FR2949333A1 - Dye composition, useful for coloring keratin fibers, preferably human hair, comprises hydrophobic direct dye, mineral bases comprising carbonates and/or bicarbonates, and carbonyl compounds - Google Patents

Abstract

Dye composition (A) comprises: one or more hydrophobic direct dye with a logarithm of the partition coefficient (logP) of >= 2; one or more mineral bases comprising carbonates and/or bicarbonates; and one or more carbonyl compounds (I). Dye composition (A) comprises: one or more hydrophobic direct dye with a logarithm of the partition coefficient (logP) of >= 2; one or more mineral bases comprising carbonates and/or bicarbonates; and one or more carbonyl compounds of formula (-C(=O)-(CH 2) n-X-a) (I). X-a : -C(=O)-, -CH(OH)- or -C(OH)=; and n : 0-4.

Description

A compound comprising a hydrophobic dye, a mineral base and a particular compound (I), and its use in coloration Invention of: Boris LALLEMAN Alain LAGRANGE Composition comprising a hydrophobic dye, a mineral base and a particular compound (I), and its use in coloring

The present invention relates to a dyeing composition for human keratin fibers, comprising at least one hydrophobic dye, at least one particular compound (I) and at least one particular mineral base, and to a dyeing process. Two major modes of staining human keratin fibers, and in particular hair, are known.

The first, called oxidation or permanent staining, consists in using 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, by a process of oxidative condensation, colored species which remain trapped inside the fiber. 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. The variety of molecules involved in the oxidation bases and couplers allows a rich palette of colors to be obtained. This type of coloration also makes it possible to obtain permanent dyes, but the use of oxidizing agents may lead to degradation of the keratin fibers. The second mode of staining, called direct or semi-permanent staining, comprises the application of direct dyes which are molecules having an affinity for the fibers and dyes even in the absence of 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 colorations are particularly chromatic but temporary or semi-permanent colorations because the nature of the interactions that bind the direct dyes to the keratin fiber, and their desorption of the surface and / or the core of the fiber are responsible for their low dyeing power and their poor resistance to washes or light.

To effectively stain keratinous fibers, most hydrophobic direct dyes must be used in the presence of particular solvents whose role is to vectorize them in the fiber. Among the known cosmetic solvents for this purpose, aromatic solvents are frequently used. Mention may more particularly be made of benzyl alcohol, benzyloxyethanol or phenoxyethanol. However, the presence of aromatic solvents, very poorly soluble in aqueous medium, requires the use of large amounts of co-solvents (usually ethanol) to make them compatible with conventional dye formulations. Moreover, even under these conditions, the intensity of the colorations obtained remains insufficient or the selectivity remains too high In addition, reducing agents such as hydrosulfites are sometimes used in the textile field, in order to reduce reducible hydrophobic dyes. However, these compounds are harmful to the environment, and particularly contaminate wastewater. On the other hand, they emit very uncomfortable odors, which make them unsuitable for use in the cosmetics field. There is therefore a need to provide new hydrophobic dye-based compositions for dyeing human hair that are more effective, while being compatible with hydrophobic dyes, and which respect both the environment and the nature of the hair. These compositions must also make it possible to obtain powerful, not very selective and resistant dyes. The Applicant has surprisingly discovered that this technical problem could be solved by a dye composition comprising one or more hydrophobic direct dyes of logP greater than or equal to 2, one or more particular compounds (I), and one or more mineral bases chosen from carbonates and hydrogenocarbonates.

The subject of the invention is therefore a composition comprising: one or more hydrophobic direct dyes of logP greater than or equal to 2, one or more mineral bases chosen from carbonates, hydrogenocarbonates and their mixtures, and one or more compounds ( I) comprising in their structure a sequence: CH2) nx O with n denoting an integer ranging from 0 to 4, and designating a group: C ùCH C Il O or OH or OH The value of logP represents in a conventional manner the coefficient of sharing of the dye between octanol and water. The logP 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 LogP based on the structure of a molecule. By way of example, mention may be made of the Epiwin software from the United States Environmental Agency. It should be noted that the logP value is usually given for a temperature of 25 ° C. In particular, the hydrophobic direct dye (s) present in the composition according to the invention may be chosen from the following compounds, alone or as a mixture: Dyestuff Chemical structure logP Disperse Red 17 OH 3.69 02N N 1 \ 1 N OH Disperse Violet 1 ~ 3.0 NH2 NH2 5 OH HC Yellow 7 HZN N 2.38 "" OH Disperse Blue O HN 3.21 377 O OH O HNOH Disperse Red 13 NN ~ 5.22 02N N OH Disperse Green 9N NOZ 4.23 'NN ~ OZN HN O Solvent Black 3 7.50 Disperse Blue N OZ 4.81 148 1 Ns NN 0 o ~ Disperse Purple NN ~ 5.30 63 02N N HN CN a O CI Disperse Blue 60 O NH2 3.38 O NH2 \\ O \ O HN Disperse Blue 14 ~ 4.25 O HN ~ Solvent Orange I NNN 1 3.90 15 Solvent Orange 7 HO 4.40 NN Solvent Blue 14 O HN 8.18 ~ O HN ~~ Disperse Yellow N 3.68 82 N ~ \ NOOJ The hydrophobic direct dye (s) present in the composition according to the invention can also be chosen from indigo dyes.

