EP1432389A1

EP1432389A1 - Dyeing composition comprising a diaminopyrazole-type oxidation base, a paraphenylenediamine-type oxidation base with cyclic amino group and a coupling agent

Info

Publication number: EP1432389A1
Application number: EP02783225A
Authority: EP
Inventors: Sylvain Kravtchenko; Alain Lagrange
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 2001-09-28
Filing date: 2002-09-27
Publication date: 2004-06-30
Also published as: US20040231066A1; US7070629B2; FR2830191B1; FR2830191A1; WO2003028689A1

Abstract

The invention relates to a dyeing composition comprising a first diaminopyrazole-type oxidation base, a second paraphenylediamine-type oxidation base with cyclic amino group and a coupling agent. The invention also relates to the use of said composition for the dyeing of keratin fibres and to the dyeing method using said composition.

Description

Enter the TEXT OF THE PATENT below TINCTORIAL COMPOSITION INCLUDING A DIAMINOPYRAZOLE-BASED DOXIDATION, A PARAPHENYLENEDIAMINE-TYPE AMINO-CYCLIC-BASED DOXIDATION AND A COUPLER

The subject of the invention is a dye composition comprising a first oxidation base of the diaminopyrazole type, a second oxidation base of the paraphenylediamine type with a cyclic amino group and a coupler. Another subject of the invention is the use of this composition for dyeing keratin fibers as well as the dyeing process using this composition.

It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho or paraphenylenediamines, ortho or paraaminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored compounds.

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 metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as as indole compounds.

The variety of molecules involved in the oxidation bases and couplers, allows obtaining a rich palette of colors. The so-called "permanent" coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. Thus, it must be without drawbacks from the toxicological point of view, it must make it possible to obtain nuances in the desired intensity and have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and rubbing.

The dyes must also make it possible to cover gray hair, and finally to be the least selective possible, that is to say allow to obtain deviations from weakest coloration possible throughout the same keratin fiber, which is generally sensitized differently (ie damaged) between its tip and its root.

Dye compositions are already known comprising, as the oxidation base, diaminopyrazole derivatives. For example, patent application DE 3843892 describes dye compositions for dyeing keratinous fibers comprising 4,5-diaminopyrazole derivatives which can be substituted in position 2 by alkyl or hydroxyalkyl radicals. Patent application EP 692 245 describes dye compositions comprising 4,5-diaminopyrazole derivatives associated with particular metaphenylenediamines. Patent application DE 19643059 describes dye compositions combining 4,5-diaminopyrazole derivatives with metaaminophenol and metaphenylenediamine couplers. Patent application DE 19646609 describes dye compositions combining 4,5-diaminopyrazole derivatives with benzoxazine couplers.

It is moreover known in patent application JP 11158048 to use dye compositions comprising derivatives of paraphenylenediamine in which one of the nitrogen atoms is included in a 5 to 7-membered ring. US Patent 5,851,237 proposes the use of 1- (4-aminophenyl) pyrrolidine derivatives optionally substituted on the benzene ring in order to replace paraphenylenediamine. US Patent 5,993,491 proposes the use of N- (4-aminophenyl) -2- (hydroxymethyl) -pyrrolidines derivatives optionally substituted on the benzene nucleus in order to replace paraphenylenediamine.

The shades obtained from dye compositions containing this type of oxidation base are however not sufficiently powerful, chromatic and / or tenacious. The object of the present invention is to provide new dye compositions for dyeing keratin fibers containing diaminopyrazole derivatives which do not have the drawbacks of those of the prior art. In particular, the object of the present invention is to provide dye compositions containing diaminopyrazole derivatives which are not very selective and particularly resistant, while being capable of generating intense colorings in various shades. This JDut is achieved with the present invention which relates to a dye composition comprising, in an appropriate dyeing medium, • at least one 4,5-diaminopyrazole oxidation base of formula (I) or the corresponding addition salts

in which R1 is a C ₆ -C ₆ alkyl radical substituted by one or more OR radicals, R being a CC ₆ alkyl radical,

