FR2971708A1 - Composition, useful for coloring human keratin fibers, comprises oxidation dye precursor comprising oxidation bases and/or couplers comprising heterocycle containing non-saturations, and propionic acid compound - Google Patents

Abstract

Composition comprises (a) at least one oxidation dye precursor comprising oxidation bases and/or couplers comprising at least one heterocycle containing one or more non-saturations, and (b) at least one propionic acid compound (I). Composition comprises (a) at least one oxidation dye precursor comprising oxidation bases and/or couplers comprising at least one heterocycle containing one or more non-saturations, and (b) at least one propionic acid compound of formula (N +>((R1)(R2)(R3))-CH 2-CH(OH)-CH(R4)-C(=O)-O ->) (I). R1-R3 : 1-30C alkyl, 2-30C alkenyl, 2-30C alkynyl (all optionally substituted by 6-30C aryl, 1-30C alkyl-6-30C aryl or 6-30C aryl-1-30C alkyl, and/or optionally interrupted by at least one O or 6-30C aryl (optionally substituted by R1-R3)), or 1-20C (preferably 1-14C) alkyl (all optionally substituted by at least one halo, preferably F, NH 2, OH or 1-2C alkoxy); R4 : H, 1-30C alkyl, 2-30C alkenyl, 2-30 alkynyl (optionally substituted and/or optionally interrupted by at least one O, -NR-, -N +>(R) 2- groups, 5-6-membered heterocycle (optionally substituted by one or more heteroatom comprising O, N or optionally carrying at least one cationic charge)), 1-30C alkoxy (optionally substituted), OH or NH 2, where the amino carries one or two 1-30C (preferably 2-20C) alkyl (optionally substituted); and R : H or 1-30C alkyl (optionally substituted). Independent claims are included for: (1) dyeing human keratin fibers, comprising applying the composition to the fibers in the presence of at least one oxidizing agent; and (2) a multi-compartment device comprising a first compartment, and another a composition comprising at least one oxidizing agent.

Description

The subject of the present invention is a dyeing composition comprising, in a suitable medium, at least one dye precursor of at least one dye precursor and at least one dye precursor comprising at least one dyestuff precursor and at least one dye precursor. heterocyclic oxidation and carnitine and / or one of its derivatives, as well as a staining method using such a composition in the presence of an oxidizing agent and a multi-compartment device usable for this purpose. It also relates to the use for improving the storage stability of compositions intended for the oxidation dyeing of human keratin fibers, carnitine and / or its derivatives.

Among the methods for staining human keratinous fibers, such as the hair, mention may be made of oxidation or permanent staining. More particularly, this mode of staining uses one or more oxidation dye precursors, more particularly one or more oxidation bases possibly associated with one or more couplers.

Usually, oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or para-aminophenols as well as heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, combined with oxidizing products, make it possible to access colored species by a process of oxidative condensation.

Very often, the shades obtained with these oxidation bases are varied by combining them with one or more couplers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds. The variety of molecules involved in the oxidation bases and couplers makes it possible to obtain a rich palette of colors. This staining mode can also be combined with direct or semipermanent staining. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and dyeing molecules, having an affinity for the fibers, to be allowed to pausate to allow the molecules to penetrate, by diffusion, inside. fiber, then rinse them. The direct dyes generally employed are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine or triarylmethane direct dyes.

One of the disadvantages of staining methods is that the compositions used practically comprise reducing agents or antioxidants. These agents contribute in particular to the stabilization of the composition during the dyeing process itself, in particular to avoid a too rapid reaction of the ingredients (essentially the oxidation dyes) with the oxidizing agent, which would have the consequence of limiting the penetration of the reagents into the hair and thus make the color less stubborn. They also make it possible to stabilize the composition during storage.

When small antioxidants, such as ascorbic acid, are used in the dyeing compositions, it has been observed that they interfere negatively with the coloring in the hair.

One of the aims of the present invention is therefore to color in a powerful and homogeneous manner, while having compositions that do not significantly alter storage.

It is also noted that the phenomenon of variation of the coloration of the composition just after the mixing with the oxidizing agent and after the pause time of the composition on the fibers, was greatly slowed down. This phenomenon, quite conventional in oxidation dyeing, is characteristic of the degree of progress of the aforementioned oxidative condensation reaction, leading to the appearance of the colored species.

This slowdown is an advantage in many ways.

In particular, it reduces the discomfort that this color variation may have on the user, especially when the coloring of the composition does not correspond exactly to that obtained on the hair. This slowdown also reduces the risk of staining of the skin and textiles.

It is also a sign of an increase in coloring efficiency since the colored species appearing during the pause time is in the fiber itself rather than outside.

Thus, the subject of the invention is a composition for the dyeing of human keratin fibers, comprising a) at least one oxidation dye precursor chosen from oxidation bases and / or couplers comprising at least one heterocycle containing one or more unsaturations, and b) at least one compound of the following formula (1), optionally salified: R ~ OH O I + R2 NO Ra R 4 In which:

the radicals R 1 to R 3, which may be identical or different, represent:

a C1-C30 alkyl radical; a C2-C30 alkenyl radical;

a C2-C30 alkynyl radical;

said alkyl, alkenyl and alkynyl radicals possibly being substituted by an optionally substituted C 6 -C 30 aryl radical; a (C 1 -C 3) alkyl radical (C 6 -C 30), optionally substituted; a (C 6 -C 30) aryl radical (C 1 -C 30), optionally substituted; and / or possibly being interrupted by at least one oxygen atom, an optionally substituted C6-C30 aryl radical; the radical R4 represents: o a hydrogen atom; a C1-C30 alkyl radical; a C2-C30 alkenyl radical; a C2-C30 alkynyl radical; o said alkyl, alkenyl, alkynyl radicals may optionally be substituted, and / or may optionally be interrupted by at least one oxygen atom; o a -NR- group, a -N + (R) 2- group, in which the radicals R, which may be identical or different, represent - a hydrogen atom, - an optionally substituted C1-C30 alkyl radical; a 5- or 6-membered heterocycle, optionally substituted, comprising one or more heteroatoms such as oxygen, nitrogen, possibly carrying at least one cationic charge; an optionally substituted C1-C30 alkoxy radical; a hydroxyl radical; an amino radical; an amino radical bearing one or two alkyl radicals, C 1 -C 30, preferably C 2 -C 20; optionally substituted.

The subject of the invention is also a method for staining human keratinous fibers, in which the above-mentioned composition is applied to the fibers in the presence of at least one oxidizing agent.

The invention further relates to a multi-compartment device comprising in a first compartment a staining composition as described above, and in another compartment, a composition comprising, in a medium suitable for staining human keratin fibers, at least an oxidizing agent.

The invention finally relates to the use, for improving the storage stability of compositions intended for the oxidation dyeing of human keratin fibers, of at least one compound of formula (1) above.

