The invention relates to a composition for dyeing keratin fibres, and in particular human keratin fibres such as the hair, comprising 2,3.-diamino-6,7-dihydro-lH,5H-pyrazolofl,2-a]pyrazol-1-one as first oxidation base, para-phenylenediamine or para-tolylenediamine as second oxidation base and a substituted meta-aminophenol as first coupler.
It is known practice to dye keratin fibres, and in particular human keratin fibres such as the hair, with dye compositions comprising oxidation dye precursors, in particular ortho- or para-phenylenediamines, ortho-or para-aminophenols, and heterocyclic compounds such as diaminopyrazole derivatives, pyrazolo[l,5-a]-pyrimidine derivatives, pyrimidine derivatives, pyridine derivatives, indole derivatives and indoline derivatives, which are generally known as oxidation bases. Oxidation dye precursors, or oxidation bases, are colourless or weakly coloured compounds that, when combined with oxidizing products, can give rise to dyes or coloured compounds via a process of oxidative condensation. Permanent colorations are thus obtained.
It is also known that the shades obtained with these oxidation bases may be varied by combining them with couplers qr coloration modifiers, the latter being chosen especially from meta-phenylenediamines, meta-aminophenols, meta-hydroxyphenols and certain hetero-cyclic compounds.
The variety of molecules used as regards the oxidation bases and couplers allows a wide range of colours to be obtained.

The use of oxidation bases such as para-phenylene-diamine and para-aminophenol derivatives allows a quite broad range of colours to be obtained at basic pH without, however, achieving shades with good chromaticity, while at the same time giving the hair excellent properties in terms of strength of colour, uniformity of the colour and fastness with respect to external agents.
The use of these bases at neutral pH does not allow a varied range of shades to be produced, in particular for warm shades such as reds and oranges .
The aim of the present invention is to provide novel compositions for dyeing keratin fibres that make it possible to obtain a strong, chromatic, aesthetic and sparingly selective coloration in particularly visible deep red shades, which shows good resistance to the various attacking factors to which the hair may be subjected, such as shampoo, light, sweat and permanent reshaping operations .
One subject of the present invention is thus a
composition for dyeing keratin fibres, comprising, in a
suitable medium:
• at least one first oxidation base chosen from 2,3-
diamino-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-1-one
of formula (I) below, and the addition salts thereof:
(Formula Removed)
• at least one second oxidation base chosen from para-
phenylenediamine and para-tolylenediamine, and the
addition salts thereof; and
• at least one first coupler chosen from the
substituted meta-aminophenols of formula (II) below,
and the addition salts thereof:
(Formula Removed) (II)
in which:
R1 and R2, which may be identical or different, represent a hydrogen atom; an alkyl radical; a monohydroxyalkyl radical; a polyhydroxyalkyl radical; a monoaminoal.kyl radical; or
R1 and R2 form, together with the nitrogen atom to which they are attached, a saturated or unsaturated, 5- to 1-membered cyclic group containing one or more heteroatoms, which may be unsubstituted or substituted with one or more radicals chosen from carboxyl, carboxamido, hydroxyl, amino, monoalkylamino and dialkylamino radicals, and alkyl radicals optionally substituted with one or more hydroxyl, amino, monoalkylamino or dialkylamino radicals; R3 represent, independently of each other, a halogen atom; an alkyl radical; an alkoxy radical; a monohydroxyalkyl radical; a polyhydroxyalkyl radical; a monohydroxyalkoxy radical; a polyhydroxyalkoxy radical; n is an integer between 0 and 4;
with the proviso that when n is equal to 0, then at least one of the radicals R1 and R2 is other than a hydrogen atom;
it being understood that the first coupler/first oxidation base mole ratio is greater than 1, the first oxidation base/second oxidation base mole ratio is between 0.5 and 1.5 and the molar amount of the first oxidation base is greater than or equal to 2.5x10-3 mol per 100 g of composition.
The present invention allows keratin fibres to be coloured in particularly visible deep red shades, in particular a coloration, on natural or permanent-waved grey hair containing 90% white hairs having, according to the CIELab notation, a value for L* of less than or

equal to 50, a value for a* of between 10 and 25, a value for b* of between 3 and 25 and a ratio b*/a* of between 0.3 and 1 and preferably between 0.3 and 0.7.
The present invention also makes it possible to obtain. a strong, aesthetic, sparingly selective coloration that shows good resistance to the various attacking factors to which the hair may be subjected, such as shampoo, light, sweat and permanent reshaping operations. The invention furthermore makes it possible to obtain an intense coloration at neutral pH.
Another subject of the invention is. a process for dyeing keratin fibres using the composition of the present invention, and also the use of this composition for dyeing keratin fibres.
Finally, a subject of the invention is a dyeing kit comprising, firstly, a dye composition containing 2,3-diamino-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-i-one as first oxidation base, para-phenylenediamine or para-tolylenediamine as second oxidation base and a substituted meta-aminophenol as coupler, and, secondly, a composition containing an oxidizing agent.