• at least one oxidation base chosen from the para-phenylenediamine derivatives of formula (II) below, or their addition salts

in which

Z represents the atoms necessary to form a saturated 3 to 8-membered ring, these atoms being able to be carbon or nitrogen atoms, preferably only carbon atoms, the ring being able to be substituted,

- R2 represents a hydrogen atom; a halogen atom chosen from a chlorine and bromine atom; a saturated or unsaturated, linear or branched C _r C ₇ hydrocarbon chain of which one or more carbon atoms may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and whose atoms carbons can be, independently of each other, substituted by one or more halogen atoms; said radical R ₂ not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals,

- at least one coupler. The composition of the present invention makes it possible in particular to obtain a coloration of the keratin fibers chromatic, very powerful, not very selective and tenacious.

Another subject of the invention is the use of the composition of the present invention for dyeing keratin fibers, in particular human keratin fibers such as the hair.

The subject of the invention is also a device and a dyeing process using the composition of the invention.

In the context of the present invention, the term “alkyl” means linear or branched radicals, comprising, unless otherwise indicated, from 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl , isopropyl, butyl, etc. The term alkoxy means alkyl-O-, the alkyl radical being as defined above.

According to a particular embodiment, the 4,5-diaminopyrazole oxidation base of formula (I) is such that R1 represents a C _r C ₄ , preferably C ₂ -C ₄ , alkyl radical substituted by an OR radical, R being a C ₁ -C ₄ alkyl radical. preferably in C1-C2. Preferably, the oxidation base of formula (I) is 4,5-diamino-1- (2'-methoxyethyl) -pyrazole.

According to the present invention, the cycle formed with Z and the nitrogen atom of paraphenylenediamine can be a pyrrolidine, piperidine, homopiperidine, imidazoline, pyrazolidine, piperazine ring. The saturated cycle thus formed can be substituted. By way of example, there may be mentioned as a substitute for the halogen atoms, the hydroxyl radical, the amino radical, the C _r C ₄ alkyl radicals optionally substituted by one or more hydroxy, amino, (di) alkylamino radicals CC ₂ , carboxy; the carboxy radical; carbamoyl or sulfonamido radicals; -OR5 radicals in which R5 represents a C1-C4 alkyl radical substituted by one or more radicals chosen from a halogen atom, C1-C2 alkoxy radicals, amino, C1- aminoalkyl

C2 or C3-C4 alkyl substituted by one or more hydroxyl radicals; a methylcarbonyl radical; a radical -NR6R7 in which R6 and R7 represent, independently of each other, a hydrogen atom, a C1-C4 alkyl radical substituted by one or more radicals chosen from a halogen atom, hydroxyl radicals , C1-C2 alkoxy, amino or C1-C2 aminoalkyl. According to a particular embodiment, Z represents the carbon atoms necessary to form a ring comprising from 5 to 8 members, preferably a pyrrolidine ring, substituted or not.

According to the invention, a saturated or unsaturated, linear or branched hydrocarbon chain of formula (II) is a chain which can comprise one or more double bonds and / or one or more triple bonds, and can form one or more rings comprising 3 to 6 links, the double bonds possibly leading to aromatic groups. When it is indicated that one or more of the carbon atoms of R2 can be replaced by an oxygen, nitrogen or sulfur atom or by an SO _2l group and / or that said radical R2 can be unsaturated, this means that we can, for example, make the following transformations:

I - CH— H can become -O-H

can become

According to the invention, R2 preferably represents a hydrogen atom, an alkyl radical, an alkenyl radical, an alkynyl radical, an alkoxyalkyl radical, a hydroxyalkyl radical, an alkoxy radical, an allyloxy radical, a hydroxyaminoalkyl radical, a hydroxyalkoxy radical. , a carboxyalkyl radical, an aminoalkyl radical.