Other characteristics and advantages of the invention will emerge more clearly on reading the description and examples which follow. It should be noted that in what follows, and unless otherwise indicated, the boundaries of a range of values are within this range. The human keratin fibers treated according to the invention are preferably the hair. The words "at least one" are understood to mean "one or more". As indicated above, the composition according to the invention comprises at least one

compound of formula (1) below, optionally salified: R ~ OH O I + R2 N _ O Ra R 4 In which:

The radicals R 1 to R 3, which may be identical or different, represent:

a C1-C30 alkyl radical; preferably C1-C20;

a C2-C30 alkenyl radical; preferably C2-C20;

a C2-C30 alkynyl radical; preferably C2-C20;

said alkyl, alkenyl and alkynyl radicals possibly being

Substituted by an optionally substituted C6-C30 aryl radical; an optionally substituted (C 1 -C 30) aryl (C 6 -C 30) aryl radical; an optionally substituted aryl radical (C 6 -C 30) alkyl (C 1 -C 30); and / or possibly being interrupted by at least one oxygen atom, an optionally substituted C6-C30 aryl radical;

The radical R4 represents:

o a hydrogen atom;

a C1-C30 alkyl radical; preferably C1-C20;

a C2-C30 alkenyl radical; preferably C2-C20;

a C2-C30 alkynyl radical; preferably C2-C20;

Wherein said alkyl, alkenyl, alkynyl radicals may optionally be substituted, and / or may optionally be interrupted by at least one oxygen atom;

o a group -NR-, a group -N + (R) 2-,

in which the radicals R, which may be identical or different, represent a hydrogen atom,

an optionally substituted C1-C30 alkyl radical;

a 5- or 6-membered heterocycle, optionally substituted, comprising one or more heteroatoms such as oxygen, nitrogen, possibly carrying at least one cationic charge;

A C1-C30 alkoxy radical, preferably a C2-C20 alkoxy radical,

substituted;

a hydroxyl radical; an amino radical; an amino radical bearing one or two alkyl radicals, C 1 -C 30, preferably C 2 -C 20; optionally substituted. The compounds of formula (1) can be in the form of internal salts or be salified with agents, preferably acidic, such as hydrochloric acid.

The alkyl, alkenyl or alkynyl radicals can be linear, or branched when the number of carbon atoms in the longest chain allows it. The alkenyl radicals comprise at least one carbon-carbon double bond (denoted C = C), optionally conjugated if the radical comprises two or more. The alkynyl radicals comprise at least one carbon-carbon triple bond (denoted C = C), optionally conjugated if the radical comprises two or more.

Unless otherwise specified, the alkyl, alkenyl, alkynyl radicals or the alkyl, alkenyl and alkynyl radicals of complex radicals may optionally be substituted by at least one group chosen from halogen atoms, preferably fluorine, amino groups optionally substituted with one or two C1-C6 alkyl, hydroxyl, C1-C6 alkoxy, preferably C1-C2 alkoxy radicals; C1-C6 hydroxyalkyls Preferably, the aryl radicals, or aryl moieties of complex radicals comprising an aryl moiety, are C6 (benzene) radicals.

Unless otherwise specified, the aryl radicals or even the aryl portions of complex radicals may optionally be substituted with at least one group chosen from C 1 -C 6 alkyl radicals optionally carrying at least one a hydroxyl or amino group optionally carrying one or two C 1 -C 4 alkyl radicals; C 1 -C 4 alkoxy; halogen such as chlorine; The 5- or 6-membered heterocycles may comprise one or more unsaturations, conjugated or otherwise. They can also be aromatic. Said heterocycles are advantageously chosen from pyrrolidinyl, imidazolyl, piperidinyl, piperazinyl, morpholinyl, pyridinyl and pyrimidinyl heterocycles, as well as their cationic derivatives when they exist. Preferably the heterocycles are saturated.

The heterocycles may optionally be substituted by at least one group chosen from C 1 -C 6 alkyl radicals optionally bearing at least one hydroxyl group, amino optionally carrying one or two C 1 -C 4 alkyl radicals; C1-C4 alkoxy. It should be noted that the substituent (s) of the heterocycle (s) may be on a ring carbon atom or on a heteroatom, provided that two heteroatoms are not directly linked to one another.

According to an advantageous variant of the invention, the compounds of formula (1) are such that the radicals R 1, R 2 and R 3, which may be identical or different, represent a C 1 -C 20, preferably C 1 -C 14, alkyl radical which is optionally substituted. by at least one halogen atom, preferably fluorine, at least one amino group, at least one hydroxyl group, at least one C1-C2 alkoxy group. Preferably, the compound or compounds of formula (1) are such that at most one of the radicals R 1 and R 2 or R 3 represents a C 6 -C 20 alkyl radical substituted by at least one halogen atom, preferably fluorine, at least one amino group, at least one hydroxyl group, at least one C1-C2 alkoxy group. According to another preferred embodiment, the compound or compounds of formula (1) are preferably such that two or three of the radicals R 1, R 2 or R 3 represent a C 1 -C 6 alkyl radical.

As regards the radical R 4, it preferably represents a hydrogen atom; a C 1 -C 2 alkyl radical; a C 1 -C 2 alkoxy radical; a hydroxyl radical.

According to an advantageous variant of the invention, the compound or compounds of formula (1) are chosen from the following compounds: LOH Me and IOH -O 2 C -CH 2 -H-CH 2 -N ± (CH 2) 10 -M i -Pr- i-CH2-CH-CH2-OO2-I i-Pr 508172-06-3 497919-92-3 Undecanaminium internal salt, N- (3- 1-Propanaminium, 3-carboxy-2-hydroxypropyl internal salt) - N, N-dimethylcarboxy-N-ethyl-2-hydroxy-N, N-bis (1-methylethyl) OH (n-Pr) 3 + N-CH 2 -CH-CH 2 -0-00-Et 3 + N-CH 2 Propanaminium internal salt, 3-Propanaminium internal salt, 3-carboxy-2-hydroxy-N, N, N-tripropyl-, carboxy-2-propanaminium N, N, N-triethyl-2-hydroxy-, -OC2 N2 (CF2) 7 ~ CF3 + (CH2) 3 0E3 g Me Nie -02C N1 ~ (CF2) ~ HM 'Me 159614-90 -1 159614-87-6 1-Decanaminium internal salt, N- (3- 1-Undecanaminium, N-carboxy-2-hydroxypropyl) - (3-carboxy-2-hydroxypropyl) -3,3,4 internal salt , 4,5,5,6,6,7,7,8,8,9,9,10,10,10- 4,4,5,5,6,6,7,7,8,8,9 9,10,10,11,11,11-heptadecafluoro-N, N-dimethylheptadecafluoro-N, N-dimethyl-, -O 2 C (CF 2) 5 \ \ CF 3 gm ~ e 15 9614-86-5 1-Octanaminium, N- (3-carboxy-2-hydroxypropyl) -3,3,4,4,5,5,6,6,7,7,8,8,8-internal salt tridecafluoro-N, N-dimethyl-, Me LO H Me -O 2 C-CH-C H-CH 2 -N + Me 3 Mea + N ss CO 2 -bH 152129-36-7 152129-38-9 Butanaminium internal salt, 3- carboxy-1-Butanaminium, 3-2-hydroxy-N, N, N-trimethyl-, carboxy-2-hydroxy-N, N, N-trimethyl- internal salt; and also the following derivative: (R *, R) *) OHOH Me3 + N-CH2-CH-CH2-OO2-Me3 + N s R CO2-H 406-76-8 56595-17-6 1-Propanaminium internal salt, 3- 1-Propanaminium internal salt, 3-carboxy-2-hydroxy-N, N, N-trimethyl-, carboxy-2,3-dihydroxy-N, N, N-trimethyl-, -O 2 C R N + Me 3 ((2 SSSSS, 3R) -) - bH -02C ~ N + Me3 H 541-15-1 541-14-0 (-) - L-Carnitine Vitamin BT (+) - D-Carnitine Even more preferentially the compound of formula (1) is carnitine in form of one of its enantiomers or their mixtures. The composition more particularly has a content of compound (s) of formula (1) between 0.001 and 10% by weight, preferably between 0.05 and 5% by weight, relative to the weight of the composition.