The ClELab notation used in the context of the invention defines a colorimetric space in which each colour is defined by three parameters (L*, a*, b*}. The parameter L* reflects the lightness of the colour, the value L* being equal to 0 for black and equal to 100 for absolute white. The higher the value of L*, the less intense the coloration. The parameter a* corresponds to the axis of the green/red antagonist pair. The parameter b* corresponds to the axis of the blue/yellow antagonist pair.
Unless otherwise indicated, the limits of the ranges of values given in the context of the present invention are included in these ranges.
In the context of the invention, the terra "alkyl radical" means, unless otherwise indicated, linear or branched C1-C10, preferentially C1-C6 and even more preferentially C1-C4, alkyl radicals, such as methyl, ethyl, propyl, isopropyl, isobutyl, tert-butyl, pentyl or hexyl radicals.
In the context of the present invention, the heteroatoms(s) may be chosen from an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom.
In the context of the present invention, a halogen atom may be chosen from a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.
According to one particular embodiment of the
invention, R1 and R2 represent, independently of each
other, a hydrogen atom; an alkyl radical, for example a
methyl or ethyl radical; a monohydroxyalkyl radical,
for example a β-hydroxyethyl or y-hydroxypropyl
radical; or R1 and R2 form, together with the nitrogen
atom to which they are attached, a ring chosen from
pyrrolidine, piperidine, homopiperidine, piperazine,
homopiperazine and morpholine heterocycles; the said
rings possibly being substituted with one or more
hydroxyl, amino, mono(C1-C2)alkylamino, di(C1-
C2)alkylamino, carboxyl or carboxamido radicals, or C1-
C4 alkyl radicals optionally substituted with one or
more hydroxyl, amino, mono(Ci-C2)alkylamino or di(C1-
C2)alkylamino radicals, 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-carboxamidbpyrrolidine, 3-
hydroxy-2-carboxamidopyrrolidine, 2-
hydroxymethylpyrrolidine, 3,4-dihydroxy-2-
hydroxymethylpyrrolidine, 3-hydroxypyrrolidine, 3,4-
dihydroxypyrrolidine, 3-aminopyrrolidine, 3-methyl-aminopyrrolidine, 3-dimethylaminopyrrolidine, 4-amino-3-hydroxypyrrolidine, 3-hydroxy-4-(β-hydroxyethyl)-aminopyrrolidine, piperidine, 2, 6-dimethylpiperidine, 2-carboxypiperidine, 2-carboxamidopiperidine, 2-hydroxymethylpiperidine, 3-hydroxy-2-hydroxymethyl-piperidine, 3-hydroxypiperidine, 4-hydroxypiperidine, 3-hydroxymethylpiperidine, homopiperidine, 2-carboxy-homopiperidine, 2-earboxamidohomopiperidine, homo-piperazine, N-methylhomopiperazine, N-(2-hydroxy-ethyl)homopiperazine, piperazine, 4-methylpiperazine, 4-ethylpiperazine, 4- (β-hydroxyethyl)piperazine and morpholine, and they more particularly form the following group: pyrrolidin-1-yl; piperidin-1-yl; piperazin-1-yl; 4-methylpiperazin-l-yl; 4-ethylpiper-azin-1-yl; 4- (β-hydroxyethyl)piperazin-1-yl; morpholin-4-yl.
According to one particular embodiment of the invention, R3 is chosen from a halogen atom, an alkyl radical, an alkoxy radical and a monohydroxyalkoxy radical. By way of example, R3 is chosen from a chlorine atom, a methyl radical, a methpxy radical and a β-hydroxyethyloxy radical.
According to one particular embodiment of the invention, n is between 0 and 2. By way of example, n is equal to 1 or 2. When n is equal to 1, R3 may be in position 2 and when n is equal to 2, R3 may be in positions 2 and 4 or in positions 2 and G.
