Composition for dyeing keratin fibres comprising 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 6-chloro 2-methyl 5-aminophenol and a substituted meta-aminophenol

0001The subject of the invention is a composition for dyeing keratin fibers, and in particular human keratin fibers such as the hair, comprising 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2 pyrazol-1-one as the first oxidation base, 6-chloro-2-methyl-5-amino phenol as the first coupler and a substituted meta-aminophenol as the second coupler.

0002It is known to dye keratinous fibers, and in particular human keratin fibers such as the hair, with dyeing compositions comprising oxidation dye precursors, in particular ortho or para-phenylenediamines, ortho or para-aminophenols, heterocyclic compounds such as diaminopyrazole derivatives, pyrazolo [1,5-a] pyrimidine derivatives, pyrimidine derivatives, pyridine derivatives, indole derivatives, indoline derivatives generally called oxidation bases. The oxidation dye precursors, or oxidation bases, are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise, by a process of oxidative condensation, to colored or coloring compounds. This produces permanent colorations.

0003It 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 meta-phenylenediamines, meta-aminophenols and meta-hydroxyphenols. and certain heterocyclic compounds.

0004The variety of molecules involved in the oxidation bases and couplers allows a rich palette of colors to be obtained.

0005The use of oxidation bases such as para-phenylenediamine and para-aminophenol derivatives makes it possible to obtain a fairly broad range of colors at basic pH without, however, achieving good chromaticity shades while giving the hair excellent results. properties of color intensity, uniformity of color and toughness to external agents.

0006The use of these bases at neutral pH does not allow to reach a range of varied shades, in particular for hot shades such as reds and oranges.

0007The object of the present invention is to provide novel compositions for dyeing keratinous fibers which make it possible to obtain a coloration with coppery hues, powerful, chromatic, aesthetic, not very selective and resistant to the various attacks that may be experienced by the hair such as shampoos, light, sweat and permanent deformities.

0008The subject of the present invention is therefore a dyeing composition for keratinous fibers comprising, in an appropriate medium:<ul id="ul0001" list-style="bullet" compact="compact"><li>at least one first oxidation base selected from 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one of the following formula (I) and its salts; addition:<chemistry id="chem0001" num="0001"><img file="EP1870084A2_D0001.tif" /></chemistry></li><li>at least one first coupler selected from 6-chloro-2-methyl-5-amino phenol and its addition salts; and</li><li>at least one second coupler chosen from the substituted meta-aminophenols of formula (II) below and their addition salts:<chemistry id="chem0002" num="0002"><img file="EP1870084A2_D0002.tif" /></chemistry></li></ul>in which :<ul id="ul0002" list-style="none" compact="compact"><li>R₁ and R₂, identical or different, represent a hydrogen atom; an alkyl radical; a monohydroxyalkyl radical; a polyhydroxyalkyl radical; a monoaminoalkyl radical; or</li><li>R₁ and R₂ form between them and with the nitrogen atom to which they are attached a cyclic group containing one or more heteroatoms, from 5 to 7 members, saturated or unsaturated, unsubstituted or substituted with one or more radicals chosen from carboxy, carboxamido radicals hydroxyl, amino, mono or dialkylamino, alkyl optionally substituted by one or more hydroxyl, amino, mono or dialkylamino radicals;</li><li>R₃ represent, independently of one another, a halogen atom; an alkyl radical; an alkoxy radical; a monohydroxyalkyl radical; a polyhydroxyalkyl radical; a monohydroxyalkoxy radical; a polyhydroxyalkoxy radical;</li><li>n is an integer from 0 to 4;<ul id="ul0003" list-style="none" compact="compact"><li>provided that :<ul id="ul0004" list-style="none" compact="compact"><li>when n is equal to 0, then at least one of the radicals R₁ and R₂ is different from a hydrogen atom;</li><li>when n is 2 and R₃ represent a methyl radical and a chlorine atom respectively in positions 2 and 6, then R₁ and R₂ do not simultaneously represent a hydrogen atom;</li><li>it being understood that the molar ratio of the first oxidation base / first coupler is less than 1.5, the molar ratio of the first oxidation base / second coupler is greater than 1, and the molar quantity of the first oxidation base is greater than 1, and the molar quantity of the first oxidation base is greater than 1; or equal to 2.5.10^-3 mole per 100 g of composition.</li></ul></li></ul></li></ul>