The composition according to the invention comprises at least one oxidation dye precursor chosen from oxidation bases and / or couplers comprising at least one heterocycle containing one or more unsaturations (hereinafter referred to as oxidation base). heterocyclic and heterocyclic coupler). It should be noted that the term unsaturation here denotes a carbon-carbon double bond. In particular, the oxidation dye precursor (s) that are suitable for carrying out the invention are chosen from oxidation dye precursors conventionally used. in the field of hair dyeing, which comprise at least one 5- to 6-membered heterocycle containing one to three heteroatoms, identical or different, chosen from nitrogen and optionally oxygen; comprising one or more unsaturations, aromatic or not; condensed or not with a benzene ring; the rings or heterocycles being optionally substituted. More particularly, the heterocycle, optionally fused to at least one benzene ring, is chosen from pyridines, pyrimidines, indoles, indolines, benzomorpholines, benzimidazole, pyrazoles, pyrazolones which may be partially hydrogenated, or combinations thereof; the heterocycle (s) and / or the benzene ring (s) being optionally substituted. As regards the substituent (s), the latter are advantageously chosen from the following groups: (C 1 -C 4) alkyl, hydroxyl, (C 1 -C 4) alkoxy, amino optionally substituted with one or two identical or different alkyl radicals, C1-C4, optionally carrying at least one hydroxyl or amino, or forming together with the nitrogen atom to which they are attached, a heterocycle, saturated or containing at least one initiating, comprising from 5 to 7 members; , optionally comprising another heteroatom selected from oxygen or nitrogen, hydroxycarbonyl, C 1 -C 4 alkoxycarbonyl, aminocarbonyl optionally carrying a C 1 -C 4 alkyl radical, C 6 -C 20 aryl, preferably phenyl optionally substituted arylalkyl, the optionally substituted aryl ring being C6-C20, preferably C6, and the alkyl radical being C1-C2, 5- or 6-membered heterocycle, saturated or comprising at least one unsaturation or even aromatiq ue, containing 1 to 3 heteroatoms selected from nitrogen, oxygen, optionally substituted. It should be noted that the substituent (s) of the heterocycle (s) may be on a ring carbon atom or on a heteroatom, provided that two heteroatoms are not directly linked to one another.

In particular, the oxidation dye precursor may be chosen from oxidation bases, from couplers, or mixtures thereof.

According to a first variant of the invention, the composition comprises, as oxidation dye precursor, at least one heterocyclic oxidation base comprising at least one heterocycle containing one or more unsaturations. Among such heterocyclic bases, mention may be made, by way of example, of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives. Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1,026,978 and GB 1,153,196, such as 2,5-diamino pyridine, 244-methoxyphenyl) amino 3-amino pyridine, 3,4 diamino pyridine, and their salts. Other 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 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-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-aminopyrazolo [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 salts. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2 , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their salts and tautomeric forms, when tautomeric equilibrium exists. Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 1-methyl pyrazole, 4,5-diamino [3-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-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 1 - ([3-hydroxyethyl) 3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 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 - ([3-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts. It is also possible to use 4-5-diamino-14 [3-methoxyethyl) pyrazole. Preferably, a 4,5-diaminopyrazole and even more preferably 4,5-diamino-1 - ([3-hydroxyethyl) pyrazole and / or one of its salts will be used. As pyrazole derivatives, mention may also be made of diamino N, N-dihydropyrazolopyrazolones and especially those described in application FR-A-2 886 136 such as the following compounds and their addition salts: 2,3-diamino-6 7-Dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] ] pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3- (pyrrolidin-1) yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazole 3-one, 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-dimethylamino- 6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino [1,2- a] pyrazol-1-one, 4-amino-1,2-diethyl-5- (pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one, 4-amino-5- (3-dimethylamin) o-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1 , 2-a] pyrazol-1-one. It will be preferred to use 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and / or a salt thereof. As heterocyclic bases, use will preferably be made of 4,5-diamino-1 - ([3-hydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2 a] pyrazol-1-one and / or a salt thereof.

It should be noted that the composition according to the invention may optionally comprise one or more other oxidation bases conventionally used in the field of the coloration of human keratin fibers, different from the heterocyclic bases mentioned above. By way of example, the additional oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols and ortho-aminophenols, and their salts. Among the paraphenylenediamines, there may be mentioned, for example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl paraphenylenediamine, 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 - ([3-hydroxyethyl) paraphenylenediamine, 4-N, N-bis- (3-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (3-hydroxyethyl) amino 2-chloro aniline, 2- [3-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N - ([3-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine N, N- (ethyl, [3-hydroxyethyl) paraphenylenediamine, N - ([3, γ-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl-para-phenylenediamine, 2- [3-hydroxyethyloxy-para-phenylenediamine, 2- [3-acetylaminoethyloxy-para-phenylenediamine, N - ([3-methoxyethyl) para-phenylenediamine, 2-thienyl paraphenylenediamine, 2- [3-hydroxyethylamino-5-amino toluene, and their salts. Among the paraphenylenediamines mentioned above, para-phenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2- [3-hydroxyethyl paraphenylenediamine, 2- [3-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, , 6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (3-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2- [3-acetylaminoethyloxy-para-phenylenediamine, and their addition salts with an acid are particularly preferred. Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis ((3-hydroxyethyl) N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, N, N'-bis - ([3-hydroxyethyl) N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis - ([3-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, and their salts.

Among para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-chlorophenol, 4- amino 3-hydroxymethyl phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2 - ([ 3-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, and their salts. Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their salts.

According to a second variant of the invention, the composition comprises, as oxidation dye precursor, one or more heterocyclic couplers comprising at least one heterocycle containing one or more unsaturations. By way of example of heterocyclic couplers suitable for the implementation of the invention, mention may be made of 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3- hydroxy pyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazole 5-one 1-phenyl-3-methyl-pyrazole-5-one, 2,6-dimethyl-pyrazolo [1,5-b] -1,2,4-triazole, 6-methyl-pyrazolo [1,5-a] -benzimidazole , their salts, and mixtures thereof.

Of course, the composition may comprise one or more additional couplers chosen from those conventionally used in hair dyeing, different from the heterocyclic couplers described above. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, as well as their salts, and mixtures thereof. By way of example, mention may be made of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene and 2,4-diamino-1- (13- hydroxyethyloxy) benzene, 2-amino 4- (13-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido-dimethylamino benzene, sesamol, 1-13-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, their addition salts, and mixtures thereof.

In general, the salts of the oxidation bases and couplers that can be used in the card of the invention are chosen from acid addition salts such as hydrochlorides, hydrobromides, sulphates and citrates. succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates or from addition salts with an organic or inorganic base such as hydroxides or carbonates of sodium, potassium or ammonium, organic amines.

The oxidation base (s) each advantageously represent from 0.0001 to 10% by weight relative to the total weight of the composition, and preferably from 0.005 to 5% by weight relative to the total weight of the composition.