Among the substituted meta-aminophenols of formula (II) that are 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-methylphenol, 5-N-(β-hydrbxyethyl)amino-2-methylphenol, 5-N-(β-hydroxyethyl)amino-4-methoxy-2-methylphenpl, 5-amino-4-methoxy-2-methylphenol, 5-amino-4-chloro-2-methylphenol, 6-chloro-2-methyl-5-
aminophenol, 5-amino-2,4-dimethoxyphenol, 5- (y-hydroxy-propylamino)-2-methylphenol, 3-dimethylaminophenol; 2-methyl-5-diraethylaminophenol; 2-ethyl-5-dimethylaminc-phenol; 2-methoxy-5-dimethylaminophenol; 2-ethoxy-5-dimethylaminophenol; 2-(β-hydroxyethyl)-5-dimethyl-aminophenol; 3-diethylaminophenol; 2-methyl-5-diethyl-aminophenol; 2-ethyl-5-diethylaminophenol; 2-methoxy-5-diethylaminophenol; 2-ethoxy-5-diethylaminophenol; 2-tp-hydroxyethyl) -5-diethylaminophenol; 3-di (β-hydroxy-ethyl) euidnophenol; 2-methyl-5-di(β-hydroxyethyl)amino-phenol; 2-ethyl-5-di(β-hydroxyethyl)aminophenol; 2-methoxy-5-di(β-hydroxyethyl)aminophenol; 2-ethoxy-5-di(β-hydroxyethyl)aminophenol; 2-(p-hydroxyethyl)-5-di(β-hydroxyethyl)aminophenol; 3-pyrrolidin-l-ylphenol; 2-methyl-5-pyrrolidin-l-ylphenol; 2-ethyl-5-pyrrolidin-1-ylphenol; 2-methoxy-5-pyrrolidin-l-ylphenol; 2-ethoxy-5-pyrrolidin-l-ylphenol; 2-(p-hydroxyethyl)-5-pyrrolidin-1-ylphenol; 3-piperidin-l-ylphenol; 2-methyl-5-piperidin-l-ylphenol; 2-ethyl-5-piperidin-l-ylphenol; 2-methoxy-5-piperidin-l-ylphenol; 2-ethoxy-5-piperidin-1-ylphenol; 2-(β-hydroxyethyl)-5-piperidin-l-ylphenol; 3-piperazin-l-ylphenol; 2-methyl-5-piperazin-1-ylphenol; 2-ethyl-5-piperazin-l~ylphenol; 2-methoxy-5-piperazin-l-ylphenol; 2-ethoxy-5-piperazin-l-yl-phenol; 2- (β-hydroxyethyl)-5-piperazin-l-ylphenol; 3-(4-methylpiperazin-l-yl)phenol; 2-methyl-5-(4-methyl-piperazin-1-yl)phenol; 2-ethyl-5-(4-methylpiperazin-l-yl)phenol; 2-methoxy-5-(4-methylpiperazin-l-yl)phenol; 2-ethoxy-5- (4-methylpiperazin-l-yl)phenol; 2- (β-hydroxyethyl)-5-(4-methylpiperazin-l-yl)phenol; 3-(4-ethylpiperazin-l-'yl)phenol; 2-methyl-5- (4-ethylpiper-azin-l-yl)phenol; 2-ethyl-5-(4-ethylpiperazin-l-yl)-phenol; 2-methoxy-5-(4-ethylpiperazin-l-yl)phenol; 2-ethoxy-5-(4-ethylpiperazin-l-yl)phenol; 2-(β-hydroxy-ethyl)-5-(4-ethylpiperazin-l-yl)phenol; 3- 14-(β-hydroxyethyl)piperazin-l-yl)phenol; 2-methyl-5-(4- (β-hydroxyethyl)piperazin-l-yl)phenol; 2-ethyl-5-(4-(β-hydroxyethyl)piperazin-l-yl)phenol; 2-methoxy-5-(4-(β-hydroxyethyl)piperazin-l-yl)phenol; 2-ethoxy-5-(4-(β-

hydroxyethyl)piperazin-l-yl)phenol; 2-(p-hydroxyethyl)-5-(4-(β-hydroxyethyllpiperazin-l-yl)phenol; 3-morphc-lin-4-ylphenol; 2-methyl-5-morpholin-4-ylphenol; 2-ethyl-5-morpholin-4-ylphenol; 2-methoxy-5-morpholin.-4-ylphenol; 2-ethoxy-5-morpholin-4-ylphenol; 2-(|3-hydroxyethyl)-5-morpholin-4-ylphenol.
Among the substituted meta-aminophenols of formula (II) mentioned above, 5-N-(β-hydroxyethylamino)-2-methyl-phenol, 5-amino-2-methylphenol and 6-chloro-2-methyl-5-aminophenol are particularly preferred.
In the composition in accordance with the present invention, the first coupler/first oxidation base mole ratio is greater than 1. Preferably, the first coupler/first oxidation base mole ratio is between 2 and 5.
In the composition in accordance with the present invention, the first oxidation base/second oxidation base mole ratio is between 0.5 and 1.5. Preferably, the first oxidation base/second oxidation base mole ratio is between 0.7 and 1.3.
The dye composition of the invention may contain oxidation bases other than those that are useful in the present invention and conventionally used for the dyeing of keratin fibres.
The composition of the present invention may comprise, for example, at least one additional oxidation base chosen from para-phenylenediamines other than para-phenylenediamine and para-tolylenediamine and the addition salts thereof, bis(phenyl)alkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-amino-phenols, ortho-phenylenediamines and heterocyclic bases other than 2,3-diamino-6, 7-dihydro-lH,5H-pyrazolo[1,2-a]pyrazol-1-one, and the addition salts thereof.