The indigo dyes that can be used in the composition according to the invention can be chosen from: Name dyeing principles Indigo OHHO Isoindigo OO Indirubin HONHOO Isoindirubin NH 4,4'-Dibromo Indigo ON ~ Br HNNH 6,6'-Dibromo Indigo Br ~ Br HO Br ~ ON o H 5,5'-dibromo indigo Br H _ O Br NOH cis-6,6'-dibromo indigo Br OO NH H, Br, 5 ', 7.7' - Br Br HO Br Br tetrabromo indigo N ù NOH 4,4 ', 7,7' Cl HO Cl tetrachloroindigo Cl N Cl NOH 3H-Indol-3-one, 1,2-dihydro-O 2- (3-oxobenzo [b] thien-2 (3H) -N ylidene) O Thioindigo O (other names: S CI 73300 or CI Disperse Red 364 O CI Solvent Red 242 CI Vat Red 41 Ciba Pink B Disperse Red 364) Vat Red 1 Cl O O Cl (Oralith) S ù SO Cis-Thioindigo OO (Benzo [b] thiophen-3 (2H) -one, SS 2- (3-oxobenzo [b] thien-2 (3H) -ylidene) -, (2Z)) 6,6'-dichloro-Cl HO Cl 4 4'-dimethylthioindigo NNOH, 5'-dichloro-1H-chloro 7,7'-dimethylthioindigo NNOH 4,4 ', 7,7'-HO tetramethylthioindigo NNOH Thioindigo Scarlet R N (other names: 2H Indol 2 one, O 1,3-dihydro-3- (3-oxobenzo [b] thien-2 (3H) -ylidene; CI 73635) 2H-Indol-2-one, 1,3-dihydro-H 3- (3-oxobenzo [b] thien-2 (3H) -NO-ylidene) -, (3E) -ES Thioindirubine SS (Benzo [b ] thiophen-3 (2H) -one, 2- (2-oxobenzo [b] thiophen-3 (2H) -ylidene)) 2H-indol-2-one, 1,3-dihydro-3- (2- oxobenzo [b] thiophen-N 3 (2H) -ylidene) -benzo [b] thiophen-2 (3H) -one, O 3- (2-oxobenzo [b] thiophen-3 (2H) -ylidene) can also use, as hydrophobic direct dyes of LogP greater than or equal to 2, the following indigo direct dyes: leucoindigo, leucoisoindigo, leucoindirubine, leucoisoindirubine. Preferably, the direct dyes of LogP greater than or equal to 2 are chosen from indigo dyes.

The hydrophobic direct dye (s) of LogP greater than or equal to 2 generally represents from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, better still from 0.1 to 5% by weight of the total weight. of the cosmetic composition. As explained above, the composition according to the invention also comprises one or more particular compounds (I). Preferably, the integer n denotes 0, 1 or 2. The particular compound or compounds (I) are preferably chosen from the following compounds: Hydroxyacetone O OH Acetoin O OH Glutaroin O 0 OH Adipoin O OH Dihydroxyacetone HOC / OH O Glycol Aldehyde HOC O15 Benzoin O OH 2,3-OJ OH dihydroxyacryl-OH aldehyde Cyclopentane O dione Acetonyl acetone OO Acetyl acetone OO diacetyl oo dipropionyl o O acid 2- HOOH O ketoglutaric OO acid 3- HO OOO ketoglutaric OH Pyruvic acid o OH oo Levulinic acid HO) ro Acid HO OO acetoacetic acid HO OO propionylacetic acid Acetoneyl Ho oz -, - / malonic o OH o Methyl aceto OO acetate acetate Ethyl acetoyl-oo Oo acetopyruvic acid o Cyclohexane OO dione Preferably the compound (s) present in their structure a sequence: ## STR1 ## where ## STR2 ## or OH OH (B). (B) being the tautomeric form of (A). Preferred compound (s) (I) are hydroxyacetone compounds such as hydroxyacetone, acetoin, glutaroin, adipoin and benzoin.

The compound (s) (I) generally represent from 0.01% to 20% by weight, preferably from 0.05% to 10% by weight and better still from 0.1% to 5% by weight relative to the total weight of the cosmetic composition.

The composition according to the invention also comprises one or more mineral bases chosen from carbonates, hydrogenocarbonates and mixtures thereof. By carbonate, in a manner known per se, is meant a salt containing the CO32- anion. By hydrogencarbonate, also known as bicarbonate, is denoted in a known manner a salt containing the anion HCO3-. Preferably, the mineral base (s) are chosen from alkali metal carbonates, alkali metal hydrogen carbonates, and mixtures thereof. The preferred alkali metals are lithium, sodium and potassium. According to a particularly preferred embodiment, the mineral base (s) are chosen from sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogencarbonate, and mixtures thereof. The particular mineral base or bases of the invention generally represent from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, and more preferably from 1 to 5% by weight, relative to the total weight. of the composition. The composition according to the invention may also advantageously comprise one or more organic compounds (II) having a Hansen solubility parameter value 8H of less than or equal to 16, preferably less than 16, more preferably between 5 and 15.8 MPa.sup.-2 and even more preferably between 8 and 15.8 MPa.sup.-2, and with a molecular weight of less than 250 g / mol. Preferably, these compounds are liquid at a temperature of 25 ° C and at atmospheric pressure (760 mm Hg).