0009The present invention makes it possible to obtain a coloration of the keratinous fibers with coppery hues, in particular a coloration on gray hair with 90% of natural or permanent whites having according to the CIELAB notation a value of L * less than or equal to 50, a value of a * greater than or equal to 20, preferably greater than or equal to 25, even more preferably between 25 and 50, a value of b * greater than or equal to 20, preferably greater than or equal to 25, even more preferably between 25 and 50 and a ratio b * / a * of between 0.5 and 1.5, preferably between 0.7 and 1.2.

0010The present invention also makes it possible to obtain a powerful, highly chromatic, aesthetic, low-selective coloring and resistant to the various attacks that hair can undergo, such as shampoos, light, sweat and permanent deformations. It also makes it possible to obtain intense coloration at neutral pH.

0011Another subject of the invention is a process for dyeing keratin fibers using the composition of the present invention, as well as the use of this composition for dyeing keratinous fibers.

0012The invention finally relates to a staining kit comprising on the one hand a staining composition containing 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1 one as the base of oxidation, 6-chloro-2-methyl-5-amino phenol as the first coupler and a substituted meta-aminophenol as a second coupler and secondly a composition containing an oxidizing agent.

0013The CIELAB notation used in the context of the invention defines a color space in which each color is defined by 3 parameters (L *, a *, b *). The parameter L * reflects the clarity of the color, the value L * being equal to 0 for black and equal to 100 for absolute white. The higher the L * value, the less intense the color. The parameter a * corresponds to the axis of the green / red antagonistic pair. The parameter b * corresponds to the axis of the blue / yellow antagonist couple.

0014Unless otherwise indicated, the ranges of the ranges of values ​​which are given within the scope of the present invention are included in these ranges.

0015In the context of the invention, the term "alkyl radical" means linear or branched C-alkyl radicals.₁-C₁₀ unless otherwise indicated, preferably in C₁-C₆, even more preferentially in C₁-C₄such as the methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, pentyl and hexyl radicals.

0016In the context of the present invention, the heteroatom (s) may be chosen from an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom.

0017In the context of the present invention, a halogen atom may be selected from a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

0018According to a particular embodiment of the invention, R₁ and R₂ represent, independently of one another, a hydrogen atom; an alkyl radical such as a methyl or ethyl radical; a monohydroxyalkyl radical such as a β-hydroxyethyl or γ-hydroxypropyl radical; or R₁ and R₂ form with each other and with the nitrogen atom to which they are attached a ring selected from pyrrolidine, piperidine, homopiperidine, piperazine, homopiperazine and morpholine heterocycles; said rings may be substituted with one or more hydroxyl, amino, mono or dialkyl radicals (C₁-C₂) amino, carboxy, carboxamido, C-alkyl₁-C₄ optionally substituted with one or more hydroxyl, amino, mono or dialkyl radicals (C₁-C₂) Alkylamino, and more particularly chosen from pyrrolidine, 2,5-dimethylpyrrolidine, pyrrolidine-2-carboxylic acid, 3-hydroxypyrrolidine-2-carboxylic acid, 4-hydroxypyrrolidine-2-carboxylic acid, 2,4-dicarboxypyrrolidine, 3-hydroxy-2-hydroxymethylpyrrolidine, 2-carboxamidopyrrolidine, 3-hydroxy-2-carboxamidopyrrolidine, 2-hydroxymethyl pyrrolidine, 3,4-dihydroxy-2-hydroxymethyl pyrrolidine, 3-hydroxypyrrolidine, 3,4-dihydroxy pyrrolidine, 3-amino pyrrolidine, 3-methylamino pyrrolidine, 3-dimethylamino-pyrrolidine, 4-amino-3-hydroxy pyrrolidine, 3-hydroxy-4- (β-hydroxyethyl) amino-pyrrolidine, piperidine, 2,6-dimethylpiperidine, 2-carboxypiperidine, 2-carboxamidopiperidine, 2-hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethylpiperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine, homopiperidine, 2-carboxyhomopiperidine, 2-carboxamidohomopiperidine, homopiperazine, N-methyl-homopiperazine, N- (2-hydroxyethyl) homopiperazine, piperazine, 4-methylpiperazine, 4-ethyl-piperazine, 4- (β-hydroxyethyl) -piperazine, morpholine, and more particularly they form a pyrrolidin-1-yl group; piperidin-1-yl; piperazin-1-yl; 4-methyl-piperazin-1-yl; 4-ethyl-piperazin-1-yl; 4- (β-hydroxyethyl) piperazin-1-yl; morpholin-4-yl.