The coupler (s), if present, are each advantageously from 0.0001 to 10% by weight relative to the total weight of the composition, and preferably from 0.005 to 5% by weight relative to the total weight of the composition. .

The composition according to the invention may also comprise one or more direct dyes. These direct dyes are, for example, chosen from neutral, acidic or cationic nitro-benzene direct dyes, neutral azo, acid or cationic direct dyes, tetraazapentamethine dyes, neutral or acidic or cationic quinone dyes, in particular neutral anthraquinone dyes and direct azine dyes. , triarylmethane direct dyes, indoamine direct dyes and natural direct dyes. Among the nitrobenzene direct dyes, mention may be made in a nonlimiting manner of the following compounds: 1,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4- (3-hydroxyethylaminobenzene, 1-amino-2-nitro-4 -bis ([3-hydroxyethyl) -aminobenzene, 1,4-Bis ([3-hydroxyethylamino) -2-nitrobenzene, 1- (3-hydroxyethylamino-2-nitro-4-bis - ((3-hydroxyethylamino) -benzene 1- [3- Hydroxyethylamino-2-nitro-4-aminobenzene, 1- (3-hydroxyethylamino-2-nitro-4- (ethyl) (3-hydroxyethyl) -aminobenzene, 1-amino-3-methyl-4 - (3-Hydroxyethylamino-6-nitrobenzene, 1-amino-2-nitro-4- (3-hydroxyethylamino) -5-chlorobenzene, 1,2-Diamino-4-nitrobenzene, 1-amino-2- (3-hydroxyethyl) amino 5-Nitrobenzene, 1,2-Bis - ((3-hydroxyethylamino) -4-nitrobenzene, 1-amino-2-tris (hydroxymethyl) methylamino-5-nitrobenzene, 1-Hydroxy-2-amino-5-nitrobenzene , 1-Hydroxy-2-amino-4-nitrobenzene, 1-Hydroxy-3-nitro-4-aminobenzene, 1-Hydroxy-2-amino-4,6-dinitrobenzene, 1- (3-hydroxyethyloxy-2-) - hydroxyethylamino-5-n itrobenzene, 1-methoxy-2- (3-hydroxyethylamino-5-nitrobenzene, 1- [3-hydroxyethyloxy-3-methylamino-4-nitrobenzene, 1- (3-yl) dihydroxypropyloxy-3-methylamino-4-nitrobenzene, 1 - (3-hydroxyethylamino-4- (3-yl) dihydroxypropyloxy-2-nitrobenzene, 1- [3, y-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene, 1- [3-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene] 1-8-Hydroxyethylamino-3-methyl-2-nitrobenzene, 1- [3-aminoethylamino-5-methoxy-2-nitrobenzene, 1-Hydroxy-2-chloro-6'-ethylamino-4-nitrobenzene, 1-Hydroxy-2 chloro-6-amino-4-nitrobenzene, 1-hydroxy-6-bis- (8-hydroxyethyl) -amino-3-nitrobenzene, 1-8-hydroxyethylamino-2-nitrobenzene, 1-hydroxy-4-p-hydroxyethylamino 3-nitrobenzene. Among the azo direct dyes, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO95 / 01772 and EP714954. Among these compounds, mention may be made in particular of the following dyes: 1,3-dimethyl-2 - [[4- (dimethylamino) phenyl] azo] -1H-imidazolium chloride, 1,3-dimethyl-2-chloride [(4-Aminophenyl) azo] -1H-imidazolium, 1-methyl-4 - [(methylphenyl-hydrazono) methyl] -pyridinium methylsulphate. The following dyes, described in the COLOR INDEX INTERNATIONAL 3rd Edition Disperse Red 17, Acid Yellow 9, Acid Black 1, Basic Red 22, Basic Red 76, Basic Yellow 57, Basic Brown 16, Acid, may also be mentioned among the azo direct dyes. Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 35, Basic Brown 17, Acid Yellow 23, Acid Orange 24, Disperse Black 9. Mention may also be made of 1- (4'-aminodiphenylazo) -2-methyl-4bis - (8-hydroxyethyl) aminobenzene and 4-hydroxy-3- (2-methoxyphenylazo) -1-naphthalenesulfonic acid.

Among the quinone direct dyes, mention may be made of the following dyes: Disperse Red 15, Solvent Violet 13, Acid Violet 43, Disperse Violet 1, Disperse Violet 4, Disperse Blue 1, Disperse Violet 8, Disperse Blue 3, Disperse Red 11, Acid Blue 62, Disperse Blue 7, Basic Blue 22, Disperse Violet 15, Basic Blue 99, as well as the following compounds: 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone, 1-Aminopropyl-amino-4-methylaminoanthraquinone, 1-Aminopropylaminoanthraquinone, 8-hydroxyethyl-1,4-diaminoanthraquinone, 2-aminoethylaminoanthraquinone, 1,4-bis (8,4-dihydroxypropylamino) anthraquinone. Among the azine dyes, mention may be made of the following compounds -Basic Blue 17 and Basic Red 2.

Among the triarylmethanic dyes, mention may be made of the following compounds: Basic Green 1, Acid Blue 9, Basic Violet 3, Basic Violet 14, Basic Blue 7, Acid Violet 49, Basic Blue 26, Acid Blue 7, among indoamine dyes, mention may be made of the following compounds: 2-O-hydroxyethlyamino-5- [bis- (R-4'-hydroxyethyl) amino] anilino-1,4-benzoquinone; -2-R-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1,4-benzoquinone; 3-N (2'-Chloro-4'-hydroxy) phenyl-acetylamino-6-methoxy-1,4-benzoquinone imine 3-N (3'-chloro-4'-methylamino) phenyl-ureido-6-methyl- 1,4-benzoquinone imine; -3- [4'-N- (ethyl, carbamytmethyl) amino-phenyl-ureido-6-methyl-1,4-benzoquinone imine.

Among the natural direct dyes include lawsone, juglone alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin, curcumin, spinulosin , apigenidine. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna. When present, the direct dye (s) more particularly represent from 0.0001 to 10% by weight of the total weight of the composition, and preferably from 0.005 to 5% by weight.

The medium of the composition according to the invention, suitable for coloring human keratin fibers, advantageously comprises water or a mixture of water and one or more organic solvents. Examples of organic solvents that may be mentioned include linear or branched C 2 -C 4 alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, dipropylene 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 solvent or solvents may be present in proportions ranging preferably from 1 to 90% by weight, relative to the total weight of the composition, and still more preferably from 5 to 80% by weight.

The composition according to the invention may also optionally comprise one or more substantive, cationic or amphoteric polymers. The substantive character (ie the hair depositability) of the polymers is conventionally determined by means of the test described by Richard J. Crawford, Journal of the Society of Cosmetic Chemists, 1980, 31 - (5) - pages 273-278 (disclosure by Red 80 acid dye). These substantive polymers are described in particular in patent application EP 557203. More particularly, it is possible to use polymers chosen from cellulose cationic derivatives, homopolymers of dimethyldiallylammonium halide and copolymers of dimethyldiallylammonium halide and of acid. (meth) acrylic; homopolymers and copolymers of methacryloyloxyethyltrimethylammonium halide; quaternary polyammonium polymers; vinylpyrrolidone polymers with cationic units; their mixtures.