By way of example, there may be mentioned for R2 the methyl, ethyl, isopropyl, vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl radicals,

1-aminomethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl,

1, 2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, methoxy, ethoxy, allyloxy or

2-hydroxyethyloxy. Preferably, R2 represents a hydrogen atom, a radical methyl, hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, methoxy, or 2-hydroxyethoxy, preferably a hydrogen atom or a methyl radical.

According to a particular embodiment, the oxidation base chosen from paraphenylenediamine derivatives is a paraphenylediamine derivative with a pyrrolidine grouping corresponding to the following formula (IIa)

in which

- R2 is as defined above, - R3 represents a hydrogen atom; a hydroxyl radical; an amino radical; a radical -OR5 in which R5 represents a C1-C4 alkyl radical substituted by one or more radicals chosen from a halogen atom, C1-C2 alkoxy, amino, C1-C2 aminoalkyl or mono- or poly- C1-C4 hydroxyalkyl; a methylcarbonyl radical; a radical -NR6R7 in which R6 and R7 represent, independently of one another, a hydrogen atom, a C1-C4 alkyl radical which may be substituted by one or more radicals chosen from a halogen atom, the hydroxyl radicals, C1-C2 alkoxy, amino of C1-C2 aminoalkyl,

- R4 represents a hydrogen atom; a carbamoyl radical, an amido radical; a C1-C5 mono- or poly-hydroxyalkyl radical. According to a particular embodiment, R3 represents a hydrogen atom, a hydroxyl, acetoxy, amino, alkylamino, hydroxyalkylamino radical. By way of example, there may be mentioned for R3 a hydrogen atom, a hydroxyl, acetoxy, amino, methylamino, dimethylamino or 2-hydroxyethylamino radical. Preferably, R3 represents a hydrogen atom, a hydroxyl radical or an amino radical. In the formula (IIa), R4 preferably represents a hydrogen atom, a carbamoyl radical, a hydroxy radical, a C1-C4 hydroxyalkyl radical, a methyl radical.

By way of example, the para-phenylenediamine derivatives of formula (II) are chosen from N- (4-aminophenyl) -3-hydroxy-pyrrolidine, N- (4-amino-2-methylphenyl) -3-hydroxypyrrolidine, N- (4-amino-2-ethylphenyl) -3-hydroxypyrrolidine, N- (4-amino-2-methoxyphenyl) -3-hydroxy-pyrrolidine, N- (4-amino-2- (2-hydroxyethyl ) phenyl) -3-hydroxypyrrolidine, N- (4-amino-2- (1-hydroxyethyl) phenyl) -3- hydroxypyrrolidine, N- (4-amino-2- (1, 2-dihydroxy-ethyl) phenyl ) -3-hydroxypyrrolidine, N- (4-amino-3-methyl-phenyl) -3-hydroxypyrroIidine, N- (4-amino-3-ethylphenyl) -3- hydroxypyrrolidine, N- (4-amino- 3-methoxyphenyl) -3-hydroxypyrrolidine, N- (4- amino-3- (2-hydroxy-ethyl) phenyl)) -3-hydroxypyrrolidine, N- (4-amino-3- (1- hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3- (1, 2-dihydroxyethyl) phenyl) - 3-hydroxy-pyrrolidine, N- (4-amino-phenyl) -3-aminopyrrolidine, N- ( 4-amino-2- methyl-phenyl) -3-aminopyrrolidine, N- (4-amino-2-ethylphenyl) -3- aminopyrrolidine, N- (4-amino-2-methoxyphenyl) -3-aminopyrrolidine, N- (4-amino-2- (2-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4-amino -2- (1-hydroxyethyl) phenyl) -

