FR2954148A1 - Composition, useful for dyeing keratin fibers, preferably human hair, comprises hair colorant and polycondensate of ethylene oxide and propylene oxide consisting of polyethylene glycol and polypropylene glycol blocks, in a medium - Google Patents

Abstract

Composition (I) comprises, in a medium: one or more hair colorant; and one or more polycondensate of ethylene oxide and propylene oxide consisting of polyethylene glycol and polypropylene glycol blocks. Composition (I) comprises, in a medium: one or more hair colorant; and one or more polycondensate of ethylene oxide and propylene oxide consisting of polyethylene glycol and polypropylene glycol blocks having a structure of formula (H-(O-CH 2-CH 2) a-(O-CH(CH 3)-CH 2) b-(O-CH 2-CH 2) a1-OH) with the exception of a composition, which is obtained by mixing an emulsion A1 comprising (gram%) beheneth-10 (6), sorbitol (5), Vaseline oil (60.25), water (10), ethanol (2), poloxamer 184 (5), potassium bicarbonate (1.75), water (4.302), monoethanolamine (5), p-phenylenediamine (0.216) and 2,4-diaminophenylethanol dichlorhydrate (0.482) with an aqueous composition (B) comprising a fatty alcohol dispersion in water (8%) and hydrogen peroxide (6%) in a weight ratio of (A1) and (B) of 1:1.5. a, a1 : 2-150; and b : 1-100. Independent claims are included for: (1) process for dyeing keratin fibers comprising applying (I) on the keratin fibers in the presence of one or more oxidizing agents for a sufficient time to develop the desired coloration; and (2) multi-compartment device comprising a first compartment containing a dye composition and a second compartment containing one or more oxidizing agents.

Description

COMPOSITION COMPRISING A CAPILLARY DYE AND A POLYCONDENSATE OF ETHYLENE OXIDE AND PROPYLENE OXIDE

The subject of the invention is a composition for dyeing keratinous fibers, and in particular human keratinous fibers such as the hair, comprising, in a medium which is suitable for dyeing, at least one hair dye and at least one oxide polycondensate. of ethylene and propylene oxide consisting of polyethylene glycol and polypropylene glycol blocks. It is known to dye keratinous fibers, and in particular human keratinous fibers such as the hair, with dyeing compositions comprising oxidation dye precursors, in particular ortho or para-phenylenediamines, ortho or para-aminophenols, compounds heterocyclic such as diaminopyrazole derivatives, pyrazolo [1,5-a] pyrimidine derivatives, pyrimidine derivatives, pyridine derivatives, indole derivatives, indoline derivatives generally referred to as oxidation bases. The oxidation dye precursors, or oxidation bases, are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise, by a process of oxidative condensation, to colored or coloring compounds. This produces permanent colorations.

It is also known that the shades obtained with these oxidation bases can be varied by combining them with other oxidation dye precursors which are couplers or color modifiers, the latter being chosen in particular from phenylenediamines, meta-aminophenols, metahydroxyphenols and certain heterocyclic compounds.

The variety of molecules involved in the oxidation bases and couplers allows a rich palette of colors to be obtained. The so-called "permanent" coloration obtained by virtue of these oxidation dyes, also known as oxidation dyeing, must moreover satisfy a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity and to have good resistance to external aggressions such as light, bad weather, washing, permanent ripples, sweating and friction. The dyes must also make it possible to cover the white hairs, and finally be the least selective possible, that is to say to make it possible to obtain the lowest possible color differences throughout a single keratinous fiber, which comprises in general, differently sensitized (ie damaged) areas from tip to root. The second mode of staining, called direct or semipermanent staining, comprises the application of direct dyes which are molecules having an affinity for the fibers and dyes even in the absence of an oxidizing agent added in the compositions containing them. Given the nature of the molecules used, these remain rather on the surface of the fiber and penetrate relatively little inside the fiber, compared to the small molecules of precursors of oxidation dyes.

The direct dyes generally employed are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, methine, azomethine, xanthene, acridine, azine or triarylmethane direct dyes. The chemical species used may be nonionic, anionic (acidic dyes) or cationic (basic dyes). Direct dyes can also be natural dyes. Most of the direct dyes used have sufficient aqueous solubility and there are now many suitable dye supports for carrying them out. These compositions containing one or more direct dyes are applied to the keratinous fibers for a time necessary to obtain the desired coloration, and then rinsed. However, the resulting dyes are particularly chromatic coloring but temporary or semi-permanent because their desorption of the surface and / or the core of the fiber are responsible for their low dyeing power and their poor resistance to washing. These colorations are moreover generally selective. On the other hand, it is necessary in certain cases, for example when it is desired to improve the rise of the dyes or to prepare stock solutions in dyes intended to be diluted during the preparation of the shades, to increase the concentration of the dyes in the composition. . However, the increase in the concentration of dyes is limited by the solubility limit of the dyes in the appropriate medium for the dyeing used for the preparation of the composition, the latter being constituted by one or more cosmetically acceptable solvents such as water or alcohols.