Among t.he para-phenylenediamines that may be mentioned/ for example, are 2-chloro-para-phenylenediamine, 2, 3-dimethyl-para-phenylenediamine, 2, 6-dimethyi-para-phenylenediamine, 2,6-dietny.l-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(β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(β-ydroxyethyl)amino-2-methylaniline, 4-N,N-bis(β-hydroxyethyl)amino-2-chloroanilin.e, 2-β-hydroxyethyl-para-phenylene-diamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (β-hydroxypropyl) -para-phenyl-enediamine, 2-hydroxymethyl-para-phenyl.enediamine, N,K-dlmethyl-3-jnethyl-^para-phenyienediainine, N-ethyl-N- (β-hydroxyethyl)-para-phenylenediamine, N- (β,y-dihydroxy-propyl)-para-phenylenediamine, N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetyl-aminoethyloxy-para-phenylenediamine, N- (β-methoxy-ethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-l-(4'-aminophenyl)-pyrrolidine, and the addition salts thereof.
Among the para-phenylenediamines mentioned above, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl -para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylene-diamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(β-hydroxyethyl]-para-phenyl-enediamine, 2-chloro-para-phenylenediamine and 2-β-acetylaminoethyloxy-para-phenylenediamine, and the addition salts thereof are particularly preferred.
Among the bis (phenyl) alkylenediamihes that may be mentioned, for example, are N,N'-bis (β-hydroxyethyl) -N,N' -bis (4'-aminophenyl) -1, 3-diaminopropanol, N,N'-bis-(β-hydroxyethyl) -N,N'-bis (4'-aminophenyl) ethylene-
diamine, 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) ethyl enediamine and l,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane, and the addition salts thereof.
Among the para-aminophenols that may be used as oxidation bases in the dye compositions in accordance with the invention, mention may be made especially of the compounds corresponding to formula (III) below, and the addition salts thereof:
(Formula Removed) (III)
in which:
R4 represents a hydrogen atom; a halogen atom; an alkyl
radical; a monohydroxyalkyl radical; an alkoxyalkyl
radical; an aminoalkyl radical; a hydroxyalkylamino-
alkyl radical;
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;
it being understood that at least one of the radicals
R4 or R5 represents a hydrogen atom.
Among the para-aminophenols of formula (III) above, mention may be made more particularly of pars-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro-phenol, 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 and 4-amino-2-fluorophenol, and the addition salts thereof.
Among the ortho-aminophenols that may be mentioned, for example, are 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and the addition salts thereof.
Among the heterocyclic bases, mention may be made, for example, of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
Among the pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminc-pyridine, 2- (4-methoxyphenyl)amino-3-aminopyridine, 2, 3--diamino-6-methoxypyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxypyridine and 3,4-diaminopyridine, and the addition salts thereof.
Other pyridine oxidation bases that are useful in the present invention are the 3-aminopyrazolc-[1,5-a]pyridine oxidation bases or the addition salts thereof described, for example, in patent application FR 2 801 308. By way of example, mention may be made of pyrazolo[l,5-a]pyrid-3-ylamine; 2-acetylaminopyrazolo-[1,5-a]pyrid-3-ylamine; 2-morpholin-4-ylpyrazolo-[1,5-a]pyrid-3-ylamine; 3-aminopyrazolo[l,5-a]pyridine-2-carboxylic acid; 2-methoxypyrazolo [1,5-a]pyrid-3-yl-amine; (3-aminopyrazolo[1,5-a]pyrid-7-yl)methanol; 2-(3-aminopyrazolo[l,5-a]pyrid-5-yl)ethanol; 2-(3-amino-pyrazolo[1,5-a]pyrid-7-yl)ethanol; (3-aminopyrazolo-[1,5-a]pyrid-2-yl)methanol; 3, 6-diaminopyrazolo[1,5-a]-pyridine; 3,4-diaminopyrazolo[l,5-a]pyridine; pyrazolo-[1, 5-a]pyridine-3,7-diamin.e; 7-morpholin-4-ylpyrazolo-[1,5-a]pyrid-3-ylamine; pyrazolo[l,5-a]pyridine-3,5-diamine; 5-morpholin-4-ylpyrazolo[l,5-a]pyrid-3-yl-amine; 2-[(3-aminopyrazolo[1,5-a]pyrid-5-yl)(2-hydroxy-ethyl)amino]ethanol; 2-[(3-aminopyrazolo[1,5-a]pyrid-7-yl) (2-hydroxyethyl)amino]ethanol; 3-aminopyrazolo-[1,5-a]pyrid-5-ol; 3-aminopyrazolo[1,5-a]pyrid-4-ol;
3-aminopyrazolo f 1, 5-a]pyrid-6-ol; 3-aminopyrazolo-[1,5-a]pyrid-7-ol, and also the addition salts thereof.