3-aminopyrrolidine, N- (4-amino-2- (1, 2-dihydroxyethyl) phenyl) -3-hydroxy-pyrrolidine, N- (4-amino-3-methylphenyl) -3-aminopyrrolidine, N- (4-amino-3-ethylphenyl) -3- aminopyrrolidine, N- (4-amino-3-methoxyphenyl) -3-amino-pyrrqlidine, N- (4-amino- 3- (2-hydroxy-ethyl) phenyl) -3-aminopyrroiidine, N- (4-amino-3- (1-hydroxyethyl) phenyl) - 3-aminopyrrolidine, N- (4-amino-3- (1, 2-dihydroxyethyl) phenyl) -3 -aminopyrrolidine, 1- (4-aminophenyl) -pyrrolidine, 1- (4-aminophenyl) -2-pyrrolidinemethanol, 1- (4- aminophenyl) -4-hydroxy-2-pyrrolidinemethanol, N- (4- aminophenyl) -prolineamide and their addition salts with an acid. Preferably, the para-phenylenediamine derivatives of formula (IIa) are chosen from 3-hydroxy 1- (4'-aminophenyl) pyrrolidine, 3-amino 1- (4'aminophenyl) pyrrolidine, 1- (4-aminophenyl) - pyrrolidine, 1- (4-aminophenyl) -2-pyrrolidinemethanol, 1- (4-aminophenyl) -4- hydroxy-2-pyrrolidinemethanol, N- (4-aminophenyl) -prolineamide and their addition salts.

The coupler useful in the composition of the present invention can be any coupler conventionally used in the field of coloring. This coupler can be chosen from metaphenylenediamines, meta-aminophenols, metadiphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

By way of example, mention may be made of 2-methyl 5-aminophenol, 5-N- (β-hydroxyethyl) amino 2-methyl phenol, 6-chloro-2-methyl-5-aminophenol, 3-amino phenol, 1,3-dihydroxy benzene, 1,3-dihydroxy 2-methyl benzene, 4-chloro 1,3-dihydroxy benzene, 2,4-diamino l- (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 , sesamol, 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2 methyl-1-nàphtoI, 6-hydroxy indole, 4-hydroxy indole, 4-hydroxy N-methyl indole, 2-amino-3-hydroxy pyridine, 6-hydroxy benzomorpholine 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 with an acid. In the composition of the present invention, the ^'the couplers are each present in an amount between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%.

The composition of the present invention may also comprise one or more additional oxidation bases conventionally used in oxidation dyeing other than those described above. By way of example, these additional oxidation bases are chosen from para-phenylenediamines other than those described above, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases other than those described above and 'addition. Among the paraphenylenediamines, there may be mentioned by way of example, paraphenylenediamine, paratoluylenediamine, 2-chloro paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino N, N-diethyl 3-methyl aniline, N, N- bis- (β- hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino 2-methyl aniline, 4-N, N-bis- (β-hydroxyethyl) amino 2-chloro aniline, 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, 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- N- (β-methoxyethyl) paraphenylenediamine, 2-thienyl paraphenylenediamine, 2-β hydroxyethylamino 5-amino toluene, and their addition salts with an acid. Among the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine para-phenylenediamine, 2,3-dimethyl para-phenylenediamine, N, N-bis- (β-hydroxyethyl) para-phenylenediamine, 2-chloro para-phenylenediamine, 2-beta-acetylaminoethyloxy para-phenylenediamine, and their acid addition salts are particularly preferred .

Among the bis-phenylalkylenediamines, there may be mentioned by way of 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-methyl-aminophenyl) 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 the para-aminophenols, there may be mentioned by way of example, para-aminophenol, 4-amino 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4- amino 2-methyl phenol, 4-amino 2-hydrpxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- (β-hydroxyethyl aminomethyl) phenol, 4- amino 2-fluoro phenol, and their addition salts with an acid. Among the ortho-aminophenols, there may be mentioned by way of example, 2-amino phenol, 2-amino 5-methyl phenol, 2-amino 6-methyl phenol, 5-acetamido 2-amino phenol, and their addition salts with an acid.

Among the heterocyclic bases other than those useful in the present invention, there may be mentioned by way of example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives other than those of the invention.

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- (β-methoxyethyl) amino 3-amino 6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid or a base.