The object of the present invention is to provide novel compositions for the dyeing of human hair which allow powerful, resistant, low-selective dyes which can also give various shades, and in particular to provide new compositions for the dyeing of human hair. keratinous fibers which may be more concentrated in dyes, in particular compositions in which the dyes, although being in a greater amount at their solubility limit in the medium used for the dye composition, are dissolved in this medium, and which are stable in time. This object is achieved with the present invention which relates to a composition for dyeing keratinous fibers comprising, in a medium suitable for dyeing: one or more hair dyes; and one or more polycondensates of ethylene oxide and propylene oxide consisting of polyethylene glycol and polypropylene glycol blocks of the following chemical structure: H- (O-CH 2 -CH 2) a- (O-CF-CH 2) b- (O-CH2-CH2) a'-OH, wherein a, a 'is from 2 to 150, and b is from 1 to 100; With the exception of the following composition obtained by mixing the emulsion Al: Emulsion Al Phase INCI name g% Beheneth-10 6.00 Sorbitol 5.00 A Vaseline oil 60.25 Water 10.00 Ethanol 2, 00 Poloxamer 184 5.00 Potassium bicarbonate 1.75 B Water 4.302 Monoethanolamine 5.00 p-phenylenediamine 0.216 2,4-diaminophenoxyethanol dichlorohydrate 0.482 INCI name g% Beheneth-10 6.00 Sorbitol 5.00 Vaseline oil 60, Water 10.00 Ethanol 2.00 Poloxamer 184 5.00 Bi potassium carbonate 1.75 Water 4.302 Monoethanolamine 5.00 p-phenylenediamine 0.216 2,4-d iaminophenoxyethanol dihydrochloride 0.482 with an aqueous composition (B) comprising a dispersion of fatty alcohols in water (8%) and 6% of hydrogen peroxide in a ratio of 1 weight of (Al) to 1.5 weight of (B). The present invention makes it possible to obtain a composition for dyeing keratinous fibers which is more concentrated in dyes, for example a composition in which the dyestuffs solubilized in the medium are in an amount greater than their solubility limit in this medium, and which is stable in the time, for example storage at 45 ° C. The present invention also makes it possible to obtain powerful, chromatic, aesthetic, low-selective colorings that are resistant to the various attacks that hair can undergo, such as shampoos, light, sweat and permanent deformities. Another object of the invention is a process for dyeing keratinous fibers implementing the composition of the present invention, as well as the use of this composition for dyeing keratinous fibers. The invention finally relates to a dyeing kit comprising firstly a dyeing composition containing one or more hair dyes and one or more polycondensates of ethylene oxide and of propylene oxide consisting of polyethylene glycol blocks and polypropylene glycol and secondly a composition containing one or more oxidizing agents. Unless otherwise indicated, the ranges of the ranges of values which are given within the scope of the present invention are included in these ranges. For the purposes of the present invention, the term "dyestuff" is intended to mean synthetic direct dyes, natural dyes and oxidation dye precursors. These hair dyes may be nonionic or ionic, in particular cationic or anionic.

The precursor (s) of oxidation dyes present in the composition of the present invention may be chosen from oxidation bases and couplers conventionally used in oxidation dyeing. The oxidation base (s) may be chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, ortho-phenylenediamines, heterocyclic bases and their addition salts. Among the para-phenylenediamines, there may be mentioned, by way of example, para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-ethyl-para-phenylenediamine, N, N-dipropyl para phenylenediamine, 4-amine N, N-diethyl-3-methylaniline, N, N-bis- (3-hydroxyethyl) para-phenylenediamine, 4-N, N-bis- (6-hydroxyethyl) amino 2- methyl aniline, 4-N, N-bis- (6-hydroxyethyl) amino-2-chloroaniline, 2-6-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl para- phenylenediamine, N- (0-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, R-hydroxyethyl) paraphenylenediamine, N-My-clihy hydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, t-1-phenyl-para-phenylenediamine, 2-8-hydroxyethyloxy-para-phenylenediamine, 2-6-acetylaminoethyloxy para-phenylenediamine N- (p-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl para-phenylenediamine, 2-R hydroxyethylamino 5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2- [3-hydroxyethyl-para-phenylenediamine, 2- [3-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (3-hydroxyethyl) para-phenylenediamine, 2- chloro para-phenylenediamine, 2- [3-acetylaminoethyloxy para-phenylenediamine, and their addition salts 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-diaminopropanol, 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, 1,8-bis- (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts. Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2 - ([3-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts. Among the ortho-aminophenols, there may be mentioned, by way of example, 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-amino phenol, and their addition salts.

Among the heterocyclic bases that may be mentioned, for example, pyridine derivatives, pyrimidine derivatives and pyrazole derivatives. Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 2,3-diamino-6-methoxy pyridine, 2 - ([3-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts. 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 2 801. 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-diaminopyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-ylpyrazolo [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-aminopyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-aminopyrazolo [1,5-a] pyridin-7-ol; as well as their addition. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 23 59 399; JP 88-169571; JP 05-63124; EP 0 770 375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in the patent application FR-A-2,750,048 and among which mention may be made of pyrazolo - [1,5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [ 1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-N, 7-N-7-tetramethyl-pyrazolo [1,5-a] -pyrimidine-3, 7-diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine and their addition salts and tautomeric forms, when tautomeric equilibrium exists. Among the pyrazole derivatives, mention may be made of the compounds described in DE 38 43 892, DE 41 33 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as 4,5-diamino 1- (3-hydroxyethyl) pyrazole, 4,5-diamino-1-methyl pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole , 4,5-diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3 dimethyl 5-hydrazino pyrazole, 1-benzyl 4,5-diamino-3-methyl pyrazole, 4,5-diamino-3-tert-butyl-1-methyl pyrazole, 4,5-diamino-1-tert-butyl-3-methyl pyrazole, 4,5-diamino 1 - ([3-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-diamino-1-ethyl-3- (4'-methyl) 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 - ([3-hydroxyethyl) amino-1-methyl pyrazole, 2,3-diamino-6,7-dihydro-1H, 5H pyrazolo [1,2-a] pyrazol-1-one and their addition salts. The coupler or couplers present in the composition according to the present invention may be chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. By way of examples, mention may be made of 3-amino phenol, 2-methyl-5-amino phenol, 2-methyl-5- (3-hydroxyethylamino) phenol, 2-chloro-6-methyl-3-amino phenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (3-hydroxyethyloxy) benzene, 2-amino-4- (R-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol , 1-β-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxy pyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2, 6-bis (3-hydroxyethylamino) toluene and their addition salts. The oxidation base (s) present in the composition of the invention are generally each in an amount of between 0.001 and 10% by weight approximately of the total weight of the dyeing composition, preferably between 0.005 and 6%. The coupler or couplers present in the composition of the invention are in general each in an amount of between 0.001 and 10% by weight of the total weight of the dyeing composition, preferably between 0.005 and 6%.

In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, (C 1 -C 4) alkyl sulfonates, and in particular methylsulfonates, tosylates, benzenesulfonates, phosphates and acetates and base addition salts such as soda, potash, ammonia, amines or alkanolamines. By natural dyes is meant any dye or dye precursor having a natural occurrence and produced either by extraction (and optionally purification) from a plant matrix, or by chemical synthesis. By contrast, synthetic dyes are understood to mean any dye that does not have a natural occurrence. As examples of suitable synthetic direct dyes, mention may be made of azo direct dyes; methinic; carbonyls; azinic; nitro (hetero) aryl; tri- (hetero) aryl methanes; alone or in mixtures. More particularly, the azo dyes comprise a function -N = N-whose two nitrogen atoms are not simultaneously engaged in a ring. However, it is not excluded that one of the two nitrogen atoms of the sequence -N = N-is engaged in a cycle.