0019According to a particular embodiment of the invention, R₃ is selected from a halogen atom, an alkyl radical, an alkoxy radical, a monohydroxyalkoxy radical. For example, R₃ is chosen from a chlorine atom, a methyl radical, a methoxy radical, a β-hydroxyethyloxy radical.

0020According to a particular embodiment of the invention, n is between 0 and 2. For example, n is equal to 1 or 2. When n is 1, R₃ can be in position 2 and when n is 2, R₃ can be in positions 2 and 4.

0021Among the substituted meta-aminophenols of formula (II) useful in the context of the invention, mention may be made more particularly of 5-amino-2-methoxyphenol; 5-amino 2- (β-hydroxyethyloxy) phenol; 5-amino-2-methyl phenol; 5-N- (β-hydroxyethyl) amino-2-methyl phenol; 5-N- (β-hydroxyethyl) amino-4-methoxy-2-methyl phenol; 5-amino-4-methoxy-2-methyl phenol; 5-amino-4-chloro-2-methyl phenol; 5-amino-2,4-dimethoxyphenol; 5- (γ-hydroxypropylamino) 2-methyl phenol; 3-dimethylamino phenol; 2-methyl-5-dimethylaminophenol; 2-ethyl-5-dimethylamino phenol; 2-methoxy-5-dimethylaminophenol; 2-ethoxy-5-dimethylaminophenol; 2- (β-hydroxyethyl) -5-dimethylaminophenol; 3-diethylamino phenol; 2-methyl-5-diethylamino phenol; 2-ethyl-5-diethylamino phenol; 2-methoxy-5-diethylamino phenol; 2-ethoxy-5-diethylamino phenol; 2- (β-hydroxyethyl) -5-diethylaminophenol; 3-di (β-hydroxyethyl) amino phenol; 2-methyl-5-di (β-hydroxyethyl) amino phenol; 2-ethyl-5-di (β-hydroxyethyl) aminophenol; 2-methoxy-5-di (β-hydroxyethyl) amino phenol; 2-ethoxy-5-di (β-hydroxyethyl) amino phenol; 2- (β-hydroxyethyl) -5-di (β-hydroxyethyl) amino phenol; 3-pyrrolidin-1-yl-phenol; 2-methyl-5-pyrrolidin-1-yl-phenol; 2-ethyl-5-pyrrolidin-1-yl-phenol; 2-methoxy-5-pyrrolidin-1-yl-phenol; 2-ethoxy-5-pyrrolidin-1-yl-phenol; 2- (β-hydroxyethyl) -5-pyrrolidin-1-yl-phenol; 3-piperidin-1-yl-phenol; 2-methyl-5-piperidin-1-yl-phenol; 2-ethyl-5-piperidin-1-yl-phenol; 2-methoxy-5-piperidin-1-yl-phenol; 2-ethoxy-5-piperidin-1-yl-phenol; 2- (β-hydroxyethyl) -5-piperidin-1-yl-phenol; 3-piperazin-1-yl-phenol; 2-methyl-5-piperazin-1-yl-phenol; 2-ethyl-5-piperazin-1-yl-phenol; 2-methoxy-5-piperazin-1-yl-phenol; 2-ethoxy-5-piperazin-1-yl-phenol; 2- (β-hydroxyethyl) -5-piperazin-1-yl-phenol; 3- (4-methyl-piperazin-1-yl) -phenol; 2-methyl-5- (4-methyl-piperazin-1-yl) -phenol; 2-ethyl-5- (4-methyl-piperazin-1-yl) -phenol; 2-methoxy-5- (4-methyl-piperazin-1-yl) -phenol; 2-ethoxy-5- (4-methyl-piperazin-1-yl) -phenol; 2- (β-hydroxyethyl) -5- (4-methyl-piperazin-1-yl) -phenol; 3- (4-ethyl-piperazin-1-yl) -phenol; 2-methyl-5- (4-ethyl-piperazin-1-yl) -phenol; 2-ethyl-5- (4-ethyl-piperazin-1-yl) -phenol; 2-methoxy-5- (4-ethyl-piperazin-1-yl) -phenol; 2-ethoxy-5- (4-ethyl-piperazin-1-yl) -phenol; 2- (β-hydroxyethyl) -5- (4-ethyl-piperazin-1-yl) -phenol; 3- (4- (β-hydroxyethyl) piperazin-1-yl) phenol; 2-methyl-5- (4- (β-hydroxyethyl) piperazin-1-yl) phenol; 2-ethyl-5- (4- (β-hydroxyethyl) -piperazin-1-yl) -phenol; 2-methoxy-5- (4- (β-hydroxyethyl) piperazin-1-yl) phenol; 2-ethoxy-5- (4- (β-hydroxyethyl) piperazin-1-yl) phenol; 2- (β-hydroxyethyl) -5- (4- (β-hydroxyethyl) piperazin-1-yl) phenol; 3-morpholin-4-yl-phenol; 2-methyl-5-morpholin-4-yl-phenol; 2-ethyl-5-morpholin-4-yl-phenol; 2-methoxy-5-morpholin-4-yl-phenol; 2-ethoxy-5-morpholin-4-yl-phenol; 2- (β-hydroxyethyl) -5-morpholin-4-yl-phenol.