Among the pyrimidine derivatives that may be mentioned are the compounds described, for example, in patents DE 2 359 399; JP 88-169 571; JP 05-63 124; EP 0 770 375 or patent application WO 96/15765, .such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triamino-pyrimidine, 2-hydroxy-4,5,6-triaminopyritnidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6-triamino-pyrimldine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which mention may be made of pyrazolo [1,5-a]-pyrimidine-3,7-diamine; 2,5-dimethylpyrazolo[1,5-a]-pyrimidine-3,7-diamine; pyrazolo[1,5-a]pyrimidine-3,5-diamine; 2,7-dimethylpyrazolo[l,5-a]pyrimidine-3,5-diamine; 3-aminopyrazolo[l,5-a]pyrimidin-7-ol; 3-amino-pyrazolo[l,5-a]pyrimidin-5-ol; 2-(3-aminopyrazolo[l,5-a]pyrimidin-7-ylamino)ethanol, 2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol, 2-[(3-aminopyrazolo[l,5-a]py£iraidin-7-yl)(2-hydroxyethyl) amino]ethanol, 2- [ (7-aminopyrazolo[1,5-a]pyrimidin-3-yl)[2-hydroxyethyl)-amino]ethanol, 5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine, 2,6-dimethylpyrazolo[l,5-a]pyrimidine-3,7-diamine, 2,5,N7,N7-tetzamethylpyrazolotl,5-a]pyrimi-dine- 3, 7-diamine and 3-amino-5-methyl-7-imidazolyl-propylaminopyrazolo[1,5-a]pyrimidine, and the addition salts thereof and the tautomeric forms thereof, when a tautomeric equilibrium exists.
Among the pyrazole derivatives that may be mentioned are the compounds described in patents DE 3 843 892 and DE 4 133 957 and patent applications, WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988, such as 4,5-diamino-l-methylpyrazole, 4,5-diamino-l-(β-hydroxy-ethyl)pyrazole, 3,4-diaminopyrazole, 4,5-diamino-l-(4'-chlorobenzyl)pyrazole, 4,5-diamino-l,3-dimethyl-pyrazole, 4,5-diamino-3-methyl-l-phenylpyrazole, 4,5-diamino-l-methyl-3-phenylpyrazole, 4-araino-l,3-
dimethyl-5-hydrazinopyrazole, l-benzyl-4, 5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-l-methyl-pyrazole, 4,5-diamino-l~tert-butyl-3-methylpyrazole, 4,5-diamino-l-(P-hydroxyethyl)-3-methylpyrazole, 4, 5-diamino-l-ethyl-3-methylpyrazole, 4,5-diamino-l-ethyl-3-(4' -methoxyphenyl)pyrazole, 4, 5-diamino-l-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-l-methylpyrazole, 4,5-diamino-3-hydroxymethyl-l-isopro-pylpyrazole, 4,5-diamino-3-methyl-l-isopropylpyrazole, 4-amino-5-(2'-arainoethyl)amino-l,3-dimethylpyrazole, 3, 4, 5-triaminopyrazole, l-methyl-3, 4,5-triaminopyra-zole, 3,5-diamino-l-methyl-4-methylaminopyrazole and 3, 5--diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole, and the addition salts thereof.
Preferably, the composition in accordance with the invention comprises at least one additional oxidation base chosen from para-aminophenols. Even. more preferentially, the composition in accordance with the invention comprises at least one additional oxidation base chosen from para-aminophenol, and the addition salts thereof.
The dye composition of the invention may contain additional couplers other than those that are useful in the present invention and conventionally used for dyeing keratin fibres.
The composition of the present invention may comprise, for example, at least one additional coupler chosen from meta-phenylenediamines, meta-aminophenols other than the meta-aminophenols of formula (II) , and the addition salts thereof, meta-diphenols, naphthalene-based couplers' and heterocyclic couplers.
Examples that may be mentioned include 3-aminophenol, 1,3-dihydroxybenzene, l,3-dihydroxy-2-methylbenzene, 4-chloro-l,3-dihydroxybenzene, 2, 4-diamino-l-(β-hydroxy-ethyldxy)benzene, 2-amino-4-(β-hydroxyethylamino)-1-
methoxybenzene, 1,3-diaminobenzene, l,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylaminobenzene, sesamol, l-β-hydroxyethylamino-3,4-methylenedioxybenzene, a-naphthol, 2-methyl-l-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxy-benzomorpholine 3, S-diamino-2,6-diffiethoxypyridine, 1-N-(β-hydroxyethyl) amino-3, 4-raethylenedioxybenzene and 2,6-bia (β-hydroxyethylamino) toluene, and the addition salts thereof.
Preferably, the composition in accordance with the invention comprises at least one additional coupler chosen from 2-amino-3-hydroxypyridine and 1,3-dihydroxy-2-methylbenzene., and the addition salts thereof.
The oxidation base(s) present in the composition of the invention is (are) each generally present in an amount of between 0.001% and 10% by weight approximately, and preferably between 0.005% and 6% by weight, relative to the total weight of the dye composition.
The coupler(s) present in the composition of the invention is (are) each generally present in an amount of between 0.001% arid 10% by weight approximately, and preferably between 0.005% and 6% by weight, relative to the total weight of the dye composition.
In general, the addition salts of the oxidation bases and of the couplers that may be used in the context of the invention are chosen especially from the addition salts with an acid, such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, (C1-C4)alkylsulfonates, tosylates, benzenesulfonates, phosphates and acetates, and the addition salts: with a base, such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.