Other pyridine oxidation bases useful in the present invention are the 3-amino pyrazolo- [1,5-a] -pyridine oxidation bases or their addition salts described for example in patent application FR 2801308. By way of example, mention may be made of pyrazolo [1, 5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo- [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yI-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridine-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridine-7-yI) -methanol; 2- (3-amino-pyrazolo [1,5-a] pyridine-5-yl) -ethanol; 2- (3-amino-pyrazolo [1,5-a] pyridine-7-yl) - ethanol; (3-amino-pyrazolo [1,5-a] pyridine-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazoIo [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] pyπidin-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] pyridine-5-ol; 3-amino-pyrazolo [1,5-a] pyridine-4-ol; 3-amino-pyrazolo [1,5-a] pyridine-6-oi; 3-amino-pyrazolo [1,5-a] pyridine-7-ol as well as their addition with an acid or with a base.

Among the pyrimidine derivatives, mention may be made of the compounds described for example in patents DE 2,359,399; JP 88-169,571; JP 05 163 124; EPO 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetra-aminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy 5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolo-pyrimidine derivatives such as those mentioned in patent application FR-A-2 750 048 and among which may be mentioned 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-hydroxy-ethyl) -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 there is a tautomeric equilibrium. Among the pyrazole derivatives, mention may be made of the compounds described in patents DE 3 843 892, DE 4 133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 such as 4,5-diamino 1-methyl pyrazole, 4,5-diamino l- (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 l- (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 with an acid. The oxidation base or bases present in the composition of the invention are generally each present in an amount of between 0.001 to 10% by weight approximately of the total weight of the dye composition, preferably between 0.005 and 6%.

In general, the addition salts of the oxidation bases and of the couplers which can be used in the context of the invention are in particular chosen from addition salts with an acid such as hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as soda, potash, ammonia, amines or alkanolamines. The dye composition in accordance with the invention may also contain one or more direct dyes which can in particular be chosen from nitro dyes from the benzene series, azo direct dyes and methine direct dyes. These direct dyes can be of nonionic, anionic or cationic nature. . The medium suitable for dyeing, also called dye support, generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvent, mention may, for example, be made of lower C _r C ₄ alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

The 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.

The dye composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or their mixtures, anionic polymers, cationic, non-ionic, amphoteric, zwitterionic or mixtures thereof, mineral or organic thickening agents, and in particular associative polymeric thickeners anionic, cationic, nonionic and amphoteric, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example volatile or non-volatile silicones, modified or not modified, film-forming agents, ceramides, preserving agents, opacifying agents.

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 composition. Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the oxidation dye composition according to the invention are not, or not substantially, altered. spoke or the 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 basifying agents usually used in dyeing keratin fibers or even using conventional buffer systems.

Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulfonic acids.

Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and triethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of formula (III) below:

in which W is a propylene residue optionally substituted by a hydroxyl group or a C ₁ -C ₄ alkyl radical; R _a, R _b, R _c and R _d, identical or different, represent a hydrogen atom, an alkyl radical with C, -C ₄ alkyl or hydroxy C ₁ -C _4. The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair. According to the dyeing process of the present invention, the composition according to the present invention 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 mixed with the composition of the invention just at the time of use or it can be implemented from an oxidizing composition containing it ,

10. applied simultaneously or sequentially to the composition of the invention.

According 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 enough to develop color.

The mixture obtained is then applied to the keratin fibers. After an exposure time of 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, the keratin fibers are rinsed, washed with shampoo, rinsed again and then dried.

The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are for example hydrogen peroxide, urea peroxide,

20 alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes among which may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred.

The oxidizing composition may also contain various adjuvants used

25 conventionally in compositions for dyeing hair and as defined above for the composition of the invention.

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 fibers varies between 3 and 12 approximately, and preferably

30 between 5 and 11. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above. The ready-to-use composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers, and especially human hair. Another object of the invention is a device with several compartments or

Dye "kit" in which a first compartment contains the dye composition of the invention defined above and a second compartment contains an oxidizing composition. This device can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.

