical 4. Composition according to any one of the preceding claims, characterized in that the content of each of the compound (s) of formula (I) and (II) or (III) is each of between 0.001 to 10% by weight approximately of the weight total of the dyeing composition, preferably between 0.005 and 6%. 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.