The medium that is suitable for dyeing, also known as the dye support, is a cosmetic medium that generally consists of water or a mixture of water and at least one organic solvent to dissolve the compounds which would not be sufficiently soluble in water. As organic solvent, mention may be made, for example, of C1-C4 lower alkanols, such as ethsnol 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.
The solvents are present in proportions preferably cf between 1% and 401 by weight approximately relative to the total weight of the dye composition, and even more preferentially between 5% and 30% by weight approximately.
The dye composition in accordance with the invention can also contain various adjuvants conventionally used in compositions for dyeing the hair, such as .anionic, cationic, nonionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic or amphoteric associative polymeric thickeners, antioxidants, penetrants, sequestrants, fragrances, buffers, dispersants, conditioning agents, for instance silicones, which may be volatile or non-volatile, and modified or unmodified, film-forming agents, ceramides, preserving agents and opacifiers.
The above adjuvants are generally present in an amount for each of them of between 0.01% and 20% by weight relative to the weight of the dye composition.
Needless to say, a person skilled in the art will take
care to select this or these optional additional compounds such that the advantageous properties intrinsically associated with the oxidation dye composition in accordance with the invention are not, or are not substantially, adversely affected by the addition(s) envisaged,
The pH of the dye composition in accordance with the invention is generally between about 3 and 12 and preferably between about 5 and 11. It may be adjusted to the desired value using acidifying or basifying agents usually used in the dyeing of keratin fibres, cr alternatively using standard buffer systems.
Among the acidifying agents that may be mentioned, for example, are inorganic or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid and lactic acid, and sulfonic acids.
Among the basifying agents that may be mentioned, for example, are aqueous ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamine and derivatives thereof, sodium hydroxide, potassium hydroxide and the compounds of formula (IV) below:
(Formula Removed) (IV)
in which W is a propylene residue that is unsubstituted or substituted with a hydroxyi group or a C1-C4 alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical.
The dye composition according to the invention may be in various forms, such as in the form of liquids, creams or gels, or in any other form that is suitable for dyeing keratin fibres, and especially human hair.
The process of the present invention is a process in which the composition according to the present invention as described above is applied to the fibres, and the colour is developed using an oxidizing agent. The colour may be developed at acidic, neutral cr alkaline pH and the oxidizing agent may be added to the composition of the invention just at the time of use, or it may be used starting with an oxidizing composition containing it, which is applied simultaneously or sequentially to the composition of the invention. Preferably, this coloration is developed at neutral pH.
According to one particular embodiment, the composition according to the present invention is mixed, preferably at the time of use, with a composition containing, in a medium that is suitable for dyeing, at least one oxidizing agent, this oxidizing agent being present in an amount that is sufficient to develop a coloration. The mixture obtained is then applied to the keratin fibres. After a leave-on time of 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, the keratin fibres are rinsed, washed with shampoo, rinsed again and then dried.
The oxidizing agents conventionally used for the oxidation dyeing of keratin fibres are, for example, hydrogen peroxide, urea peroxide, alkali metal bxomates, persalts such as perborates and persulfates, peracids and oxidase enzymes, among which mention may be made of peroxidases, 2-electron oxidoreductases such as uricases, and 4-electron oxygenases, for instance laccases. Hydrogen peroxide is particularly preferred.
The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.

The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibres ranges preferably between 3 and 12 approximately and even more preferentially between 5 and 11. It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres and as defined above.
The ready-to-use composition that is finally applied to the keratin fibres may be in various forms, such as in the form of liquids, creams or gels or any other form that is suitable for dyeing keratin fibres, and especially human hair.
A subject of the invention is also a multi-compartment dyeing device or "kit", 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 an oxidizing composition. This device may be equipped with a means for applying the desired mixture to the hair, such as the devices described in patent FR-2 586 913 in the name of the Applicant.
A subject of the present invention is also the use, for
the oxidation dyeing of keratin fibres, and in
particular of human keratin fibres such as the hair, of
a composition as defined above.
According to one particular embodiment, the use of the composition in accordance with the invention on natural or permanent-waved grey hair containing 90% white hairs makes it possible to obtain a coloration having, according to the CIE.Lab notation, a value for L* of less than or equal to 50, a value for a* of between 10 and 25, a value for b* of between 3 and 25 and a ratio b*/a* of between 0.3 and 1 and preferably between 0.3

and 0.7.
The examples that follow serve to illustrate the invention without, however, being limiting in nature.
EXAMPLES
Bxamplo 1:
Composition 1 below was prepared:

(Table Removed)
At the time of use, 1 part by weight of composition 1 is mixed with 1.5 parts by weight of a 25-volumes hydrogen peroxide solution at pH 2.2. A final pH of 9.6 is obtained.
The mixture obtained is applied to locks of natural or permanent-waved grey hair containing 90% white hairs. After a leave-on time of 20 minutes at room temperature, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.
The hair coloration is evaluated visually. A red-chestnut shade is obtained.
The colour of the hair is measured using a Minolta CM 2002® spectrocolorimeter (illuminant D65 - 10° CSI) in the CIELab system.