The diaminopyrazole compounds useful in the composition of the present invention are known compounds which can be obtained from general preparation methods known to those skilled in the art. For example, the synthetic approach shown below is described in the literature up to intermediary (2) (JHP Juffermanns, C. L; Habraken; J. Org.Chem., 1986, 51, 4656; Klebe and al.; Synthesis, 1973, 294; R. Hϋttel, F. Bϋchele; Chem. Ber.; 1955, 88, 1586.). In the present case, the passage from compound 3 to compound 2 is carried out by means of a NH ₃ / EtOH mixture.

The alkylation and amination to arrive at the compounds of formula (!) According to the invention are mentioned in document DE 42 34 885.

The paraphenylediamine derivatives useful in the context of the present invention are known compounds which can be obtained from conventional syntheses within the reach of those skilled in the art. In particular, the paraphenylediamine derivatives with a pyrrolidine group can be prepared according to the synthetic methods described in particular in patent application DE 4 241 532 (AGFA), FR 2806299, American patents N ° - 5851237, 5876464, and 5993491.

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

EXAMPLES Example 1. Synthesis of 4,5-Diamino-1- (2 ^, -methoxyethyl) -pyrazole dichlorhvdrate

A mixture of 5-benzylamino-3-bromo-1- (2'-methoxyethyl) -4- nitropyrazole (4 g, 2.8 mmol) in ethanol (500 ml) containing a 10% Pd / C catalyst ( Johnson-Mattey Type 487, dry weight 0.5 g) and 36% hydrochloric acid (0.57 g, 5.6 mmol) is hydrogenated in a Parr Autoclave (1 I) at 1 MPa for 1 hour. The catalyst is then removed by filtration, washed with ethanol and the filtrate evaporated under reduced pressure. A crude orange solid (2.8 g) is thus obtained which has been triturated in AcOEt (20 ml) for 1 h. The solid is then filtered and washed with cold AcOEt (20 ml) then dried under vacuum to give 4,5-Diamino-1- (2'- methoxyethyl) -pyrazole in the form of a beige solid (0, 7 g, 27%). HPLC (purity): 99.5% m.p .: 168.1-173.0 ° C

NMR: ¹ H (400 MHz, d ⁶ -DMSO): 7.34 (1 H, s, NH _arom ), 5.18 (1 H, s _broad , NH), 4.09 (2 H, t, J = 5.5 Hz, CH ₂ N), 3.61 (2 H, t, J = 5.5 Hz, CH ₂ O), 3.23 (3 H, s, OCH ₃ ).

Example 2. Dye composition containing 4,5-Diamirto-1- (2-methoxyethvD-pyrazole dichlorhvdrate

The following dye composition was prepared:

Dye support

Benzyl alcohol 2 g Polyethylene glycol 8 EO 3 g Ethanol 18 g

Alkyl (C8-C10) polyglucoside in aqueous solution at 60% of active material buffered by ammonium citrate sold under the name ORAMIX CGT10 by SEPPIC 5 g as is

Ammonia at 20% NH3 10 g

Sodium metabisulfite 0.205 g

Sequestering q.s.

At the time of use, the composition is mixed with an equal weight of hydrogen peroxide at 20 volumes (6% by weight).

The mixture obtained is applied to locks of gray hair containing 90% natural and permanent whites at a rate of 10 g per 1 g of hair. After 30 min of laying, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried.

The wicks are evaluated visually. This gives an ashy purple color.

Claims

1. Dye composition comprising, in an appropriate dyeing medium, • • at least one 4,5-diaminopyrazole oxidation base of formula (I) or the corresponding addition salts

in which R1 is a CC ₆ alkyl radical substituted by one or more OR radicals, R being a C ^ Ce alkyl radical,

in which

Z represents the atoms necessary to form a saturated ring of 3 to 8 members, these atoms being able to be carbon or nitrogen atoms, the ring being able to be substituted,

- R2 represents a hydrogen atom; a halogen atom chosen from a chlorine and bromine atom; a saturated or unsaturated, linear or branched C _r C ₇ hydrocarbon chain, one or more carbon atoms of which may be replaced by an oxygen, nitrogen or sulfur atom or by an SO ₂ group, and whose atoms carbons can be, independently of each other, substituted by one or more halogen atoms; said radical R ₂ not comprising a peroxide bond, nor of diazo, nitro or nitroso radicals, - at least one coupler.