The organic compound or compounds having a Hansen solubility parameter value 6H as defined above are, for example, described in the reference book Hansen solubility parameters. A user's handbook, Charles H. Hansen, CRC Press, 2000, pages 167 to 185 or in the Handbook of Solubility Parameters and Other Cohesion Parameters CRC, Press, pages 95 to 121 and pages 177 to 185. This value of the solubility parameter 6H is related to the formation of hydrogen bonds.

In particular, the book Handbook of Solubility Parameters and other cohesion parameters CRC Press, pages 95 to 121 and pages 177 to 185, gives the equation 6H = (E-zUh / V) 1/2 where ZUh (in J. mol-1) describes the contributions of the functional group considered in the hydrogen bond-related solubility parameters (table values 14 page 183); this parameter ZUh is also described in the book The relation between surface tension and solubility parameter in liquids, Bagda, E, Farbe Lack, 84, 212, 1978; and V is the volume of the molecule.

It should be noted that the value of the solubility parameter 6H is usually given for a temperature of 25 ° C. The at least one organic compound (II) may be chosen from alkanols, aliphatic esters, ethers, aromatic alcohols, alkylaryl alcohols, aromatic acids, aliphatic acids and alkylene carbonates, such as propylene carbonate. lactones such as ybutyrolactone, and mixtures thereof. Preferably, said organic compound (s) (II) are chosen from alkanols, aliphatic esters, ethers, aromatic alcohols, alkylaryl alcohols, aromatic acids, aliphatic acids, and mixtures thereof. Even more preferentially, said one or more organic compounds (II) are chosen from 1-octanol, 1-decanol, tridecyl alcohol, dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol and the like. butyl ether, propylene glycol n-propyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, 3-phenyl-1-propanol, 2-phenyl-1-propanol, benzyl alcohol, benzyloxyethanol, phenoxyethanol.

The organic compound (II) is preferably chosen from aromatic alcohols, alkylaryl alcohols and even more preferably benzyl alcohol. The organic compound (s) (II), when present, generally represent from 0.1 to 20%, preferably from 1 to 5%, by weight of the total weight of the composition. The composition according to the invention may also comprise one or more additional dyes. In particular, the composition according to the invention may also comprise at least one additional dye different from the hydrophobic dyes of logP greater than or equal to 2 chosen from natural dyes and non-natural direct dyes, oxidation dye precursors, or their combinations. 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. The additional natural dyes that are suitable in particular for the implementation of the invention may be chosen for example from carminic acid, kermesic acid, isatin, chlorophyllins, haematein, hematoxylin, brazilin, braziline, betanin, flavonoids, anthocyanins. It is also possible to use the extracts or decoctions containing these natural dyes and in particular the henna extracts.

The composition may also comprise one or more additional non-natural direct dyes different from the hydrophobic dyes described above, and chosen from ionic or nonionic species, preferably cationic or nonionic. As examples of suitable additional direct dyes, mention may be made of azo direct dyes; methinic; carbonyls; azinic; nitro (hetero) aryl; tri- (hetero) aryl methanes; porphyrins and phthalocyanines, 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 one cycle. More particularly, the dyes of this family are derived from true methine-type compounds (comprising one or more -C = C- above-mentioned sequences); azomethine (comprising at least one or more -C = N- chains) with, for example, azacarbocyanines and their isomers, diazacarbocyanines and their isomers, tetraazacarbocyanines; mono- and di-arylmethane; indoamines (or diphenylamines); indophenols; indoanilines. With regard to the dyes of the carbonyl family, mention may be made, for example, of non-natural 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, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole, coumarin. As regards the dyes of the family of cyclic 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. As examples of additional direct synthetic dyes particularly suitable, mention may be made of nitro dyes of the benzene series; azo direct dyes; methine azomethines; azacarbocyanines such as tetraazacarbocyanines (tetraazapentamethines); quinone direct dyes and in particular anthraquinone, naphthoquinone or benzoquinone dyes; direct azine dyes; triarylmethane xanthenics; indoamines; phthalocyanines and porphyrins alone or in mixtures. Even more preferably, these additional direct dyes are chosen from nitro dyes of the benzene series; azo direct dyes; methine azomethines and tetraazacarbocyanines (tetraazapentamethines) alone or as a mixture. These dyes may be monochromophoric dyes (that is to say comprising only one dye) or polychromophoric, preferably di- or tri-chromophoric dyes; the chromophores which may be identical or different, of the same chemical family or not. It should be noted that a polychromophoric dye comprises several radicals each derived from an absorbing molecule in the visible range between 400 and 800 nm. In addition, this absorbance of the dye does not require any prior oxidation thereof, or association with other (s) species (s) chemical (s).