The results obtained are given in the table below.

(Table Removed)
Example 2:
Composition 2 below was prepared:

(Table Removed)
The dyeing procedure is the same as that used in Example 1.
The hair coloration is evaluated visually. A red-light chestnut shade is obtained.
The colour of the hair is measured using a Minolta CM 2002® apectrocolorimeter (illurainant D65 - 10° CSI) in the CIELab system.
The results obtained are given in the table below.

(Table Removed)

1, Composition for dyeing keratin fibres, comprising, in a suitable medium:
• at least one first oxidation base chosen from 2,3-
diamino-6,7-dihydro-lH,5H-pyrazolo[l,2-a]pyrazol-l-one,
and the addition salts thereof;
• at least one second oxidation base, chosen from para-
phenylenediamine and para-tolylenediamine, and the
addition salts thereof; and
• at least one first coupler chosen from -che
substituted meta-aminophenols of formula (II) below,
and the addition salts thereof:

(Formula Removed)
in which:
R1 and R2, which may be identical or different,
represent a hydrogen atom; an alkyl radical; a
monohydroxyalkyl radical; a polyhydroxyalkyl radical; a
monoaminoalkyl radical; or
R1 and R2 form, together with the nitrogen atom to which
they are attached, a saturated or unsaturated, 5- to 7-
membered cyclic group containing one or more
heteroatoms, which may be unsubstituted or substituted
with one or more radicals chosen from carboxyl,
earboxamido, hydroxyl, amino, monoalkylamino and
dialkylamino radicals, and alkyl radicals optionally
substituted with one or more hydroxyl, amino,
monoalkylamino or dialkylamino radicals;
R3 represent, independently of each other, a halogen
atom; an alkyl radical; an alkoxy radical; a.
monohydroxyalkyl radical; a polyhydroxyalkyl radical; a
monohydroxyalkoxy radical; a polyhydroxyalkoxy radical;
n is an integer between 0 and 4;
with the proviso that when n is equal to O, then at
least one of the radicals R1 and R2 is other than a

hydrogen atom;
it being understood that the first coupler/first oxidation base mole ratio is greater than 1, the first oxidation base/second oxidation base mole ratio is between 0.5 and 1.5 and the molar amount of the first oxidation base is greater than or equal to 2.5x10-3 mol per 100 g of composition.
2. Composition according to Claim 1, in which R1 and
R2 represent, independently of each other, a hydrogen
atom; an alkyl radical; a monohydroxyalkyl radical; or
R1 and R2 form, together with the nitrogen atom to which
they are attached, a ring chosen from pyrrolidine,
piperidine, homopiperidine, piperazine, homopiperazine
and morpholine heterocyeles; the said rings possibly
being substituted with one or more hydroxyl, amino,
mono(C1-C2)alkylamino, di(C1-C2}alkylamino, carboxyl or
carboxaraido radicals, or CT.-C« alkyl radicals optionally
substituted with one or more hydroxyl, amino, mono(C1-C2
)alkylamino or di(C1-C2)alkylamino radicals.
3, Composition according to Claim 1 or 2, in which R3
is chosen from a halogen atom, an alkyl radical, an
alkoxy radical and a monohydroxyalkoxy radical.
4. Composition according to any one of the preceding
claims, in which n is between 0 and 2.
5, Composition according to any one of the preceding
claims, in which the substituted meta-aminophenol(s) of
formula (II) is (are) chosen from 5-amino-2-
methoxyphenol, 5-amino-2- ((3-hydroxyethyloxy)phenol, 5-
amino-2-methylphenol, 5-N-(β-hydroxyethyl)amino-2-
methylphenol, 5-N- (β-hydroxyethyl) amino-4-methoxy-2-
methylphenol, 5-amino-4-methoxy-2-methylpnenol, 5-
amino-4-chloro-2-methylphehol, 6-chloro-2-methyl-5-
aminophenol, 5-amino-2,4-dimethoxyphenol, 5-(y-hydroxy-
propylamino)-2-methylphenol, 3-dimethylaminophenol; 2-
methyl-5-dimethylaminophenol; 2-ethyl-5-dimethylaminc-