Among the substantive polymers of the dimethyldiallylammonium halide copolymer type that may be used according to the invention, mention may be made in particular of: copolymers of diallyldimethylammonium chloride and of acrylic acid such as that of proportions (80/20 by weight) sold under the Merquat 280 denomination by Calgon; copolymers of dimethyldiallylammonium chloride and of acrylamide sold under the names Merquat 550 and Merquat S by the company Merck. Among the polymeric polymers of the methacryloyloxyethyltrimethylammonium halide polymer type that may be used according to the invention, mention may be made in particular of the products which are named in the CTFA dictionary (5th edition, 1993) "Polyquaternium 37", "Polyquaternium 32" and "Polyquaternium" 35 ", which respectively correspond, as regards" Polyquaternium 37 ", to the cross-linked poly (methacryloyloxyethyltrimethylammonium) chloride, in a 50% dispersion in mineral oil, and sold under the name Salcare SC95 by the company Allied Colloids, as regards "Polyquaternium 32", to the crosslinked copolymer of acrylamide and methacryloyloxyethyltrimethylammonium chloride (20/80 by weight), in a 50% dispersion in mineral oil, and sold under the name Salcare SC92 by the company Allied Colloids, and as regards the "Polyquaternium 35", with the methosulfate of the copolymer of methacryloyloxyethyltrimethylammon and methacryloyloxyethyldimethylacetylammonium, sold under the name Plex 7525L by Rohm GmbH. The substantive polymers of the quaternary polyammonium type that may be used according to the invention are the following: the polymers prepared and described in French Patent 2,270,846, consisting of repeating units corresponding to the following formula (II): H 3 I H 3 N (( CH 2) 3 N + - (CH 2) 6 T 1 Cl - CH 3 CH 3 (II), in particular those whose molecular weight, determined by gel permeation chromatography, is between 9500 and 9900; - the polymers prepared and described in French Patent 2,270,846, consisting of repeating units corresponding to the following formula (III): ## STR3 ## III) especially those whose molecular weight, determined by gel permeation chromatography, is about 1200; -the polymers described and prepared in US Pat. Nos. 4,157,388, 4,390,689, 4,702,906, 4,719,282, and consisting of recurring units corresponding to the following formula (IV): CH3Cl Cl CH3 I + 1+ N - (CH2V N H- CO - D - N H (CH 2) p - N - (CH 2) 2 - O - (CH 2) 2 CH 3 CH 3 (IV)

in which p denotes an integer ranging from 1 to about 6, D may be zero or may represent a group - (CH 2) r CO- in which r denotes a number equal to 4 or to 7, and in particular those whose molecular mass is less than 100,000, preferably less than or equal to 50,000; such polymers are in particular sold by Miranol under the names "Mirapol A15", "Mirapol AD1", "Mirapol AZ1" and "Mirapol 175"; Among the vinylpyrrolidone polymers (PVP) with cationic units that can be used in accordance with the invention, mention may be made in particular of:

a) Vinylpyrrolidone polymers having dimethylaminoethyl methacrylate units; we can mention among these:

the vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer (20/80 by weight) sold under the trade name COPOLYMER 845 by the company I.S.P. the vinylpyrrolidone / dimethylaminoethyl methacrylate copolymers quaternized with diethyl sulfate, sold under the names GAFQUAT 734, 755, 755 and 755 L by the company I.S.P.

PVP / dimethylaminoethyl methacrylate / hydrophilic polyurethane, sold under the trade name Pecogel GC-310 by the company U.C.I.B. or else under the names AQUAMERE C 1031 and C 1511 by the company BLAGDEN CHEMICALS,

the C 8 to C 16 dimethylaminoethyl dimethylaminoethyl methacrylates, quaternized or non-quarternized, sold under the names Ganex ACP 1050 to 1057, 1062 to 1099, 1079 to 1086, by the company I.S.P. PVP / dimethylaminoethyl methacrylate / vinylcaprolactam, sold under the name GAFFIX VC 713 by the company I.S.P.

b) vinylpyrrolidone polymers comprising methacrylamidopropyltrimethylammonium (M.A.P.T.A.C.) units, among which mention may be made in particular of: - Vinylpyrrolidone / M.A.P.T.A.C. copolymers, sold under the trade names GAFQUAT ACP 1011 and GAFQUAT HS 100 by the company I.S.P.

c) vinylpyrrolidone polymers containing methylvinylimidazolium units, and among which may be mentioned more particularly:

PVP / methylvinylimidazolium chloride, sold under the names Luviquat FC 370, FC 550, FC 905 and HM 552 by the company B.A.S.F.

PVP / Methylvinylimidazolium Chloride / Vinylimidazole, sold under the name Luviquat 8155 by the company B.A.S.F. PVV / methylvinylimidazolium methosulfate, sold under the name LUVIQUAT MS 370 by the company B.A.S.F.

Among the cationic polysiloxanes that may be mentioned in particular: (a) the compounds corresponding to the following formula (V): (R 1) a (T) 3-a-Si [OSi (T) 2] n- [OSi (T) b (R 1 ) 2Am-OSi (T) 3a (R 1) a (V) in which, T is a hydrogen atom, or a phenyl, hydroxyl (-OH) or C 1 -C 3 alkyl radical, and preferably methyl or alkoxy; in C1-C3, preferably methoxy, a denotes the number 0 or an integer of 1 to 3, and preferably 0, b is 0 or 1, and in particular 1, m and n are numbers such that the sum ( n + m) may vary in particular from 1 to 2,000 and in particular from 50 to 150, n being able to designate a number from 0 to 1,999 and in particular from 49 to 149 and m possibly being a number from 1 to 2,000, and in particular from 1 to 10; R1 is a monovalent radical of the formula -CgH2gL wherein q is a number from 2 to 8 and L is an optionally quaternized amino group selected from the groupings: - N (R2) -CH2-CH2-N (R2) 2; - N (R2) 2; -N "R2) 3 Q-; N + (R2) (H) 2 Q-; -N "R2) 2HQ-; - N (R 2) -CH 2 -CH 2 -N "R 2) (H) 2 Q-, in which R 2 may denote a hydrogen atom, a phenyl, a benzyl, or a monovalent saturated hydrocarbon radical, for example an alkyl radical C1-C20, and Q-represents a halide ion such as, for example, fluoride, chloride, bromide or iodide.

In particular, the amino silicones corresponding to the definition of formula (V) are chosen from compounds corresponding to the following formula: ## STR2 ## in which R, R ', R ", identical or different, denote a C1-C4 alkyl radical, preferably CH3, a C1-C4 alkoxy radical, preferably methoxy, or OH; A represents a linear or branched C3-C8 alkylene radical, preferably C3-C6; m and n are integers dependent on the molecular weight and whose sum is between 1 and 2000. CH3 R 'CH3 O-Si-R "1 CH3 m According to a first possibility, R, R', R ", which may be identical or different, represent a C 1 -C 4 alkyl or hydroxyl radical, A represents a C 3 alkylene radical and m and n are such that the weight average molecular weight of the compound is between about 5,000 and 500,000. Compounds of this type are referred to in the CTFA dictionary as "amodimethicone". R, R ', R ", which may be identical or different, represent a C 1 -C 4 alkoxy or hydroxyl radical, at least one of R or R" is an alkoxy radical and A represents a C 3 alkylene radical. The hydroxyl / alkoxy molar ratio is preferably between 0.2 / 1 and 0.4 / 1 and advantageously equal to 0.3 / 1. Moreover, m and n are such that the weight average molecular weight of the compound is between 2000 and 106. More particularly, n is between 0 and 999 and m is between 1 and 1000, the sum of n and m being between 1 and 1000. In this category of compounds, mention may be made inter alia of the Belsil®ADM 652 product marketed by Wacker.