The dyes of the family of methines are more particularly compounds comprising at least one sequence chosen from> C = C <and -N = C <whose two atoms are not simultaneously engaged in a ring. It is however specified that one of the nitrogen or carbon atoms of the chains can be engaged in a cycle. More particularly, the dyes of this family are derived from true methine-type compounds (comprising one or more C = C-chains referred to above); azomethine (comprising at least one or more sequences - C = N-) with, for example, azacabocyanines and their isomers, diazacarbocyanines and their isomers, tetraazacarbocyanines; mono- and diarylmethane; indoamines (or diphenylamines); indophenols; indoanilines.

As regards the dyes of the carbonyl family, mention may be made, for example, of the dyes chosen from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone, (iso) violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigo, thioindigo, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole, coumarin. As regards the dyes of the family of azines, there may be mentioned in particular azine, xanthene, thioxanthene, fluorindine, acridine, (di) oxazine, (di) thiazine, pyronine. The nitro (hetero) aromatic dyes are more particularly nitrobenzene or nitro pyridinic direct dyes. With regard to porphyrin or phthalocyanine dyes, it is possible to use cationic or non-cationic compounds, optionally comprising one or more metals or metal ions, for example alkali and alkaline earth metals, zinc and silicon. By way of example of particularly suitable direct dyes, mention may be made of the nitro dyes of the benzene series; azo direct dyes; methinic; azomethines with more particularly diazacarbocyanines and their isomers and tetraazacarbocyanines (tetraazapentamethines); quinone direct dyes and in particular anthraquinone, naphthoquinone or benzoquinone dyes; direct azine dyes; xanthenics; triarylmethanics; indoamines; indigoids; phthalocyanines and porphyrins; alone or in mixtures. Preferably, the direct dyes are chosen from nitro dyes of the benzene series; azo; azomethines with diazacarbocyanines and their isomers, tetraazacarbocyanines (tetraazapentamethines); anthraquinone direct dyes; triarylmethane direct dyes; alone or in mixtures. Even more preferably, these direct dyes are chosen from nitro dyes of the benzene series; azo direct dyes; azomethines with diazacarbocyanines and their isomers, tetraazacarbocyanines (tetraazapentamethines); alone or in mixture. Among the nitrobenzene direct dyes that may be used according to the invention, the following compounds may be mentioned in a nonlimiting manner: 1,4-diamino-2-nitrobenzene -1-amino-2-nitro-4-G3-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) (G3-hydroxyethyl) -aminobenzene-1-amino-3-methyl-4-13 hydroxyethylamino-6-nitrobenzene-1-amino-2-nitro-4-13-hydroxyethylamino-5-chlorobenzene-1,2-diamino-4-nitrobenzene-1-amino-2-13-hydroxyethylamino-5-nitrobenzene -1 2-Bis- (13-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-1-13-hydroxyethyl loxy-2-13-hydroxyethylamino-5-nitrobenzene-1-methoxy-2-13-hydroxyethylamino-5-nitrobenzene-1-13-hydroxyethyloxy-3-methylamino-4-nitrobenzene-1-r-dihydroxypropyloxy-3-methylamino 4-nitrobenzene -1-13-hydroxyethylamino-4-13, γ-dihydroxypropyloxy-2-nitrobenzene-1-Ry-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene-1-13-hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene - 1-13-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- (13-hydroxyethyl) -amino-3-nitrobenzene-1-3-hydroxyethylamino-2-nitrobenzene-1-hydroxy-4- (3-hydroxyethyl) amino 3-nitrobenzene.

Among the azo, azomethine and methine direct dyes that may be used according to the invention, mention may be made of the cationic dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714954; FR 2189006, FR 2285851, FR 2140205, EP 1378544, EP 1674073. For example, the synthetic direct dye (s) may be chosen from azo-type monochromophoric cationic direct dyes; methines; azomethines with diazacarbocyanines and their isomers, tetraazacarbocyanines; anthraquinone; alone or in mixture. Thus, mention may in particular be made of the cationic direct dyes corresponding to the following formulas: ## STR1 ## in which: D represents a nitrogen atom or the group -CH, R, and R 2, which may be identical or different; , represent a hydrogen atom; a C 1 -C 4 alkyl radical which may be substituted by a -CN, -OH or -NH 2 radical or form, with a carbon atom of the benzene ring, an optionally oxygenated or nitrogenous heterocycle, which may be substituted by one or more C 1 -C 4 alkyl radicals; C4; a 4'-aminophenyl radical, R3 and R'3, which may be identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano radical or a C1-C6 alkyl radical; C4, C1-C4 alkoxy or acetyloxy, X - represents an anion preferably selected from chloride, methyl sulfate and acetate, A represents a group chosen by the following structures: 11 + N + R4N \ / R4 R4 R4 \ In which R4 represents a C1-C4 alkyl radical which may be substituted by a hydroxyl radical; Wherein R 5 represents a hydrogen atom, a C 1 -C 4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine, R6 represents a hydrogen atom, a C1-C4 alkyl radical or forms, with a carbon atom of the benzene ring, an optionally oxygenated heterocycle and / or substituted with one or more C1-C4 alkyl groups, R1 represents a hydrogen or halogen atom such as bromine, chlorine, iodine or fluorine, D, and D2, which may be identical or different, represent a nitrogen atom or the group -CH, m = 0 or 1, X - represents a cosmetically acceptable anion and preferably selected from chloride, methyl sulfate and acetate, E represents a group chosen by the following structures: R 'N + N + N + R' R 'in which R' represents an alkyl radical in C1-C4; when m = 0 and D, represents a nitrogen atom, then E can also denote a group of following structure: R 'N + R' wherein R 'represents a C1-C4 alkyl radical. Among the abovementioned compounds, the following compounds are especially used: N = CHN N N- (A) CH 3 N CH 3 N = NN N + CH 3 CH 3, (A 2) N = N-NH 2 X-NH CH 3 N = N ( A3) NH2 X- (A4yH3CuN + 1C = N1NCH3X- (A5) OCH3 x- (A6) H3CN-CNNH1CH3X- representing a cosmetically acceptable anion or mixture of anions. Tetraazapentamethine type usable according to the invention include the following compounds listed in the table below: X ~ 'NJ / ~ N \ N \ N ~ N ~ ~ ^ NIIXN ~ 3 NN 1 X OOMe NNN ~ OOMe X OMe I NNNYN ~ NN OMe N nNi 1 N + '~ N NO NO XNN NO NO X -H OH OH XI NN' ~ N \ / N \ NN IX N + ~ N NO NXNNN ~ NNNXNN NO X OH OH OH X represents a anion or a mixture of cosmetically acceptable anions, preferably chosen from chloride, iodide, methyl sulphate, ethyl sulphate and acetate, etc. As other dyes that may be used according to the invention, mention may also be made of dyes azo direct colors following paragraphs, described in the COLOR INDEX INTERNATIONAL 3rd edition: - Disperse Red 17 - Disperse Red 13 - Basic Red 22 - Basic Red 76 - Basic Yellow 57 - Basic Brown 16-Basic Brown 17 - Disperse Green 9 - Disperse Black 9. - Solvent Black 3 - Disperse Blue 148 - Disperse Violet 63 - Solvent Orange 7. Mention may also be made of 1- (4'-aminodiphenylazo) -2-methyl-4bis- (13-hydroxyethyl) aminobenzene (INCI name: HC Yellow 7) . Among the quinone direct dyes are the following dyes: -Disperse Red 15 - Solvent Violet 13 - Solvent Blue 14 - Disperse Violet 1 - Disperse Violet 4 - Disperse Blue 1 - Disperse Violet 8 - Disperse Blue 3 - Disperse Red 11 - Disperse Blue 7 - Disperse Blue 14 - Basic Blue 22 - Disperse Violet 15 - Disperse Blue 377 - Disperse Blue 60 - Basic Blue 99 and the following compounds: - 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone - 1-Aminopropylamino-4-methylaminoanthraquinone 1-Aminopropylaminoanthraquinone-5-8-hydroxyethyl-1,4-diaminoanthraquinone-2-aminoethylaminoanthraquinone-1,4-bis (8-dihydroxypropylamino) anthraquinone. Another example is coumarin Disperse Yellow 82.