2. Composition according to claim 1 in which the oxidation base of formula (I) is such that R1 represents a C1-C4 alkyl radical substituted by an OR radical, R being a C1-C4 alkyl radical.

3. Composition according to claim 2 in which the oxidation base of formula (I) is 4,5-diamino-1- (2'-methoxyethyl) -pyrazole.

4. Composition according to any one of the preceding claims, in which the oxidation base chosen from the para-phenylenediamine derivatives of formula (II) is such that Z represents the carbon atoms necessary to form a saturated 5 to 8-membered ring.

5. Composition according to any one of the preceding claims, in which R ₂ represents a hydrogen atom, an alkyl radical, an alkenyl radical, an alkynyl radical, an alkoxyalkyl radical, a hydroxyalkyl radical, an alkoxy radical, an allyloxy radical. , a hydroxyaminoalkyl radical, a hydroxyalkoxy radical, a carboxylalkyl radical, an aminoalkyl radical.

6. Composition according to claim 5 in which R ₂ represents a hydrogen atom, a radical chosen from methyl, ethyl, isopropyl, vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl, 2-carboxyethyl radicals, 2-hydroxyethyl, 3-hydroxypropyl, 1, 2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, methoxy, ethoxy, allyloxy or 2-hydroxyethyloxy.

7. The composition as claimed in claim 6, in which R ₂ represents a hydrogen atom, a methyl, hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, methoxy or 2-hydroxyethoxy radical.

8. Composition according to any one of the preceding claims, in which Z represents only carbon atoms.

•

9. Composition according to any one of the preceding claims, in which the oxidation base chosen from paraphenylenediamine derivatives corresponds to the following formula (IIa)

in which - R2 is as defined in any one of claims 1 to 7,

- R3 represents a hydrogen atom, a hydroxyl radical; an amino radical; a radical -OR5 in which R5 represents a C1-C4 alkyl radical substituted by one or more radicals chosen from a halogen atom, C1-C2 alkoxy, amino, C1-C2 aminoalkyl or mono- or poly- C1-C4 hydroxyalkyl; a methylcarbonyl radical; a radical -NR6R7 in which R6 and R7 represent, independently of one another, a hydrogen atom, a C1-C4 alkyl radical which may be substituted by one or more radicals chosen from a halogen atom, the hydroxyl, C1-C2 alkoxy, amino or C1-C2 aminoalkyl radicals,

- R4 represents a hydrogen atom; a carbamoyie radical, an amido radical, a C1-C5 mono- or poly-hydroxyalkyl radical.

10. Composition according to Claim 9, in which 'R3 represents a hydrogen atom, a hydroxyl, acetoxy, amino, alkylamino, hydroxyalkylamino radical.

11. Composition according to claim 10 in which R3 represents a hydrogen atom, a hydroxyl, acetoxy, amino, methylamino, dimethylamino or 2-hydroxyethylamino radical.

12. Composition according to claim 11 in which R3 represents a hydrogen atom, a hydroxyl radical or an amino radical.

13. Composition according to any one of claims 9 to 12 in which R4 represents a hydrogen atom, a carbamoyie radical, a C1-C4 hydroxyalkyl radical, a methyl radical.