According to a third possibility, R, R ", different, represent a C 1 -C 4 alkoxy or hydroxyl radical, at least one of the radicals R, R" is an alkoxy radical, R 'represents a methyl radical and A represents a C3 alkylene radical. The molar ratio of hydroxy / alkoxy is preferably between 1 / 0.8 and 1 / 1.1, and advantageously is equal to 1 / 0.95. Furthermore, m and n are such that the weight average molecular weight of the compound is between 2000 and 200000. More particularly, n is between 0 and 999 and m is between 1 and 1000, the sum of n and m being ranging from 1 to 1000. More particularly, mention may be made of FluidWR® 1300, sold by Wacker.

According to a fourth possibility, R, R "represent a hydroxyl radical, R 'represents a methyl radical and A is a C4-C8 alkylene radical, preferably a C4 radical, and m and n are such that the average molecular mass by weight of the compound is between 2000 and 106. More particularly, n is between 0 and 1999 and m is between 1 and 2000, the sum of n and m being between 1 and 2000.

A product of this type is especially marketed under the name DC28299 by Dow Corning. Note that the molecular mass of these silicones is determined by gel permeation chromatography (ambient temperature, polystyrene standard, p styragem columns, THF eluent, flow rate of 1 mm / m, and 200 μl of a 0.5% solution are injected by weight of silicone in THF and the detection is carried out by refractometry and UV-metry). A product corresponding to the definition of the formula (XVI) is in particular the polymer referred to in the CTFA dictionary "trimethylsilylamodimethicone", corresponding to the following formula (VII): H 3 CH 3 (CHI SiO SiO SiO (CH 3) 3 1 1 CH 3 Wherein n and m have the meanings given above according to formula (VI).

Such compounds are described for example in EP 95238; a compound of formula (VII) is for example sold under the name Q2-8220 by the company OSI. (b) the compounds of formula (VIII) below:

R4 CH2 CHOH-CH2-N + (R3) 3 Q 19 R3 Si - O R3 r s (VIII) in which,

R3 represents a C1-C13 monovalent hydrocarbon radical, and in particular a C1-C13 alkyl or C2-C18 alkenyl radical, for example methyl;

R4 represents a divalent hydrocarbon radical, in particular a C1-C18 alkylene radical or a divalent C1-C18, for example C1-C8, alkyleneoxy radical;

Q- is a halide ion, especially chloride;

r represents an average statistical value of 2 to 20 and in particular 2 to 8;

15 s represents an average statistical value of 20 to 200 and in particular 20 to 50.

Such compounds are described more particularly in US Patent 4185087.

A compound in this class is that sold by Union Carbide under the name "Ucar Silicone ALE 56".

c) the quaternary ammonium silicones of formula (IX): ## STR1 ## ## STR5 ## - N - R8 II 1 1 R7 R7 R7 R7

R (IX)

in which: XX

R ,, identical or different, represent a monovalent hydrocarbon radical having 1 to 18 carbon atoms, and in particular a C1-C13 alkyl radical, a C2-C18 alkenyl radical or a ring comprising 5 or 6 carbon atoms, for example methyl; R 6 represents a divalent hydrocarbon radical, in particular a C 1 -C 18 alkylene radical or a divalent C 1 -C 18, for example C 1 -C 8, alkyleneoxy radical connected to Si by an SiC bond; R8, which may be identical or different, represent a hydrogen atom, a monovalent hydrocarbon radical having from 1 to 18 carbon atoms, and in particular a C 1 -C 18 alkyl radical, a C 2 -C 18 alkenyl radical or a -R 6 radical; -NHCOR,; X - is an anion such as a halide ion, especially chloride or an organic acid salt (acetate, etc.); r represents an average statistical value of 2 to 200 and in particular 5 to 100; These silicones are for example described in application EP-A-0530974. d) the amino silicones of formula (X): R 3 Si - R 5 1 x Ra 3 NH 1 (CmH 2 m) NH 2 (X) in which: R 1, R 2, R 8 and R 4, which may be identical or different, denote an alkyl radical in C 1 -C 4 or a phenyl group; R 5 denotes a C 1 -C 4 alkyl radical or a hydroxyl group; n is an integer varying from 1 to 5; m is an integer ranging from 1 to 5; which x is chosen so that the amine number is between 0.01 and 1 meq / g.

When they are present, the concentration of cationic or amphoteric substantive polymer may vary between about 0.01 and 10% relative to the weight of the composition, and preferably between 0.1 and 5% by weight relative to the weight of the composition. composition. The coloring composition according to the invention may also comprise various additives conventionally used in the field of human keratin fiber staining. The composition may thus comprise inorganic or organic thickeners, and in particular fillers such as clays, nonionic, cationic or amphoteric, optionally associative anionic polymers; binders such as vinylpyrrolidone; lubricants such as polyol stearates or stearates of alkali or alkaline earth metals; hydrophilic or hydrophobic silicas; pigments; matting agents such as titanium oxides; anionic, nonionic, cationic, amphoteric or zwitterionic surfactants; penetrating agents, sequestering agents, such as ethylenediamine tetraacetic or its salts; moisture-absorbing agents such as amorphous silicas, certain polyacrylates crosslinked or modified with hydrophobic groups such as, for example, Luquasorb 1010 products from BASF, Polytrap 6603 Adsorber from AMCOL; buffers; dispersants; film-forming agents; preservatives; opacifying agents; vitamins other than carnitine or its derivatives; perfumes ; ceramides; volatile silicones The additives as defined above may be present in an amount for each of them ranging between 0.01 and 40% by weight, preferably between 0.1 and 30% by weight, relative to the total weight of the composition .

The pH of the composition according to the invention is usually between 2 and 11, preferably between 6 and 11, more particularly between 7.5 and 11. It can be adjusted to the desired value by means of acidifying agents or alkalizing agents usually used in the field. Among the acidifying agents, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid citric acid, lactic acid, sulphonic acids. Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and the following formula: wherein R is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 6 alkyl radical; Rx, Ry, Rz and Rt, identical or different, represent a hydrogen atom, a C 1 -C 6 alkyl radical or a C 1 -C 6 hydroxyalkyl radical.

The composition according to the invention may also comprise one or more oxidizing agents. The oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as, for example, persulfates, perborates and alkali metal or alkaline metal percarbonates. earthy, like sodium, potassium, magnesium. The use of hydrogen peroxide is particularly preferred. This oxidizing agent is advantageously constituted by hydrogen peroxide and in particular by an aqueous solution whose title may vary, more particularly, from 1 to 40 volumes, and even more preferably from 5 to 40 volumes. The process according to the invention consists of to apply the composition which has just been detailed on human keratin fibers, the latter being dry or wet.