Among the azine dyes that may be mentioned are the following compounds: - Basic Blue 17 - Basic Red 2 - Solvent Orange 15. Among the triarylmethane dyes that can be used according to the invention, mention may be made of the following compounds: - Basic Green 1 - Basic Purple 3 - Among the indoamine dyes that may be used according to the invention, mention may be made of the following compounds: 2- [3-hydroxyethylamino-5- [bis (3-hydroxyethyl) -benzyl) amino] anilino-1,4-benzoquinone - 2- [3-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1,4-benzoquinone -3-N (2'-chloro-4'-amino)) 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, carbamylmethyl) amino] phenyl-ureido-6-methyl-1,4-benzoquinone imine. Preferably, the cationic direct dyes are chosen from azo direct dyes; methines; azomethines with diazacarbocyanines and their isomers, tetraazacarbocyanines (tetraazapentamethines); anthraquinone; alone or in mixture. For nonionic dyes, compounds having a LogP greater than or equal to 2 are particularly preferred.

For synthetic direct dyes of LogP greater than or equal to 2, it is recalled that the value of IogP conventionally represents the coefficient of partition of the dye between octanol and water. The IogP can be calculated according to the method described in the article by Meylan and Howard "Atom / Fragment contribution method for estimating octanol-water partition coefficient", J. Pharm. Sci. 84: 83-92, 1995. This value can also be calculated from many commercially available software that determines the IogP according to the structure of a molecule. By way of example, mention may be made of the Epiwin software from the United States Environmental Agency. In particular, the dyes suitable for carrying out the invention are chosen from the following compounds, alone or as a mixture: Dyestuff Chemical structure IogP Disperse Red 17 OH 3.69 02N ® N o N ® N OH O NH2 Disperse Violet 1 ® / ® 3.0 O NH2 OH HC Yellow 7 HZN N 2.38 ~ N OH Disperse Blue 377 O HN 3.21 ® / ® OH O HNOH Disperse Red 13 NN ~ 5.22 02N * "OH CI Disperse Green 9 NOZ 4.23 N ® N ~ OzN HN ~ O Solvent Black 3 N ® NN ® N 7.50 N OZ Disperse Blue 148 δ 4.81 N ~, s "N ® N o = Disperse Violet 63 'N N ~ 5,30 02N ® N HN N ° O Disperse Blue 60 O NHZ O 3,38 O NHZ \ ùo \ Disperse Blue 14 O ®, ® 4,25 O HN HN ~ Solvent Orange 15 IHII 3,90 Solvent Orange 7 H 4,40 N 2 ~ Solvent Blue 14 O HN 8,18 ®, ® O HN ~~ Disperse Yellow 82 N 3,68 N ~ \ NOOJ Even more preferentially, the direct dyes of the invention are chosen from cationic dyes azo types; methines; azomethines with diazacarbocyanines and their isomers, tetraazacarbocyanines (tetraazapentamethines); anthraquinone; alone or in a mixture, and in particular the dyestuffs (Al) to (A6) mentioned above, as well as the nonionic dyes of IogP greater than or equal to 2. Among the anionic direct dyes, mention may be made in particular of those described in the COLOR INDEX INTERNATIONAL 3rd edition under the name ACID and in particular: - Disperse Red 17 - Acid Yellow 9 - Acid Black 1 - Acid Yellow 36 - Acid Orange 7 - Acid Red 33 - Acid Red 35 - Acid Yellow 23 - Acid Orange 24 - Acid Purple 43 -Acid Blue 62 - Acid Blue 9 - Acid Violet 49 - Acid Blue 7. The synthetic direct dye (s), when present, preferably represent from 0.0001 to 10% by weight relative to the weight of the composition and preferably from 0.005 to 5% by weight with respect to the same reference. The composition according to the invention may comprise one or more natural dyes.