0022Among the substituted meta-aminophenols of formula (II) mentioned above, 5-N- (β-hydroxyethylamino) 2-methyl phenol and 5-amino-2-methyl phenol are particularly preferred.

0023In the composition according to the present invention, the molar ratio first oxidation base / first coupler is less than 1.5. Preferably, the molar ratio first oxidation base / first coupler is between 0.5 and 1.2.

0024In the composition according to the present invention, the molar ratio first oxidation base / second coupler is greater than 1. Preferably, the molar ratio first oxidation base / second coupler is between 2 and 5.

0025The dyeing composition of the invention may contain at least one second oxidation base chosen from para-aminophenols.

0026Among the para-aminophenols that can be used as oxidation bases in the dyeing compositions in accordance with the invention, there may be mentioned the compounds corresponding to the following formula (III), and their addition salts:<chemistry id="chem0003" num="0003"><img file="EP1870084A2_D0003.tif" /></chemistry>in which :<ul id="ul0005" list-style="none" compact="compact"><li>R₄ represents a hydrogen atom; a halogen atom; an alkyl radical; a monohydroxyalkyl radical; an alkoxyalkyl radical; an aminoalkyl radical; a hydroxyalkylaminoalkyl radical;</li><li>R₅ represents a hydrogen atom; a halogen atom; an alkyl radical; a monohydroxyalkyl radical; a polyhydroxyalkyl radical; an aminoalkyl radical; a cyanoalkyl radical; an alkoxyalkyl radical;</li></ul>it being understood that at least one of the radicals R₄ or R₅ represents a hydrogen atom.

0027Among the para-aminophenols of formula (III) above, mention may be made more particularly of para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol and 4-amino-3-hydroxymethylphenol. , 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethylaminomethyl) phenol 4-amino-2-fluoro phenol. Para-aminophenol is particularly preferred.

0028The dye composition of the invention may contain other oxidation bases different from those used in the present invention and conventionally used for dyeing keratinous fibers.

0029The composition of the present invention may for example comprise at least one additional oxidation base chosen from para-phenylenediamines, bis-phenylalkylenediamines, bis-para-aminophenols, ortho-aminophenols, ortho-phenylenediamines and heterocyclic bases. different from 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and its addition salts.