In the case of polychromophoric dyes, the chromophores are connected to each other by means of at least one linker which may or may not be cationic. Among the polychromophoric dyes, mention may be made more particularly of azo and / or azomethine (hydrazonic) di- or trichromophoric dyes, symmetrical or not, comprising on the one hand at least one aromatic heterocycle comprising 5 or 6 ring members, optionally fused, comprising at least one quaternized nitrogen atom engaged in said heterocycle and optionally at least one other heteroatom (such as nitrogen, sulfur, oxygen), and on the other hand, at least one phenyl or naphthyl group, optionally substituted, optionally bearing at least one OR group with R representing a hydrogen atom, an optionally substituted C1-C6 alkyl radical, an optionally substituted phenyl ring, or at least one N (R ') 2 group with R 'identical or not, representing a hydrogen atom, an optionally substituted alkyl radical C1-C6, an optionally substituted phenyl ring; the radicals R 'which can form, with the nitrogen atom to which they are bonded, a saturated 5- or 6-membered heterocycle, or else one and / or both radicals R' may each form with the carbon atom of the aromatic ring placed in ortho of the nitrogen atom, a 5- or 6-membered saturated heterocycle. As aromatic cationic heterocycle, there may be mentioned, preferably, 5- or 6-membered rings comprising 1 to 3 nitrogen atoms, preferably 1 or 2 nitrogen atoms, one being quaternized; said heterocycle being optionally further fused to a benzene ring. It should also be noted that the heterocycle may optionally comprise another heteroatom different from nitrogen, such as sulfur or oxygen.

If the heterocycles or phenyl or naphthyl groups are substituted, they are substituted, for example, with one or more C 1 -C 8 alkyl radicals optionally substituted with a hydroxyl, C 1 -C 2 alkoxy or C 2 -C 4 hydroxyalkoxy, acetylamino or substituted amino group. one or two C 1 -C 4 alkyl radicals, optionally carrying a hydroxyl group or both radicals which can form, with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle, optionally comprising another identical heteroatom or different from nitrogen; a halogen atom; a hydroxyl group; a C1-C2 alkoxy radical; a C2-C4 hydroxyalkoxy radical; an amino radical; an amino radical substituted with one or two identical or different C 1 -C 4 alkyl radicals optionally bearing a hydroxyl group. Preferably, the linker is a linear, branched or cyclic C1-C20 alkyl chain; optionally interrupted by at least one heteroatom (such as nitrogen, oxygen) and / or at least one group comprising (CO, SO2); optionally interrupted by at least one phenyl or substituted or unsubstituted naphthyl group; optionally interrupted by at least one saturated, unsaturated or aromatic heterocycle, condensed or not with a phenyl ring, said heterocycle comprising at least one quaternized nitrogen atom engaged in said ring and optionally at least one other heteroatom (such as oxygen, nitrogen or sulfur); optionally interrupted by at least one quaternary ammonium group substituted with two C 1 -C 15 alkyl groups; the linking arm does not comprise a nitro, nitroso or peroxo group. If the heterocycles or aromatic rings are substituted, they are, for example, substituted by one or more C 1 -C 8 alkyl radicals optionally substituted with a hydroxyl, C 1 -C 2 alkoxy, C 2 -C 4 hydroxyalkoxy, acetylamino or amino group substituted with one or two identical or different C1-C4 alkyl radicals, optionally bearing a hydroxyl group, or the two radicals which can form, with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle, optionally comprising another heteroatom identical or different from nitrogen; a halogen atom; a hydroxyl group; a C1-C2 alkoxy radical; a C2-C4 hydroxyalkoxy radical; an amino radical; an amino radical substituted with one or two identical or different C 1 -C 4 alkyl radicals optionally bearing a hydroxyl group. The link between the linker and each chromophore is generally by means of a heteroatom which substitutes the phenyl or naphthyl ring or by means of the quaternized nitrogen atom of the cationic heterocycle.

Among the azo, azomethine, methine or tetraazapentamethine monochromophoric direct dyes that can 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.

Thus, mention may in particular be made of the cationic direct dyes corresponding to the following formulas: R 3 in which: D represents a nitrogen atom or the group -CH, R 1 and R 2, which may be identical or different, represent a hydrogen atom; a C 1 -C 4 alkyl radical which may be substituted with 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 R4 R4 R4 R4 R4 R4N N N + R4 R4 R4 -N R4 wherein R4 represents a C1-C4 alkyl radical which may be substituted by a hydroxyl radical; in which: R5 represents a hydrogen atom, a C1-C4 alkoxy radical, a halogen atom such as bromine, chlorine, iodine or fluorine, R6 represents a hydrogen atom, an alkyl radical; C1-C4 or form with a carbon atom of the benzene ring a heterocycle optionally oxygenated and / or substituted with one or more C1-C4 alkyl groups, R7 represents a hydrogen or halogen atom such as bromine, chlorine, iodine or fluorine,