The natural dye (s) which are suitable in particular for the implementation of the invention are preferably chosen from lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid and laccaic acid. purpurogallin, anthragallol, protocatechaldehyde, indigo, isatin, curcumin, spinusolin, chlorophylls, chlorophyllins, orceins, haematein, hematoxylin, brazilin, braziline, dyes safflower (such as carthamine), flavonoids (with eg morine, apigenidine, sandalwood), anthocyanins (of the apigeninidine type), carotenoids, tannins, sorghum and cochineal carmine , or their mixtures. It is also possible to use the extracts or decoctions containing these natural dyes and in particular the henna extracts. Preferably, the natural dye (s) are chosen from among lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid, laccaic acid, purpurogalline, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidine, chlorophyllin, sorghum, orceins, cochineal carmine, haematein, hematoxylin, brazilin and braziline, and mixtures thereof. These dyes may optionally be used in the presence of mordants (eg salts of zinc, manganese, aluminum, iron, etc.). The natural dyes, when they are present, preferably represent from 0.001 to 10% by weight. preferably from 0.01 to 8% by weight, better still from 0.1 to 5% by weight, relative to the weight of the composition. Preferably, the composition according to the invention comprises one or more oxidation dye precursors. The polycondensate (s) of ethylene oxide and of propylene oxide consisting of polyethylene glycol and polypropylene glycol blocks present in the composition according to the invention are triblock copolymers polyethylene glycol / polypropylene glycol / polyethylene glycol.de chemical structure next :

H - (OC H 2 -CH 2) a- (OC H (CH 3) -CH 2) b- (OC H 2 -CH 2) a'-OH, in which a, a 'are from 2 to 150 and b is from 1 to 100. Preferably, a and a 'are from 10 to 130 and b is from 20 to 80. Preferably, a and a' are the same. According to a particular embodiment of the invention, the polycondensate (s) of ethylene oxide and of propylene oxide have a weight average molecular weight ranging from 1000 to 15000, and better still ranging from 1500 to 15000, and in particular ranging from 1500 to 10,000, and even more preferably from 1500 to 5000. Advantageously, the polycondensate (s) of ethylene oxide and of propylene oxide have a cloud temperature, at 10 g / l in distilled water, greater than or equal to 20 ° C, preferably greater than or equal to 60 ° C. The cloud temperature is measured according to the ISO 1065 standard. As polycondensate of ethylene oxide and of propylene oxide that may be used according to the invention, mention may be made of the polyethylene glycol / polypropylene glycol / polyethylene glycol triblock polycondensates sold under the names "SYNPERONIC" such as "SYNPERONIC® PE / F32" (INCI name: POLOXAMER 108), "SYNPERONIC® PE / F108" (INCI name: POLOXAMER 338), "SYNPERONIC® PE / L44" (INCI name: POLOXAMER 124), "SYNPERONIC® PE / L42 (INCI name: POLOXAMER 122)," SYNPERONIC® PE / F127 "(INCI name: POLOXAMER 407)," SYNPERONIC® PE / F88 "(INCI name: POLOXAMER 238)," SYNPERONIC® PE / L64 "INCI name: POLOXAMER 184) by the company CRODA, or" LUTROL® F68 "(INCI name: POLOXAMER 188) by BASF. The polycondensate (s) of ethylene oxide and of propylene oxide may be present in the composition according to the invention in a content at least equal to 1% by weight relative to the total weight of the composition, preferably ranging from 1% to 50%, preferably 5 to 40%, more preferably 10 to 30% by weight. According to a particular embodiment, the composition according to the present invention comprises one or more fatty substances free of carboxylic acid group.

The term "fatty substance" means an organic compound which is insoluble in water at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg) (solubility in water less than 5% by weight, and preferably less than 1% by weight). %, even more preferentially at 0.1%). They have in their structure a chain of at least two siloxane groups or at least one hydrocarbon chain containing at least 6 carbon atoms. In addition, the fatty substances are generally soluble in organic solvents under the same conditions of temperature and pressure, such as for example chloroform, ethanol, benzene or decamethylcyclopentasiloxane. The fatty substances are in particular chosen from lower alkanes, fatty alcohols, fatty acid esters, fatty alcohol esters, oils, in particular mineral, vegetable, animal or synthetic non-silicone oils, non-silicone waxes and silicones.

It is recalled that for the purposes of the invention, the alcohols, esters and fatty acids more particularly have one or more linear or branched hydrocarbon groups, saturated or unsaturated, comprising 6 to 30 carbon atoms, which are optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise. As regards the lower alkanes, the latter preferably comprise from 6 to 16 carbon atoms and are linear or branched, possibly cyclic. For example, the alkanes may be chosen from hexane and dodecane, isoparaffins such as isohexadecane and isodecane. Non-silicone oils that can be used in the composition of the invention include, for example: hydrocarbon-based oils of animal origin, such as perhydrosqualene; hydrocarbon-based oils of vegetable origin, such as liquid triglycerides of fatty acids containing from 6 to 30 carbon atoms, for instance triglycerides of heptanoic or octanoic acids or, for example, sunflower, corn or soybean oils, squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor oil, avocado, triglycerides of caprylic / capric acids such as those sold by Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil, shea butter oil; hydrocarbons with more than 16 linear or branched carbon atoms, of mineral or synthetic origin, such as liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes, hydrogenated polyisobutenes such as Parleam®. fluorinated oils such as perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, sold under the names "FLUTEC® PC1" and "FLUTEC® PC3" by BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names "PF 5050®" and "PF 5060®" by the company 3M, or bromoperfluorooctyl sold under the name "Foralkyl®" by the company Atochem; nonafluoro-methoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name "PF 5052®" by the company 3M.

The fatty alcohols that can be used in the composition of the invention are non-oxyalkylenated. They are saturated or unsaturated, linear or branched, and contain from 6 to 30 carbon atoms and more particularly from 8 to 30 carbon atoms, mention may be made of cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol or linoleic alcohol. The wax or non-silicone waxes that may be used in the composition of the invention are chosen in particular from Carnauba wax, Candelila wax, and Alfa wax, paraffin wax, ozokerite, vegetable waxes such as olive wax, rice wax, hydrogenated jojoba wax or absolute waxes of flowers such as the essential wax of blackcurrant flower sold by the company BERTIN (France), animal waxes such as waxes bees, or modified beeswaxes (cerabellina); other waxes or waxy raw materials that can be used according to the invention are, in particular, marine waxes, such as the one sold by SOPHIM under the reference M82, and polyethylene or polyolefin waxes in general. The esters are esters of saturated or unsaturated, linear or branched C 1 -C 26 aliphatic mono- or polyacids and saturated or unsaturated, linear or branched C 1 -C 26 aliphatic mono or polyalcohols, the total number of carbon of the esters being more particularly greater or equal to 10. Among the monoesters, mention may be made of dihydroabiethyl behenate; octyldodecyl behenate; isoketyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso) stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl ricinoleate acetyl; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate; , styryl, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.