phenol; 2-methoxy-5-dimethylaminophenol; 2-ethoxy-5-dimethylaminophenol; 2- (β-hydroxyerthyl) -5-dimethyl-aminophenol; 3-diethylaminophenol; 2-methyl-5-diethyl-aminophenol; 2-ethyl-5-diethylaminophenol; 2-methoxy-S-diethylaminophenol; 2-ethoxy-5-diethylaminophenol; 2-(β-hydroxyethyl)-5-diethylaminophenol; 3-di(β-hydroxy-ethyl)aminophenol; 2-methyl-5-di (β-hydroxyethyl) amino-phenol; 2-ethyl-5-di(β-hydroxyethyl)aminophenol; 2-methoxy-5-di(β-hydroxyethyl)aminophenol; 2-ethoxy-5-di(β-hydroxyethyl)aminophenol; 2-O-hydroxyethyl)-5-di(β-hydroxyethyl)aminophenol; 3-pyrrolidin-l-ylphenol; 2-methyl-5-pyrrolidin-l-ylphenol; 2-ethyl-5-pyrrolidin-1-ylphenol; 2-methoxy-5-pyrrolidin-l-ylphenol; 2-ethoxy-5-pyrrolidin-l-ylphenol; 2-(β-hydroxyethyl)-5-pyrrolidin-1-ylphenol; 3-piperidin-l-ylphenol; 2-methyl-5-piperidin-l-ylphenol; 2-ethyl-5-piperidin-l-ylphenol; 2-methoxy-5-piperidin-l-ylphenol; 2-ethoxy-5-piperidin-1-ylphenol; 2-(β-hydroxyethyl)-5-piperidin-l-ylphenol; 3-piperazin-l-ylphenol; 2-methyl-5-piperazin-1-ylphenol; 2-ethyl-5-piperazin-l-ylphenol; 2-methoxy-5-piperazin-l-ylphen.ol; 2-ethoxy-5-piperazin-l-yl-phenol; 2-(β-hydroxyethyl)-5-piperazin-l-ylphenol; 3-(4-methylpiperazin-l-yl)phenol; 2-methyl-5-(4-methylpiperazin-l-yl) phenol; 2-ethyl-5-(4-methylpiperazin-l-yl ) phenol; 2-methoxy-5-(4-methylpiperazin-l-yl)phenol; 2-ethoxy-5-(4-methylpiperazin-l-yl)phenol; 2-(β-hydroxyethyl)-5-(4-methylpiperazin-l-yl)phenol; 3- (4-ethylpiperazin-1-yl)phenol; 2-methyl-5-(4-ethylpiper-azin-l-yl)phenol; 2-ethyl-5-(4-ethylpiperazin-l-yl)-phenol; 2-methoxy-5-(4-ethylpiperazin-l-yl)phenol; 2-ethoxy-5-(4-ethylpiperazin-l-yl)phenol; 2- (β-hydroxy-ethyl)-5-(4-ethylpiperazin-l-yl)phenol; 3-(4-(β-hydroxyethyl)piperazin-l-yl)phenol; 2-methyl-5-(4- (β-hydroxyethyl)piperazin-l-yl]phenol; 2-ethyl-5-(4-(β-hydroxyethyl)piperazin-i-yl)phenol; 2-methoxy-5-(4-(β-hydroxyethyl)piperazin-l-yl)phenol; 2-ethoxy-5-(4-(β-hydroxyethyl)piperazin-1-yl)phenol; 2-(P-hydroxyethyl)-5-(4-(β-hydroxyethyl)piperazin-1-yl)phenol; 3-morpho-lin-4-ylphenol; 2-methyl-5-morpholin-4-ylphenol; 2-

ethyl-5-morpholin-4-ylphenol; 2-methoxy-5-morpholin-4-ylphenol; 2-ethoxy-5-morpholin-4-ylphenol; 2-(β-hydroxyethyl)-5-morpholin-4-ylphenol.
6. Composition according to Claim 5, in which the
substituted meta-aminophenol(s) of formula (II) is
(are) chosen from 5-N-(β-hydroxyethylaraino)-2-
methy1phenol, 5-amino-2-methylphenol and 6-chloro-2-methyl-5-aminophenol.
7. Composition according to any one of the preceding
claims, in which the first coupler/first oxidation base
mole ratio is between 2 and 5.
8. Composition according to any one of the preceding
claims, in which the first oxidation base/second
oxidation base mole ratio is between 0.7 and 1.3.
9. Composition according to any one of the preceding
claims, comprising at least one additional oxidation
base chosen from para-aminophenols.
10. Composition according to Claim 9, comprising at
least one additional oxidation base chosen from para-
aminophenol, and the addition salts thereof.
11. Composition according to any one of the preceding
claims, comprising at least one additional coupler
chosen from 2-amino-3-hydroxypyridine and 1,3-
dihydroxy-2-methylbenzene, and the addition salts
thereof.
12. Composition according to any one of the preceding
claims, also: comprising ah oxidizing agent.
13. Process for dyeing keratin fibres, characterized
in that a composition as defined in any one of Claims 1
to 11 is applied to the keratin fibres in the presence
of an oxidizing agent, for a time that is sufficient to
develop the desired coloration.
14. Multi-compartment device, in which a first
compartment contains a dye composition as defined in
any one of Claims 1 to 11 and a second compartment
contains an oxidizing agent.
15. Use, for the oxidation dyeing of keratin fibres,
of a composition as defined in any one of Claims 1 tO
12.
16. Use according to Claim 15, for obtaining a
coloration on natural or permanent- waved grey hair
containing 90% white hairs having, according to the
CIELab notation, a value for L* of leas than or equal
to 50, a value for a* of between 10 and 25, a value for
b* of between 3 and 25 and a ratio b*/a* of between 0.3 and 1.