The composition according to the invention may be applied in the presence of an oxidizing composition, comprising, in a cosmetically acceptable medium, at least one oxidizing agent, different from the oxygen of the air. Two variants of the process can be envisaged, consisting in simultaneously or successively applying the coloring composition and the oxidizing composition. According to a first possibility, the coloring composition according to the invention, which is free of an oxidizing agent, is mixed extemporaneously before application with a composition comprising one or more oxidizing agents (oxidizing composition). This oxidizing composition generally comprises water and one or more oxidizing agents as defined above. Regarding the organic solvents that may be present in the oxidizing composition, reference may be made to the list indicated previously in the context of the description of the coloring composition. Usually the pH of the oxidizing composition is less than 7. The oxidizing composition may be in the form of a solution, an emulsion or a gel. It may optionally comprise one or more additives conventionally used in the field of human keratin fiber staining, depending on the desired dosage form. Again reference can be made to the list of additives given above. Generally, the dilution ratio of the coloring composition is such that the resulting composition can be easily applied to the keratin fibers to be colored, while remaining localized to the place where it has been applied, in order to avoid the problems caused by the coulures of composition outside the area to be treated. More particularly, the dilution ratio (oxidizing composition / coloring composition) ranges from 0.5 to 3, and preferably from 1 to 2.

According to a second possibility, the coloring composition according to the invention, which is free of oxidizing agent, and an oxidizing composition, one after the other, without intermediate rinsing (successively), are applied. It is thus possible to apply the oxidizing composition and then the dye composition or vice versa. The proportions of the coloring and oxidizing compositions are such that the weight ratio oxidizing composition / coloring composition also varies from 0.5 to 3, and preferably from 1 to 2. 40 Whatever variant is chosen, the mixture present on the fibers is left in place for a duration, in general, of the order of 1 minute to 1 hour, preferably 10 minutes to 30 minutes. The temperature during the process is typically between room temperature (between 15 and 25 ° C) and 80 ° C, preferably between room temperature and 60 ° C. At the end of the treatment, the human keratinous fibers are optionally rinsed with water, washed with shampoo, rinsed again with water and then dried or left to dry.

As indicated previously, another subject of the invention consists of a multi-compartment device comprising in a first compartment a composition according to the invention for the dyeing of human keratinous fibers comprising at least one selected oxidation dye precursor (s). ) among the oxidation bases and / or couplers comprising at least one heterocycle containing one or more initiations, and at least one compound of formula (1) detailed above, and in another composition comprising, in a suitable medium for the dyeing of human keratinous fibers, at least one oxidizing agent. What has been described above concerning the composition according to the invention, the oxidizing composition, and the various ingredients, their nature and respective proportions, remains valid and will not be repeated again.

The following example serves to illustrate the invention without being limiting in nature.

EXAMPLE

The following composition A is carried out (unless otherwise indicated, the quantities are expressed in g%): Isopropyl myristate 2 Cetylstearyl alcohol 12.5 Cetyl palmitate 1.875 Behentrimonium chloride (80%) / Isopropyl alcohol (17% ) / 3,77 aqua (GENAMIN KDMP) Glyceryl stearate 1 Polyquaternium-37 (50%) + Paraffinum Iiquidum (35%) + 2 Ppg-1-trideceth-6 (7%) / Aqua (SALCARE SC 95) Ethylenediamine acid tetracetic 0.2 Sodium metabisulfite 0.48 D, L-carnitine hydrochloride 2.56x10-3 mol% Paratoluylene diamine 0.92 Resorcin 0.21 2,4-diamino phenoxy ethanol dicholorhydrate 1.25 Ammonia 20% NH3 10.2 Water qs 100 This cream presents after a month of storage in pot at room temperature a correct appearance. After manufacture, the composition A is mixed at the time of use with 1 part by weight of an oxidizing composition at pH 2 containing 6% hydrogen peroxide. The mixture thus obtained is applied to gray hair containing 90% natural whites or permed for 30 minutes at room temperature (22 ° C.). After rinsing and shampooing, the hair is dried. The hair has an intense ash brown shade and selectivity. 10

Claims (19)