14. Composition according to any one of the preceding claims, in which the paraphenylenediamine derivatives of formula (II) are chosen from N- (4-aminophenyl) -3-hydroxy-pyrrolidine, N- (4-amino-2- methylphenyl) -3- hydroxypyrrolidine, N- (4-amino-2-ethylphenyl) -3-hydroxypyrrolidine, N- (4-amino-2- 5 methoxyphenyl) -3-hydroxy-pyrrolidine, N- (4- amino-2- (2-hydroxyethyl) phenyl) -3- hydroxypyrrolidine, N- (4-amino-2- (1-hydroxyethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-2- (1 , 2-dihydroxy-ethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3-methyl-phenyl) -3-hydroxypyrrolidine, N- (4-amino-3-ethylphenyl) -3-hydroxypyrrolidine, N- (4-amino-3-methoxyphenyl) -3-hydroxypyrrolidine, N- (4-amino-3- (2-hydroxy-

[0 ethyl) phenyl) -3-hydroxypyrrolidine, N- (4-amino-3- (1-hydroxyethyl) phenyl) -

3-hydroxypyrrolidine, N- (4-amino-3- (1, 2-dihydroxyethyl) phenyl) -3-hydroxy-pyrroiidine, N- (4-amino-phenyl) -3-aminopyrroIidine, N- (4 -amino-2-methyl-pheny!) - 3-aminopyrrolidine, N- (4-amino-2-ethyiphenyl) -3-aminopyrrolidine, N- (4-amino-2-methoxyphenyl) -3-aminopyrroIidine, N- (4-amino-2- (2-hydroxy-ethyl) phenyl) -3-

15 aminopyrrolidine, N- (4-amino-2- (1-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4-amino-2- (1,2-dihydroxyethyl) phenyl) -3-hydroxy-pyrrolidine , N- (4-amino-3-methylphenyl) -3-aminopyrrolidine, N- (4-amino-3-ethylphenyl) -3-aminopyrrolidine, N- (4-amino-3-methoxyphenyl) -3- amino-pyrrolidine, N- (4-amino-3- (2-hydroxyethyl) phenyl) -3-aminopyrrolidine, N- (4-amino-3- (1-hydroxyethyl) phenyl) -3-

20 aminopyrrolidine, N- (4-amino-3- (1, 2-dihydroxyethyl) phenyl) -3-aminopyrrolidine, 1- (4-aminophenyl) -pyrrolidine, 1- (4-aminophenyl) -2-pyrrolidinemethane , 1- (4-aminophenyl) -4-hydroxy-2-pyrrolidinemethanol, N- (4-aminophenyl) -prolineamide and their acid addition salts.

15. Composition according to any one of the preceding claims, in which the coupler is chosen from metaphenylenediamines, meta-aminophenols, metadiphenols, naphthalene couplers, heterocyclic couplers and their addition salts.

16. Composition according to Claim 15, in which the amount of each of the couplers is between 0.001 and 10% by weight approximately of the total weight 0 of the dye composition.

17. Composition according to any one of the preceding claims, comprising an additional oxidation base chosen from paraphenylenediamines other than the oxidation bases of formula (II), bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases other than the oxidation bases of formula (1) and their addition salts .

18. Composition according to any one of the preceding claims, in which the amount of each of the oxidation bases is between 0.001 to 10% by weight approximately of the total weight of the dye composition.

19. Composition according to any one of claims 1 to 18 comprising an oxidizing agent.

20. Composition according to claim 19 in which the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.

21. Process for the oxidation dyeing of keratin fibers, characterized in that at least one composition as defined in any one of claims 1 to 18 is applied to the fibers, and the color is revealed using an oxidizing agent.

22. The method of claim 21 wherein the oxidizing agent is selected from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts, peracids and oxidase enzymes.

23. Method according to one of claims 21 or 22 in which the oxidizing agent is mixed at the time of use with the composition as defined according to any one of claims 1 to 18.

24. Method according to any one of claims 21 or 22 in which the oxidizing agent is applied to the fibers in the form of an oxidizing composition simultaneously or sequentially with the composition as defined according to any one of claims 1 to 18.

25. Multi-compartment device in which a first compartment contains a dye composition as defined in any one of claims 1 to 18 and a second compartment contains an oxidizing composition.

26. Use of the dye composition defined in claims 1 to 20 for the dyeing of keratin fibers.