Still in the context of this variant, it is also possible to use esters of C 4 -C 22 di or tricarboxylic acids and of C 1 -C 22 alcohols and esters of mono di or tricarboxylic acids and di, tri, alcohols. C2-C26 tetra or pentahydroxy. These include: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate, tridecyl erucate; triisopropyl citrate; triisotearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisanonate; and polyethylene glycol distearates.

Among the esters mentioned above, it is preferred to use ethyl, isopropyl, myristyl, cetyl, stearyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, myristates of alkyls such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate, cetyl octanoate. The composition may also comprise, as fatty ester, esters and diesters of C 6 -C 30, preferably C 12 -C 22, fatty acid sugars. It is recalled that "sugar" is understood to mean oxygenated hydrocarbon compounds which have several alcohol functions, with or without an aldehyde or ketone function, and which contain at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides. Suitable sugars include, for example, sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and their derivatives. especially alkylated, such as methylated derivatives such as methylglucose. The esters of sugars and fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of C 6 -C 30, preferably C 12 -C 22 fatty acids, linear or branched, saturated or unsaturated. If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise.

The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters and mixtures thereof. These esters may be for example oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonates, or mixtures thereof, such as, in particular, the mixed oleo-palmitate, oleostearate and palmitostearate esters. More particularly, the mono- and di-esters are used, and especially the mono- or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, sucrose, glucose or methylglucose.

By way of example, mention may be made of the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate. Mention may also be made, by way of examples, of esters or mixtures of esters of fatty acid sugar: the products sold under the names F160, F140, F110, F90, F70, SL40 by the company Crodesta, respectively denoting sucrose palmito-stearates of 73% monoester and 27% di- and tri-ester, 61% monoester and 39% di-, tri- and tetraester, 52% monoester and 48% monoester; % di-, tri- and tetraester, 45% monoester and 55% di-, tri- and tetraester, 39% monoester and 61% di-, tri-, and tetra. -ester, and sucrose mono-laurate; the products sold under the name Ryoto Sugar Esters, for example referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% di-triester-polyester; the sucrose mono-dipalmito-stearate marketed by Goldschmidt under the name Tegosoft® PSE.

The silicones that can be used in the composition of the present invention are volatile or non-volatile, cyclic, linear or branched silicones, modified or not with organic groups, having a viscosity of 5 × 10 -6 to 2.5 m 2 / s at 25 ° C. and preferably 1.10-5 to 1 m2 / s. The silicones that can be used in accordance with the invention can be in the form of oils, waxes, resins or gums. Preferably, the silicone is chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), and organomodified polysiloxanes comprising at least one functional group chosen from poly (oxyalkylene) groups, amino groups and alkoxy groups.

Organopolysiloxanes are further defined in Walter Noll's "Chemistry and Technology of Silicones" (1968), Academie Press. They can be volatile or nonvolatile. When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60 ° C. and 260 ° C., and even more particularly from: (i) cyclic polydialkylsiloxanes containing from 3 to 7, preferably from 4 to 5 silicon atoms. It is, for example, octamethylcyclotetrasiloxane sold in particular under the name VOLATILE SILICONE® 7207 by UNION CARBIDE or SILBONE® 70045 V2 by RHODIA, decamethylcyclopentasiloxane sold under the name VOLATILE SILICONE® 7158 by UNION CARBIDE, and SILBONE ® 70045 V5 by RHODIA, as well as their mixtures. Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the VOLATILE® SILICONE FZ 3109 marketed by the company UNION CARBIDE, of formula: ## STR5 ## where: ## STR1 ## Cyclic polydialkylsiloxane mixtures can also be mentioned with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1 '- ( hexa-2,2,2 ', 2', 3,3'-trimethylsilyloxy) bis-neopentane (ii) linear volatile polydialkylsiloxanes having 2 to 9 silicon atoms and having a viscosity of less than or equal to 5.10-6 m2 / at 25 ° C. It is, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200" by Toray Silicone, silicones entering this class are also described in the published article. in Cosmetics and Toiletries, Vol 91, Jan. 76, 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics". Non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the above organofunctional groups and mixtures thereof are preferably used.

These silicones are more particularly chosen from polydialkylsiloxanes, among which may be mentioned mainly polydimethylsiloxanes with trimethylsilyl end groups. The viscosity of the silicones is measured at 25 ° C. according to ASTM 445 Appendix C.

Among these polydialkylsiloxanes, mention may be made, without limitation, of the following commercial products: SILBIONE® oils of the 47 and 70 047 series or the MIRASIL® oils marketed by RHODIA, such as, for example, the 70 047 V 500 000 oil; the oils of the MIRASIL® series marketed by RHODIA; the oils of the 200 series of Dow Corning, such as DC200 having a viscosity of 60,000 mm 2 / s; - VISCASIL® oils from GENERAL ELECTRIC and some oils from SF series (SF 96, SF 18) from GENERAL ELECTRIC. Mention may also be made of polydimethylsiloxanes with dimethylsilanol end groups known under the name of dimethiconol (CTFA), such as the oils of the 48 series from the company RHODIA. In this class of polydialkylsiloxanes, mention may also be made of the products sold under the names "ABIL WAX® 9800 and 9801" by GOLDSCHMIDT, which are polydialkyl (C1-C20) siloxanes.

The silicone gums that can be used in accordance with the invention are in particular polydialkylsiloxanes, preferably polydimethylsiloxanes having high average molecular weights of between 200,000 and 1,000,000 used alone or in a mixture in a solvent. This solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane or their mixtures. More particularly useful products according to the invention are mixtures such as: - mixtures formed from an end-hydroxylated polydimethylsiloxane, or dimethiconol (CTFA) and a cyclic polydimethylsiloxane also called cyclomethicone (CTFA) such that the product Q2 1401 marketed by the company Dow Corning; mixtures of a polydimethylsiloxane gum and a cyclic silicone such as the product SF 1214 Silicone Fluid from the company General Electric, this product is an SF 30 gum corresponding to a dimethicone, having a number average molecular weight of 500,000 solubilized in oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane; mixtures of two PDMSs of different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company General Electric. The product SF 1236 is the mixture of an SE 30 gum defined above having a viscosity of 20 m 2 / s and an SF 96 oil with a viscosity of 5.10-6 m 2 / s. This product preferably comprises 15% of SE gum and 85% of an SF 96 oil. The organopolysiloxane resins that can be used in accordance with the invention are crosslinked siloxane systems containing the units: R 2 SiO 2/2, R 3 SiO 1/2, RSiO 3 / 2 and SiO4 / 2 wherein R represents an alkyl having 1 to 16 carbon atoms. Among these products, those that are particularly preferred are those in which R denotes a C1-C4 lower alkyl group, more particularly methyl.