REVENDICATIONS1. A composition for staining human keratin fibers comprising a) at least one oxidation dye precursor chosen from oxidation bases and / or couplers comprising at least one heterocycle containing one or more unsaturations, and b) d at least one compound of the following formula (1) optionally salified: R + OH R 2 -N R 3 R 4 In which: the radicals R 1 to R 3, which may be identical or different, represent: a C 1 -C 30 alkyl radical; a C2-C30 alkenyl radical; a C2-C30 alkynyl radical; said alkyl, alkenyl and alkynyl radicals possibly being substituted by an optionally substituted C 6 -C 30 aryl radical; a (C 1 -C 30) alkyl radical (C 1 -C 30) aryl, optionally substituted; a (C6-C30) aryl radical (C1-C3o) alkyl, optionally substituted; and / or possibly being interrupted by at least one oxygen atom, an optionally substituted C6-C30 aryl radical; the radicals R1 to R3 which are identical or different, also represent a C1-C20 alkyl radical, preferably C1-C14, optionally substituted with at least one halogen atom, preferably fluorine, at least one amino group, at least one hydroxyl group, at least one C1-C2 alkoxy group. the radical R4 represents: a hydrogen atom; a C1-C30 alkyl radical; a C2-C30 alkenyl radical; a C2-C30 alkynyl radical; o said alkyl, alkenyl, alkynyl radicals may optionally be substituted, and / or may optionally be interrupted by at least one oxygen atom; o a -NR- group, a -N + (R) 2- group, in which the radicals R, which may be identical or different, represent a hydrogen atom or an optionally substituted C1-C30 alkyl radical; o an optionally substituted 5- or 6-membered heterocycle comprising one or more heteroatoms, such as oxygen or nitrogen, optionally carrying at least one cationic charge; an optionally substituted C1-C30 alkoxy radical; a hydroxyl radical; an amino radical; an amino radical bearing one or two alkyl radicals, C 1 -C 30, preferably C 2 -C 20; optionally substituted. 2. Composition according to the preceding claim, characterized in that the compound (s) of formula (1) are such that the radicals R 1, R 2 and R 3, which may be identical or different, represent a C 1 -C 20 alkyl radical, preferably a C 1 -C 20 alkyl radical. C1, optionally substituted by at least one halogen atom, preferably fluorine, at least one amino group, at least one hydroxyl group, at least one C1-C2 alkoxy group. 3. Composition according to any one of the preceding claims, characterized in that the compound or compounds of formula (1) are such that at most one of the radicals R, and R2 or R3 represents a Cs-C20 alkyl radical. substituted by at least one halogen atom, preferably fluorine, at least one amino group, at least one hydroxyl group, at least one C 1 -C 2 alkoxy group. 4. Composition according to any one of the preceding claims, characterized in that the compound or compounds of formula (1) are such that two or three of the radicals R 1, R 2 or R 3 represent a C 1 -C 6 alkyl radical. 5. Composition according to any one of claims 1 to 4, characterized in that the compound (s) of formula (1) are such that the radical R4 represents a hydrogen atom; a C1-C2 alkyl radical; a C1-C2 alkoxy radical; a hydroxyl radical. 6. Composition according to any one of claims 1 to 5, characterized in that the compound or compounds of formula (1) are chosen from the following compounds: OH Me and OH-O 2 CH 2 CH 2 CH 2 CH 2 (CH 2 ) Internal salt of Undecanaminium, N- (3- Internal salt of 1-Propanaminium, 3-chlorobenzene) carboxy-2-hydroxypropyl) -N, N-dimethylcarboxy-N-ethyl-2-hydroxy-N, N-bis (1-methylethyl) OH (OH) n-Pr) 3 + N-CH 2 -L-CH 2 -CO2-Et3 + N-CH2-CH-CH2-OO2- 497919-91-2 386707-06-8 Propanaminium internal salt, 3- 1-Propanaminium, 3-carboxy-2-hydroxy-N, N internal salt N-tripropyl-, carboxy-N, N, N -trimethyl-2-hydroxy-, 5-yl-N- (C) -2- (C) n -O 2 -CH 2) 3- (CF2) <CF3 b H Md Me 6 H Me Me 159614-90-1 159614-87-6 1-Decanaminium internal salt, N- (3- 1-Undecanaminium internal salt, N-carboxy-2-hydroxypropyl) - (3-carboxy-2-hydroxypropyl) - 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- 4,4,5 , 5,6,6,7,7,8,8,9,9,10,10,11,11,11- heptadecafl uoro-N, N-dimethylheptadecafluor N, N -dimethyl-, -O 2 C N (CF 2) 5 OH Me F1 ~~ ~ CF 3 159614-86-5 Internal salt of 1-Octanaminium, N- (3-carboxy-2-hydroxypropyl) -3,34 , 4,5,6,6,7,7,8,8,8-tridecafluoro-N, N-dimethyl- - bH 152129-36-7 152129-38-9 Butanaminium internal salt, 3-carboxy- 1-Butanaminium inner salt, 3- 2-hydroxy-N, N, N-trimethyl-, carboxy-2-hydroxy-N , N, N-trimethyl-, (R * R *) -OH OH Me3 + N-CH2-cH-CH2-OO2-Me3 + N 9 CO2-406-76-8 56595-17-6 Inner salt of 1- Propanaminium, 3- 1-Propanaminium internal salt, 3-carboxy-2-hydroxy-N, N, N-trimethyl-, carboxy-2,3-dihydroxy-N, N, N-trimethyl-, (2S, 3R) - -02C ~ N + Me3 -02C ~ N + Me3 0H H 541-15-1 541-14-0 (-) - L-Carnitine Vitamin BT (+) - D-Carnitine 7. Composition according to any one of the preceding claims, characterized in that the compound of formula (1) is carnitine in the form of one of its enantiomers or mixtures thereof. 8. Composition according to any one of the preceding claims, characterized in that the content of compound (s) of formula (1) is between 0.001 and 10% by weight, and preferably between 0.05 and 5% by weight. , relative to the weight of the composition. 10 9. Composition according to any one of the preceding claims, characterized in that it comprises at least one oxidation dye precursor comprising at least one heterocycle having 5 to 6 members, containing one to three heteroatoms, identical or different, chosen among nitrogen and possibly oxygen; comprising one or more unsaturations, aromatic or not; condensed or not with a benzene ring; the rings or heterocycles being optionally substituted. 10. Composition according to any one of the preceding claims, characterized in that it comprises at least one oxidation dye precursor in which the heterocycle, optionally fused to a benzene ring, is chosen from pyridines and pyrimidines. , indoles, indolines, benzomorpholines, benzimidazole, pyrazoles, optionally partially hydrogenated pyrazolones, or combinations thereof; the heterocycle (s), the benzene ring (s) being optionally substituted. 11. Composition according to any one of claims 9 and 10, characterized in that it comprises at least one oxidation dye precursor wherein the substituent or substituents are advantageously chosen from the groups: o hydroxyl, o alkyl C1 -C 4 -C 1 -C 4 alkoxy, o amino optionally substituted with one or two identical or different C 1 -C 4 alkyl radicals, optionally bearing (s) at least one hydroxyl or amino, or forming together with the atom of nitrogen to which they are attached, a heterocycle, saturated or containing at least one initiation, comprising from 5 to 7 members, optionally comprising another heteroatom selected from oxygen or nitrogen, o hydroxycarbonyl, o C1-C4 alkoxycarbonyl, aminocarbonyl optionally bearing a C 1 -C 4 alkyl radical, C 6 -C 20 aryl, preferably phenyl, optionally substituted arylalkyl, the optionally substituted aryl ring being CeC 2 O, preferably C 5, and wherein the C 1 -C 2 alkyl radical is a 5- or 6-membered, saturated or at least one unsaturated or aromatic heterocycle containing 1 to 3 heteroatoms chosen from nitrogen and optionally substituted oxygen. 12. Composition according to any one of the preceding claims, characterized in that it comprises, as oxidation dye precursor, at leastan oxidation base comprising at least one heterocycle containing one or more unsaturations. 13. Composition according to any one of the preceding claims, characterized in that it comprises, as oxidation dye precursor, at least one coupler comprising at least one heterocycle containing one or more unsaturations. 14. Composition according to any one of the preceding claims, characterized in that it comprises one or more additional oxidation bases and / or one or more additional couplers. 15. Composition according to any one of the preceding claims, characterized in that it comprises from 0.0001 to 10% by weight in each of the oxidation dye precursors, relative to the total weight of the composition, preferably from 0.005 to 5% by weight. 16. Composition according to any one of the preceding claims, characterized in that it comprises one or more oxidizing agents, preferably hydrogen peroxide. 17. A process for staining human keratin fibers, wherein the composition according to any one of claims 1 to 15 is applied to the fibers in the presence of at least one oxidizing agent. 18. A multi-compartment device comprising in a first compartment a composition according to any one of claims 1 to 15, and in another a composition comprising at least one oxidizing agent. 30 19. Use, for improving the storage stability of compositions intended for the oxidation dyeing of human keratin fibers, of at least one compound of formula (1) below: ## STR1 ## in which: the radicals R 1 to R 3, which may be identical or different, represent: a C 1 -C 30 alkyl radical; a C2-C30 alkenyl radical; a C2-C30 alkynyl radical; wherein said alkyl, alkenyl and alkynyl radicals may optionally be substituted by an optionally substituted C6-C30 aryl radical; a (C 1 -C 30) alkyl radical (C 6 -C 30), optionally substituted; an optionally substituted aryl radical (C 6 -C 30) alkyl (C 1 -C 30); and / or possibly being interrupted by at least one oxygen atom, an optionally substituted CeC30 aryl radical; the radicals R 1 to R 3 which are identical or different, also represent a C 1 -C 20 alkyl radical, preferably a C 1 -C 14 radical, optionally substituted by at least one halogen atom, preferably fluorine, at least one amino group, at least one hydroxyl group, at least one C1-C2 alkoxy group. the radical R4 represents: a hydrogen atom; a C1-C30 alkyl radical; a C2-C30 alkenyl radical; a C2-C30 alkynyl radical; Said alkyl, alkenyl and alkynyl radicals being optionally substituted, and / or optionally interrupted by at least one oxygen atom; a group -NR-, a group -N + (R) 2-, in which the radicals R, which may be identical or different, represent a hydrogen atom or an optionally substituted C1-C30 alkyl radical; o an optionally substituted 5- or 6-membered heterocycle comprising one or more heteroatoms, such as oxygen or nitrogen, optionally carrying at least one cationic charge; an optionally substituted C1-C30 alkoxy radical; a hydroxyl radical; an amino radical; an amino radical bearing one or two alkyl radicals, C 1 -C 30, preferably C 2 -C 20; possibly substituted.30