0030Among the para-phenylenediamines, for example, para-phenylenediamine, para-toluenediamine, 2-chloro para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, 2,6-dimethyl para-phenylenediamine, 2,6-diethyl para-phenylenediamine, 2,5-dimethyl para-phenylenediamine, N, N-dimethyl para-phenylenediamine, N, N-diethyl para-phenylenediamine, N, N-dipropyl para-phenylenediamine, 4-amino N, N-diethyl-3-methyl aniline, N, N-bis- (β-hydroxyethyl) para-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2-β-hydroxyethyl para-phenylenediamine, 2-fluoro para-phenylenediamine, 2-isopropyl para-phenylenediamine, N- (β-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) para-phenylenediamine, N- (β, γ-dihydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2-β-acetylaminoethyloxy para-phenylenediamine, N- (β-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl para-phenylenediamine, 2-β-hydroxyethylamino-5-amino toluene, 3-hydroxy 1- (4'-aminophenyl) pyrrolidine and their addition salts.

0031Among the para-phenylenediamines mentioned above, 2-isopropyl para-phenylenediamine, 2-β-hydroxyethyl para-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl para-phenylenediamine, 2 , 6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (β-hydroxyethyl) para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, phenylenediamine, and their addition salts are particularly preferred.

0032Among the bis-phenylalkylenediamines, for example, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3-diamino propanol, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N'-bis- (4'-amino) 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts.

0033Among 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.

0034Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

0035Among the pyridine derivatives, mention may be made of the compounds described, for example, in the patents <patcit id="pcit0001" dnum="GB1026978A"><text>GB 1,026,978</text></patcit> and <patcit id="pcit0002" dnum="GB1153196A"><text>GB 1 153 196</text></patcit>such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 2,3-diamino-6-methoxy pyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts.

0036Other 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. <patcit id="pcit0003" dnum="FR2801308"><text>FR 2 801 308</text></patcit>. For exemple, 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-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] pyridin-7-ol; as well as their addition.

0037Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in the patents <patcit id="pcit0004" dnum="DE2359399"><text>DE 23 59 399</text></patcit> ; <patcit id="pcit0005" dnum="JP63169571A"><text>JP 88-169571</text></patcit> ; <patcit id="pcit0006" dnum="JP5063124A"><text>JP 05-63124</text></patcit> ; <patcit id="pcit0007" dnum="EP0770375A"><text>EP 0 770 375</text></patcit> or patent application <patcit id="pcit0008" dnum="WO9615765A"><text>WO 96/15765</text></patcit> 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 <patcit id="pcit0009" dnum="FR2750048A"><text>FR-A-2,750,048</text></patcit> 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-hydroxy-ethyl) 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; the 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 addition salts and tautomeric forms, when there is a tautomeric equilibrium.

0038Among the pyrazole derivatives, mention may be made of the compounds described in the patents <patcit id="pcit0010" dnum="DE3843892"><text>DE 38 43 892</text></patcit>, <patcit id="pcit0011" dnum="DE4133957"><text>DE 41 33 957</text></patcit> and patent applications <patcit id="pcit0012" dnum="WO9408969A"><text>WO 94/08969</text></patcit>, <patcit id="pcit0013" dnum="WO9408970A"><text>WO 94/08970</text></patcit>, <patcit id="pcit0014" dnum="FR2733749A"><text>FR-A-2,733,749</text></patcit> and <patcit id="pcit0015" dnum="DE19543988"><text>DE 195 43 988</text></patcit> such as 4,5-diamino-1-methyl pyrazole, 4,5-diamino 1- (β-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-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenyl pyrazole, 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- (β-hydroxyethyl) 3-methyl pyrazole, 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-methyl-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- (β-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts.

0039The dye composition of the invention may contain additional couplers different from those useful in the present invention and conventionally used for dyeing keratinous fibers.

0040The composition of the present invention may for example comprise at least one additional coupler chosen from meta-phenylenediamines, meta-aminophenols other than 6-chloro-2-methyl-5-amino phenol, meta-aminophenols of formula (II) and their addition salts, meta-diphenols, naphthalenic couplers, heterocyclic couplers.