D1 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 structures

in which R 'represents a C 1 -C 4 alkyl radical; when m = 0 and D1 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: CH 3 CH 3 -N-N + CH 3 CH 3 CH 3 CH + NN CH 3 1 N = NN-X-N + CH 3 CH 3 -CH 3 X-N = NN = Embedded image Among the tetraazapentamethine type dyes that may be used according to the invention, the following compounds appearing in the table below NNNN + '~ .NN, X i NNN' NX OMe OMe OMe OMe X N + ~ N_5_1 \ 1 NnN XN ~ N. ~ N ~ N, NN X- N + ^ N ~ N OH X NN% N ~ N, NnN ~ Embedded image is an anion preferably chosen from chloride, iodide, methylsulfate, ethylsulphate and / or , acetate. The dye composition may also comprise one or more oxidation dye precursors, more particularly H3C-N + C = N-N CH3, one or more oxidation bases optionally combined with one or more couplers. By way of example, the oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Among the para-phenylenediamines, 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, 2-13-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- (13, γ-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl-para-phenylenediamine, 2-13-hydroxyethyloxy-para-phenylenediamine, 2- (3-acetylaminoethyloxy) paraphenylenediamine, N - ((3-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, 2- (3-hydroxyethylamino-5-amino-toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid.

Of the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-hydroxy-3-hydroxyethyl paraphenylenediamine, 2-hydroxy-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6 ethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-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, N, N'-bis ((3-hydroxyethyl) N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, for example, is 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. aminophenols include para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-chlorophenol, 4-amino-3-hydroxymethyl, and the like; phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (3-hydroxyethylaminomethyl) phenol, the 4-friend No. 2-fluoro phenol, and their addition salts with an acid. 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 addition salts.

Among the heterocyclic bases that may be mentioned by way of example are 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, 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 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 addition 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, , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine 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 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 1 - ((3-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole, 4, 5-diamino 1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-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-methylpyrazole, 4,5-diamino-1-ethyl-3-methyl-pyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3- meth 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-1 - ((3-methoxyethyl) pyrazole, as pyrazole derivatives, mention may also be made of diamino N, N-dihydropyrazolopyrazolones and in particular those described in patent application FR 2886136, 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- (pyrrolidinyl) -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-pyrazol-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- (pyrrolid) in-1-yl) -1,2-dihydro-pyrazol-3-one, 4-amino-5- (3-dimethylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydropyrazine -3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one. As heterocyclic bases 4,5-diamino-1 - ((3-hydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2, A] will preferably be used. ] pyrazol-1-one and their addition salts.

The composition according to the invention may optionally comprise one or more couplers advantageously chosen from those conventionally used for dyeing keratinous fibers.

Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. 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- (B-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-hydroxypyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (13-hydroxyethyl) amino-3 , 4-methylene dioxybenzene, 2,6-bis- (13-hydroxyethylamino) toluene, 6-hydroxy indoline, 2,6-dihydroxy-4-methyl pyridine, 1-H 3 -methyl pyrazole 5-one, 1-phenyl-3-methyl-pyrazole-5-one, 2,6-dimethyl-pyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] -1, 2,4-triazole, 6-methyl pyrazolo [1 , 5-a] -benzimidazole, their addition salts with an acid, and mixtures thereof.

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, tosylates, benzenesulfonates, phosphates and acetates. The oxidation base or bases, when they are present in the composition, advantageously represent from 0.0001 to 10% by weight relative to the weight of the composition, and preferably from 0.005 to 5% by weight relative to the weight of the composition. the composition.

The coupler or couplers, if present, advantageously represent from 0.0001 to 10% by weight relative to the weight of the composition, and preferably from 0.005 to 5% by weight relative to the weight of the composition.

When present, the additional dye or dyes represent from 0.01 to 10% by weight and preferably from 0.5 to 5% by weight relative to the weight of the composition. The dyeing composition according to the invention may also comprise one or more conditioning agents.

By way of example, mention may be made of linear, cyclic, branched or unbranched, volatile or non-volatile silicones. These silicones can be in the form of oils, resins or gums, they can in particular be polyorganosiloxanes insoluble in the cosmetically acceptable medium.

Organopolysiloxanes are further defined in Walter Noll's "Chemistry and Technology of Silicones" (1968) Academic Press. They can be volatile or non-volatile. When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60 ° C. and 260 ° C. As a conditioning agent, it is also possible to use cationic polymers such as polyquaterniums. , 6, 10, 11, 35 and 37 and hexadimethrin chloride. The concentration of conditioning agent (s) in the composition (s) useful in the invention may vary from 0.01% to 10% by weight relative to the total weight of the composition, preferably from 0.05% to 5% and more. preferentially still from 0.1 to 3%. The composition according to the invention may also comprise one or more organic thickeners.