Among these resins may be mentioned the product marketed under the name "Dow Corning 593" or those sold under the names "Silicone Fluid SS 4230 and SS 4267" by the company General Electric and which are silicones of dimethyl / trimethyl siloxane structure. Mention may also be made of the trimethylsiloxysilicate type resins sold in particular under the names X22-4914, X21-5034 and X21-5037 by the company Shin-Etsu. The organomodified silicones that may be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group. In addition to the silicones described above, the organomodified silicones may be polydiarylsiloxanes, in particular polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned above.

The polyalkylarylsiloxanes are particularly chosen from polydimethyl / methylphenylsiloxanes, linear and / or branched polydimethyl / diphenylsiloxanes with a viscosity ranging from 1 × 10 -5 to 5 × 10 -2 m 2 / s at 25 ° C. Among these polyalkylarylsiloxanes, mention may be made by way of example of the products sold under the following names: SILBONE® oils of the 70 641 series from RHODIA; - the RHODORSIL® 70 633 and 763 RHODIA series of oils; - DOW CORNING 556 COSMETIC GRAD FLUID oil from Dow Corning; the silicones of the PK series of BAYER, such as the product PK20; the silicones of the PN, PH series of BAYER, such as the PN1000 and PH1000 products; certain oils of the SF series of GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250 and SF 1265. Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising: polyethyleneoxy and / or polypropyleneoxy groups optionally comprising C 6 alkyl groups; -C24 such as the products known as dimethicone copolyol marketed by the company Dow Corning under the name DC 1248 or the oils SILWET® L 722, L 7500, L 77, L 711 from UNION CARBIDE and alkyl (C12) -methicone copolyol sold by the company Dow Corning under the name Q2 5200; substituted or unsubstituted amine groups such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company Genesee or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amino groups are, in particular, C1-C4 aminoalkyl groups; alkoxylated groups, such as the product sold under the name "Silicone Copolymer F-755" by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by the company GOLDSCHMIDT. Preferably, the fatty substances are neither oxyalkylenated nor glycerolated. More particularly, the fatty substances are chosen from liquid or pasty compounds at ambient temperature and at atmospheric pressure. Preferably, the fatty substance is a liquid compound at a temperature of 25 ° C. and at atmospheric pressure. The fatty substances are preferably chosen from C6-C16 lower alkanes, fatty alcohols, fatty acid esters, fatty alcohol esters, non-silicone oils of mineral origin with more than 16 carbon atoms, or of vegetable or synthetic origin, silicones. In particular, the one or more fatty substances of the composition according to the invention are non-silicone. According to one embodiment of the invention, the fatty substance or fats are chosen from liquid petroleum jelly, polydecenes, esters of fatty acids or fatty alcohols, liquids or mixtures thereof. In particular, the one or more fatty substances of the composition according to the invention are non-silicone. C6-C16 lower alkanes or hydrocarbons having more than 16 carbon atoms will preferably be selected.

Vaseline oil is particularly preferred. If they are present, the amount of fatty substance in the composition according to the invention is preferably between 1 and 75%, better between 10 and 70%, even more preferably between 20 and 65% by weight. The medium suitable for dyeing, also called dyeing medium, is a cosmetic medium generally consisting of water or a mixture of water and one or more organic solvents. As organic solvent, there may be mentioned for example lower alkanols C1-C4, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof. 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 hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants or mixtures thereof, anionic polymers, cationic, nonionic, amphoteric, zwitterionic or their mixtures, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents. The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the dye composition.

Of course, one skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged. The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 11 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. Among the acidifying agents, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids.

Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and wherein R is a propylene residue optionally substituted by a hydroxyl group or a C1-C4 alkyl radical; Ra, Rb, Rc and Rd, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 hydroxyalkyl radical. The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, and especially human hair. The composition according to the invention may also comprise one or more oxidizing agents. In this case, we speak of ready-to-use compositions.

In particular, the ready-to-use composition is obtained by extemporaneous mixing, prior to application, of a composition previously described, with at least one composition comprising one or more oxidizing agents.

The oxidizing agent is preferably chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, for example alkali or alkaline earth metal persulfates, perborates and percarbonates. like sodium, potassium, magnesium.

The use of hydrogen peroxide is particularly preferred. This oxidizing agent is advantageously constituted by hydrogen peroxide in aqueous solution (hydrogen peroxide), the titre of which may vary, more particularly, from 1 to 40 volumes, and even more preferably from 5 to 40 volumes. The compositions according to the invention can result from the extemporaneous mixing of several compositions. Another object of the invention is therefore constituted by a process for dyeing keratinous fibers, which consists in applying the composition described above. According to a first embodiment, the composition applied does not comprise an oxidizing agent. This embodiment is appropriate especially in the case where the composition does not comprise oxidation dye precursor (bases, coupler) According to a second embodiment, the composition is applied in the presence of at least one oxidizing agent. According to a first variant of this embodiment, the ready-to-use composition which has just been detailed and which is obtained by extemporaneous mixing before application of a composition according to the invention without oxidizing agent with an oxidizing composition. According to a second variant of this embodiment, the composition according to the invention is applied without oxidizing agent, and an oxidizing composition, successively and without intermediate rinsing. The oxidizing composition used comprises one or more oxidizing agents as defined above. Regarding the organic solvents possibly present in the oxidizing composition, reference may be made to the list indicated previously in the context of the description of the composition according to the invention. 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. We can again refer to the list of additives given above. In one variant of the invention, the ready-to-use composition obtained by extemporaneous mixing before application, of a composition according to the invention devoid of an oxidizing agent with an oxidizing composition contains more than 20% by weight, preferably more 25%, better than 30% fat as defined above. Whatever the embodiment chosen (with or without an oxidant), the mixture applied to the fibers is left in place for a duration, in general, of the order of 1 minute to 1 hour, preferably of 10 minutes to 30 minutes. minutes. The temperature during the process is conventionally between 10 and 200 ° C. and more particularly 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. The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains the dye composition of the present invention defined above with the exception of the oxidizing agent and a second compartment contains a oxidizing composition. This device may be equipped with means for delivering the desired mixture to the hair, such as the devices described in patent FR-2 586 913 in the name of the applicant. The present invention also relates to the use for dyeing keratinous fibers, and in particular human keratin fibers such as the hair, of a composition as defined above. The subject of the present invention is also the use, for increasing the solubilitation of the hair dyes in the dyeing composition, of one or more polycondensates of ethylene oxide and of propylene oxide consisting of polyethylene glycol and polypropylene glycol blocks. as defined previously.