0041As examples, mention may be made of 3-amino phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methyl benzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino 1- (β-hydroxyethyloxy) benzene, 2-amino-4- (β-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, the sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, the α-naphthol, 2-methyl-1-naphthol, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- (β-hydroxyethylamino) toluene and their addition salts.

0042Preferably, the composition in accordance with the invention comprises at least one additional coupler chosen from 2-amino-3-hydroxy-pyridine, 1,3-dihydroxy-2-methylbenzene and their addition salts.

0043The oxidation base (s) present in the composition of the invention are generally present each in an amount of between 0.001 to 10% by weight approximately of the total weight of the dyeing composition, preferably between 0.005 and 6%.

0044The coupler or couplers present in the composition of the invention are generally present each in an amount of between 0.001 and 10% by weight of the total weight of the dye composition, preferably between 0.005 and 6%.

0045In general, the addition salts of the 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, sulphates, citrates, succinates, tartrates, lactates, alkyls (C₁-C₄) sulfonates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

0046The medium suitable for dyeing, also known as a dyeing medium, is a cosmetic medium generally consisting of water or a mixture of water and at least one organic solvent for solubilizing compounds that are not sufficiently soluble in water. water. As an organic solvent, mention may be made, for example, of lower alkanols in C₁-C₄such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

0047The solvents are preferably present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

0048The dyeing composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic surfactants, cationic, nonionic, amphoteric zwitterionics or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric zwitterionics or mixtures thereof, inorganic or organic thickeners, and in particular anionic polymeric associative thickeners, cationic, nonionic and amphoteric, antioxidants, penetration agents, sequestering agents, perfumes, buffers, dispersants, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preservatives, opacifying agents.

0049The 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.

0050Of 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.

0051The 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.

0052Among 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.

0053Among the alkalinizing agents that may be mentioned, for example, ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (IV):<chemistry id="chem0004" num="0004"><img file="EP1870084A2_D0004.tif" /></chemistry>in which W is a propylene residue optionally substituted with a hydroxyl group or a C-alkyl radical₁-C₄ ; R_at, R_b, R_c and R_d, which may be identical or different, represent a hydrogen atom or a C 1 -alkyl radical₁-C₄ or hydroxyalkyl in C₁-C₄.

0054The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, and especially human hair.

0055The process of the present invention is a process in which the composition according to the present invention as defined above is applied to the fibers, and the color is revealed using an oxidizing agent. 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. Preferably, this coloration is revealed at neutral pH.

0056According to a particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount sufficient to develop a coloration. 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.

0057The oxidizing agents conventionally used for the oxidation dyeing of keratinous fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes. among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

0058The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing hair and as defined above.

0059The 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 12. 11. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used in dyeing keratinous fibers and as defined above.

0060The ready-to-use composition which is finally applied to the keratin fibers may be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratinous fibers, and including human hair.

0061The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains the dye composition of the present invention defined above with the exception of the oxidizing agent and a second compartment contains a oxidizing composition. This device can be equipped with a means for delivering the desired mixture onto the hair, such as the devices described in the patent.<patcit id="pcit0016" dnum="FR2586913"><text>FR-2,586,913</text></patcit> in the name of the plaintiff.

0062The subject of the present invention is also the use for the oxidation dyeing of keratinous fibers, and in particular human keratinous fibers such as the hair, of a composition as defined above.

0063According to a particular embodiment, the use of the composition according to the invention on gray hair with 90% natural or permed whites makes it possible to obtain a color exhibiting, according to the CIELAB notation, a value of L * of not more than 50, a value of a * greater than or equal to 20, preferably greater than or equal to 25, even more preferably between 25 and 50, a value of b * greater than or equal to 20, preferably greater than or equal to 25, even more preferably between 25 and 50, and a ratio b * / a * of between 0.5 and 1.5, preferably between 0.7 and 1.2.