The organic thickening agents may be chosen from fatty acid amides (diethanol or coconut monoethanol amide, oxyethylenated alkyl ether carboxylic acid monoethanolamide), polymeric thickeners such as cellulosic thickeners (hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose), guar gum and its derivatives (hydroxypropylguar), gums of microbial origin (xanthan gum, scleroglucan gum), crosslinked homopolymers of acrylic acid or acrylamidopropanesulfonic acid and associative polymers (polymers comprising hydrophilic zones, and hydrophobic fatty-chain zones capable, in an aqueous medium, of reversibly associating with each other or with other molecules.) According to a particular embodiment, the thickener is polymeric and selected from cellulose thickeners (hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose), guar gum and its derivatives (hydroxypropylguar), gums of microbial origin (xanthan gum, gum scleroglucan), crosslinked homopolymers of acrylic acid or acrylamidopropanesulfonic acid. With regard to the associative thickeners, it is possible to use one or more polymers of nonionic or ionic nature, preferably anionic or cationic. Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone. Hydrophobic group is understood to mean a linear or branched, saturated or unsaturated hydrocarbon-based radical or polymer comprising at least 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms, and more preferably from 18 to 30 carbon atoms. Preferably, the hydrocarbon group comes from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene. Among the anionic amphiphilic polymers comprising at least one fatty chain (hydrophobic), mention may be made of: (I) polymers comprising at least one hydrophilic unit, and at least one fatty chain allyl ether unit, more particularly those whose hydrophilic unit is constituted by an ethylenic unsaturated anionic monomer, advantageously a vinyl carboxylic acid and very particularly by an acrylic acid or a methacrylic acid or mixtures thereof, and whose fatty-chain allyl ether unit corresponds to the monomer of following formula (A): CH 2 = CR 'CH 2 OB? R (A) in which R' denotes H or CH 3, B denotes the ethyleneoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon radical chosen from alkyl, arylalkyl, aryl, alkylaryl and cycloalkyl radicals comprising from 8 to 30 carbon atoms, preferably from 10 to 24, and even more particularly from 12 to 18 carbon atoms; . A unit of formula (A) more particularly preferred is a unit in which R 'denotes H, n is equal to 10, and R denotes a stearyl (C18) radical. Of these anionic fatty-chain polymers, polymers formed from 20 to 60% by weight of acrylic acid and / or methacrylic acid, from 5 to 60% by weight of lower alkyl (meth) acrylates are preferred. from 2 to 50% by weight of fatty-chain allyl ether of formula (A), and from 0 to 1% by weight of a crosslinking agent which is a well-known copolymerizable polyethylenic unsaturated monomer, such as sodium phthalate; diallyl, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylenebisacrylamide.

Among these, the crosslinked terpolymers of methacrylic acid, of ethyl acrylate, of polyethylene glycol (10 OE) and of stearyl alcohol (Steareth 10), in particular those sold by the company ALLIED COLLOIDS under the names, are particularly preferred. SALCARE SC 80 and SALCARE SC90 which are 30% aqueous emulsions of a crosslinked terpolymer of methacrylic acid, ethyl acrylate and steareth-10-allyl ether (40/50/10). (II) polymers comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of the (C 10 -C 30) alkyl ester of unsaturated carboxylic acid type.

Preferably, these polymers are chosen from those whose hydrophilic unit of olefinic unsaturated carboxylic acid type corresponds to the following monomer of formula (B): ## STR2 ## in which R1 denotes H or CH3 or C2H5 that is to say, acrylic acid, methacrylic acid or ethacrylic acid units, and whose hydrophobic unit of unsaturated carboxylic acid (C 10 -C 30) alkyl ester type corresponds to the following monomer of formula (C): CH2 Wherein OR3 II R2 O (C)

in which, R2 denotes H or CH3 or C2H5 (that is to say acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH3 (methacrylate units), R3 denotes a C10-C30 alkyl radical; and preferably C12-C22.

The (C 10 -C 30) alkyl esters of unsaturated carboxylic acids are, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate. and corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate.

Among this type of anionic polymers with a fatty chain, use will more particularly be made of polymers formed from a monomer mixture comprising

(i) essentially acrylic acid,

(ii) an ester of formula (C) described above and in which R 2 denotes H or CH 3, R 3 denoting an alkyl radical having from 12 to 22 carbon atoms, (iii) and a crosslinking agent, which is an unsaturated monomer polyethylene copolymerizable well known, such as diallyl phthalate, allyl (meth) acrylate, divinylbenzene, (poly) ethylene glycol dimethacrylate, and methylene-bis-acrylamide. Among this type of anionic fatty-chain polymers, use will more particularly be made of 95 to 60% by weight of acrylic acid (hydrophilic unit), 4 to 40% by weight of C 10 -C 30 alkyl acrylate (unit hydrophobic), and 0 to 6% by weight of polymerizable crosslinking monomer, or those consisting of 98 to 96% by weight of acrylic acid (hydrophilic unit), 1 to 4% by weight of C 10 alkyl acrylate. C3o (hydrophobic unit), and 0.1 to 0.6% by weight of crosslinking polymerizable monomer such as those described above. Among said polymers above, the products sold by the company Goodrich under the trade names Pemulen Tri, Pemulen TR2, Carbopol 1382, and even more preferentially Pemulen Tri, and the product sold by the company, are particularly preferred according to the present invention. SEPPIC company under the name COATEX SX.