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

EXAMPLE The following coloring compositions were carried out (amounts expressed in grams of commercial product): Composition AB Para-aminophenol 3.05 3.05 Resorcinol 1.1 1.1 2-methyl-5-hydroxyethylaminophenol 5.24 5.24 4-amino-2-hydroxytoluene 1.74 1.74 Toluene-2,5-diamine 2.12 2.17 Propylene glycol 6.2 6.2 Ethanol 8.8 8.8 Hexylene glycol 3 3 Dipropylene glycol 3 3 Monoethanolamine pure 14.5 14.5 Ascorbic acid 0.25 0.25 Demineralized water 30 51 Condensate of ethylene oxide / propylene oxide / oxide 21 0 of ethylene (MW = 2900 g / mol) (13 EO / 30OP / 13OE) or POLOXAMER 184 Composition B containing no polycondensate of ethylene oxide and propylene oxide forms a precipitate after a few hours at room temperature. On the other hand, composition A containing a polycondensate of ethylene oxide and propylene oxide remains clear, even after 2 months at 45.degree.

The following compositions C and D are also prepared (the amounts are expressed in g% of active ingredients): Composition C Disteardimonium hectorite (Bentone 38 VCG) 3 Octyldodecanol 11.55 Glycol Distearate 8 Vaseline Oil 64.5 Propylene Carbonate 1 Laureth-2 1 Polysorbate 21 11 Composition D Pentasodium pentetate 0.15 Hydrogen peroxide (50% aqueous solution) 12 Sodium stannate 0.04 Phosphoric acid Qs pH 2.2 Tetrasodium pyrophosphate 0.03 Vaseline oil 20 Homopolymer chloride of dimethyldiallylammonium 0.5 sold by NALCO under the name Merquat 100 Glycerine 0.5 Cetylstearyl alcohol (C16 / C18 30/70 to NAFOL 1618F) 8 Cetylstearyl alcohol oxyethylenated (33E) 3 Amide of oxyethylene rapeseed acids (4) 0E) 1,2 Vitamin E: DL-α-tocopherol 0.1 water Qs 100 Application method: The compositions detailed above are mixed at the time of use in the following proportions: * 10 g of the composition C * 4 g of the composition A or B * 16 g of the composition D. The resulting mixtures are then applied to hair strands natural to 90% white, at a rate of 10 g of mixture per 1 g of hair. The mixtures are left at room temperature for 30 minutes.

The hair is then rinsed, washed with standard shampoo and dried. Dyed locks are obtained in a more homogeneous and intense manner from the mixture resulting from composition A.

Claims (8)

REVENDICATIONS1. Composition for dyeing keratinous fibers comprising, in a medium suitable for dyeing: one or more hair dyes; and one or more polycondensates of ethylene oxide and propylene oxide consisting of polyethylene glycol and polypropylene glycol blocks of the following chemical structure: H - (O-C H) 2-C H 2) a- (O-C H (C H 3) -C H 2) b- (O-C H 2 -C 2 H) a'-O H, wherein a and a 'are from 2 to 150, and b is from 1 to 100; except for the following composition: INCI name g% Beheneth-10 6.00 Sorbitol 5.00 Vaseline oil 60.25 Water 10.00 Ethanol 2.00 Poloxamer 184 5.00 Potassium bicarbonate 1.75 Water 4.302 Monoethanolamine 5.00 p-phenylenediamine 0.216 2,4- 0,482 diaminophenoxyethanol dihydrochloride and the following composition obtained by mixing the emulsion Al: Emulsion Al Phase INCI name g% Beheneth-10 6,00 Sorbitol 5,00 A Vaseline 60.25 Water 10.00 with an aqueous composition (B) comprising a dispersion of fatty alcohols in water (8%) and 6% of hydrogen peroxide in a ratio of 1 weight of (Al) to 1, 5 weight of (B). 2. Composition according to claim 1, in which the hair dye or dyes are chosen from synthetic direct dyes, natural dyes and oxidation dye precursors, nonionic or ionic dyes. 3. Composition according to any one of claims 1 and 2 wherein a, a 'are from 10 to 130 and b ranges from 20 to 80. 4. Composition according to any one of claims 1 to 3 wherein a and a 'are identical. 5. Composition according to any one of claims 1 to 4 wherein the polycondensate (s) of ethylene oxide and of propylene oxide have a weight average molecular weight ranging from 1000 to 15000. 1 to 5 comprising 6. Composition according to any one of the claims of addition to one or more oxidizing agents. a composition 7. A method of dyeing keratin fibers in which as defined in any one of claims 1 to 5 is applied to the keratinous fibers in the presence of one or more oxidizing agents for a time sufficient to develop the desired coloration. first compartment 8. A multi-compartment device in which one contains a dye composition as defined in any one of claims 1 to 5 and a second compartment contains one or more oxidizing agents. Use for dyeing keratinous fibers of such a composition9. as defined in any one of claims 1 to 6. Ethanol Poloxamer 184 Potassium bicarbonate Water Monoethanolamine p-phenylenediamine 2,4-diaminophenoxyethanol dihydrochloride B 2.00 5.00 1.75 4.302 5.00 0.216 0.48210. Use, for increasing the solubilitation of hair dyes in the dyeing composition, of one or more polycondensates of ethylene oxide and of propylene oxide consisting of polyethylene glycol and polypropylene glycol blocks as defined in any one of the Claims 1 and 3 to 5.5