0064The examples which follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES

<u style="single">Example 1</u> :

0065The following composition 1 was carried out:<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2"><colspec colnum="1" colname="col1" colwidth="137mm" /><colspec colnum="2" colname="col2" colwidth="15mm" /><tbody><row><entry>Diethylene triamine pentaacetic acid, pentasodium salt in 40% aqueous solution</entry><entry>2 g</entry></row><row><entry>Ammonia in 20% aqueous solution</entry><entry>12 g</entry></row><row><entry>Sodium metabisulfite powder</entry><entry>0.71 g</entry></row><row><entry>Pure monoethanolamine</entry><entry>2.02 g</entry></row><row><entry>Pyrogenic silica with hydrophobic character</entry><entry>1.2 g</entry></row><row><entry>2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2 CH₃-SO₃H</entry><entry>1.9 g</entry></row><row><entry>5-amino-2-methylphenol</entry><entry>0.2 g</entry></row><row><entry>Titanium oxide (untreated anatase) coated with poly dimethylsiloxane (98/2)</entry><entry>0.15 g</entry></row><row><entry>Purified 6-chloro 2-methyl-5-amino phenol</entry><entry>0.8 g</entry></row><row><entry>Para-aminophenol</entry><entry>0.1 g</entry></row><row><entry>Glycol distearate</entry><entry>2 g</entry></row><row><entry>Mica-Titanium Oxide-Brown Iron Oxide (58 / 37.5 / 4.5)</entry><entry>0.5 g</entry></row><row><entry>Perfume</entry><entry>0.5 g</entry></row><row><entry>Polycondensate tetramethyl hexamethylenediamine / dichloro 1,3-propylene in aqueous solution</entry><entry>3 g</entry></row><row><entry>Poly dimethyl diallyl ammonium chloride in 40% unstabilized water</entry><entry>5 g</entry></row><row><entry>Carboxyvinyl polymer synthesized in the ethyl acetate / cyclohexane mixture</entry><entry>0.6 g</entry></row><row><entry>deionized water</entry><entry>24.57 g</entry></row><row><entry>Propylene glycol</entry><entry>7 g</entry></row><row><entry>Natural lauric acid</entry><entry>3 g</entry></row><row><entry>Oxyethylenated lauric alcohol (12 EO)</entry><entry>7 g</entry></row><row><entry>Decyl alcohol oxyethylenated (3 EO)</entry><entry>10 g</entry></row><row><entry>Cetylstearyl alcohol (C16-18 50/50) (synthetic origin)</entry><entry>11.5 g</entry></row><row><entry>Oleocetyl alcohol oxyethylenated (30 EO)</entry><entry>4 g</entry></row><row><entry>Vitamin C: L-ascorbic acid in fine powder</entry><entry>0.25 g</entry></row></tbody></tgroup></table></tables>

0066At the time of use, 1 part by weight of the composition 1 is mixed with 1.5 parts by weight of a solution of hydrogen peroxide at 25 volumes at pH 2.2. A final pH of 9.6 is obtained.

0067The mixture obtained is applied to locks of gray hair with 90% natural or permed whites. After exposure for 20 minutes at room temperature, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

0068Capillary staining is evaluated visually. We obtain a light coppery blond shade.

0069Hair color is measured using a MINOLTA CM2002® spectrocolorimeter (Illuminant D65 - 10 ° CSI) in the CIELab system. In this system, L * represents clarity, a * hue and b * saturation.

0070The results obtained are shown in the table above.<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="4"><colspec colnum="1" colname="col1" colwidth="35mm" /><colspec colnum="2" colname="col2" colwidth="12mm" /><colspec colnum="3" colname="col3" colwidth="12mm" /><colspec colnum="4" colname="col4" colwidth="12mm" /><thead><row><entry valign="top"><b>Hair type</b></entry><entry valign="top"><b>L *</b></entry><entry valign="top"><b>at*</b></entry><entry valign="top"><b>b *</b></entry></row></thead><tbody><row><entry>Natural whites</entry><entry>44.8</entry><entry>31.3</entry><entry>34.1</entry></row><row><entry>Permed whites</entry><entry>38.1</entry><entry>35.5</entry><entry>29.4</entry></row></tbody></tgroup></table></tables>