(III) terpolymers of maleic anhydride / C3-C38 α-olefin / alkyl maleate such as the product (maleic anhydride copolymer / C30-C38 α-olefin / isopropyl maleate) sold under the name PERFORMA V 1608 by the company NEWPHASE TECHNOLOGIES. (IV) acrylic terpolymers comprising: (a) 20% to 70% by weight of a carboxylic acid having α, 13-monoethylenic unsaturation, (b) 20 to 80% by weight of α-unsaturated monomer, 13 non-surfactant mono- ethylenic other than (a), (c) 0.5 to 60% by weight of a nonionic mono-urethane which is the reaction product of a monohydric surfactant with a monoisocyanate at monoethylenic unsaturation, such as those described in the patent application EP-A-0173109 and more particularly a methacrylic acid / methyl acrylate / dimethyl metaisopropenyl benzyl isocyanate terpolymer of ethoxylated behenyl alcohol (400E) in aqueous dispersion at 25%.

(V) copolymers comprising among their monomers an α, β-monoethylenically unsaturated carboxylic acid and an α, β-monoethylenically unsaturated carboxylic acid ester and an oxyalkylenated fatty alcohol (C 8 -C 30). The compounds also comprise, as monomer, an α, β-monoethylenically unsaturated carboxylic acid ester and a C 1 -C 4 alcohol ester, for example of this type of compound, mention may be made of Aculyn 22 sold by the company ROHM and HAAS, which is a methacrylic acid / ethyl acrylate / oxyalkylenated stearyl methacrylate terpolymer.

The fatty-chain (hydrophobic) nonionic amphiphilic polymers are preferably chosen from: (1) celluloses modified with groups comprising at least one fatty chain, such as in particular; hydroxyethylcelluloses modified with groups comprising at least one fatty chain such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, such as the product NATROSOL PLUS GRADE 330 CS ( C16 alkyls) sold by the company AQUALON, or the BERMOCOLL EHM 100 product sold by the company BEROL NOBEL, - those modified with polyalkylene glycol ether alkyl phenol groups, such as the product AMERCELL POLYMER HM-1500 (polyethylene glycol ( 15) nonylphenol ether) sold by the company Amerchol. (2) hydroxypropyl guars modified with groups comprising at least one fatty chain such as the product ESAFLOR HM 22 (C22 alkyl chain) sold by LAMBERTI, the products RE210-18 (C14 alkyl chain) and RE205-1 (C20 alkyl chain) sold by the company Rhone Poulenc.

(3) copolymers of vinyl pyrrolidone and hydrophobic fatty-chain monomers, with for example: ANTARON V216 or GANEX V216 products (vinylpyrrolidone / hexadecene copolymer) sold by I.S.P. products ANTARON V220 or GANEX V220 (vinylpyrrolidone / eicosene copolymer) sold by the company I.S.P.

(4) copolymers of methacrylates or of C1-C6 alkyl acrylates and of amphiphilic monomers comprising at least one fatty chain, such as, for example, the oxyethylenated methyl acrylate / stearyl acrylate copolymer sold by GOLDSCHMIDT under the name denomination ANTIL 208.

(5) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, such as, for example, polyethylene glycol methacrylate / lauryl methacrylate copolymer.

(6) polymers having an aminoplast ether skeleton having at least one fatty chain, such as the PURE THIX compounds proposed by the company SUD-CHEMIE.

(7) polyether polyurethanes comprising in their chain, both hydrophilic sequences of mostly polyoxyethylenated nature and hydrophobic sequences which may be aliphatic sequences alone and / or cycloaliphatic and / or aromatic sequences. Preferably, the polyether polyurethanes comprise at least two hydrocarbonaceous fatty chains, having from 8 to 30 carbon atoms, separated by a hydrophilic sequence, the hydrocarbon chains possibly being pendant chains or end chains of hydrophilic sequence. As examples of nonionic fatty-chain polyurethane polyethers that may be used in the invention, use may be made of the urea-functional Rheolate 205 sold by Rheox or else the Rheolates 208, 204 or 212, as well as Acrysol RM 184. Aculyn or Acrysol 44 and Aculyn or Acrysol 46 from the company Rohm & Haas Aculyn 46 is a polyethylene glycol polycondensate containing 150 or 180 moles of ethylene oxide, stearyl alcohol and methylene bis. (4-cyclohexyl isocyanate) (SMDI), 15% by weight in a matrix of maltodextrin (4%) and water (81%); ACULYN 44 is a polycondensate of polyethylene glycol with 150 or 180 moles of ethylene oxide, decyl alcohol and methylene bis (4-cyclohexylisocyanate) (SMDI), at 35% by weight in a propylene glycol mixture (39 %) and water (26%)]. Mention may also be made of the product ELFACOS T210 with a C12-C14 alkyl chain and the product ELFACOS T212 with a C8 alkyl chain from AKZO, as well as the product DW 1206B from ROHM & HAAS with a C20 alkyl chain and with urethane bond, proposed at 20% dry matter in water. It is also possible to use solutions or dispersions of these polymers, especially in water or in an aqueous-alcoholic medium. By way of example, such polymers include, for example, Rheolate 255, Rheolate 278 and Rheolate 244 sold by Rheox. It is also possible to use the product DW 1206F and the DW 1206J proposed by the company Rohm & Haas. The polyether polyurethanes that can be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci 271, 380, 389 (1993).

The cationic amphiphilic polymers comprising at least one fatty (hydrophobic) chain used may in particular be chosen from quaternized cellulose derivatives, cationic polyurethanes, cationic polyvinyllactams, and preferably from quaternized cellulose derivatives.

By way of example of polymers of this type, mention may be made in particular of: quaternized celluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups containing at least 8 carbon atoms, or mixtures thereof; quaternized hydroxyethylcelluloses modified with groups having at least one fatty chain, such as alkyl, arylalkyl, alkylaryl groups having at least 8 carbon atoms, or mixtures thereof. The alkyl radicals carried by the above-quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.

Examples of C8-C30 fatty chain quaternized alkylhydroxyethylcelluloses are QUATRISOFT LM 200, QUATRISOFT LM-X 529-18-A, QUATRISOFT LM-X 529-18B (C12alkyl) and QUATRISOFT LM-X. 529-8 (C18 alkyl) marketed by the company AMERCHOL and the products CRODACEL QM, CRODACEL QL (Ciz alkyl) and CRODACEL QS (C18 alkyl) marketed by the company CRODA. The content of thickening polymers, if present, usually ranges from 0.05% to 5% by weight, based on the weight of the coloring composition. According to a particularly advantageous embodiment, the dye composition according to the invention comprises one or more surfactants. These can be indifferently chosen, alone or in mixtures, from anionic, amphoteric, nonionic, zwitterionic and cationic surfactants. As regards the anionic surfactants, the salts, in particular the alkali metal salts such as the sodium salts, the ammonium salts, the amine salts, the aminoalcohol salts or the metal salts, are usually used. alkaline earth metals, for example, magnesium, the following compounds, alone or as a mixture: alkylsulphates, alkylethersulphates, alkylamidoethersulphates, alkylarylpolyethersulphates; alkylsulfonates, alkylamidesulfonates, alkylarylsulphonates; alkylsulfosuccinates, alkylethersulfosuccinates, alkylamide-sulfosuccinates; alkylsulfoacetates; - acylsarconisates; and the acylglutamates: alkyl and polyglycoside carboxylic acid esters such as alkyl glucoside citrates, alkyl polyglycoside tartrates, and alkyl polyglycoside sulfosuccinates; alkylsulfosuccinamates; acylisethionates, N-acyltaurates; acyllactylates; alkyl-D-galactoside uronic acids; polyoxyalkylenated alkyl ether carboxylic acids, polyoxyalkylenated alkylarylether carboxylic acids, polyoxyalkylenated alkylamidoether carboxylic acids; the alkyl or acyl group (RCO-) of these compounds having from 10 to 24 carbon atoms and the aryl group preferably denoting a phenyl or benzyl group; the number of oxyalkylenated and preferably oxyethylenated groups is between 2 and 50. As regards the nonionic surfactants, the latter may advantageously be chosen from the following compounds, alone or as a mixture: polyethoxylated, polypropoxylated fatty alcohols or polyglycerolated polyethoxylated, polypropoxylated or polyglycerolated alpha-diols, the number of ethylene oxide or propylene oxide groups ranging from 2 to 50; the number of glycerol groups ranging from 2 to 30; condensates of ethylene oxide and propylene oxide on fatty alcohols; polyethoxylated fatty amides having from 2 to 30 moles of ethylene oxide; polyglycerolated fatty amides containing from 1 to 5 glycerol groups; polyethoxylated fatty amines having from 2 to 30 moles of ethylene oxide; ethoxylated fatty acid esters of sorbitan having from 2 to 30 moles of ethylene oxide, fatty acid esters of sucrose; alkylpolyglucosides, N-alkylglucamine derivatives; these compounds comprising at least one alkyl or alkenyl chain comprising 10 to 24 carbon atoms. copolymers of ethylene oxide and of propylene oxide.

The cationic surfactants used in the composition according to the invention may in particular be chosen from the following compounds, alone or as a mixture: primary, secondary or tertiary fatty amines optionally polyethoxylated (2 to 30 moles of ethylene oxide) and their salts - quaternary ammonium salts such as tetraalkylammonium, alkylamidoalkyltrialkylammonium, trialkylbenzylammonium, trialkylhydroxyalkylammonium, alkylpyridinium chlorides or bromides; alkylimidazoline derivatives; these compounds comprising at least one alkyl chain comprising 10 to 24 carbon atoms. Finally, the amphoteric surfactants may be chosen from the following compounds, alone or as a mixture: derivatives of secondary or tertiary aliphatic amines, in which the aliphatic group is a linear or branched chain containing 10 to 24 carbon atoms and comprising at least at least one anionic water-solubilising group such as, for example, a carboxylate, sulphonate, sulphate, phosphate or phosphonate group; alkylbetaines, sulphobetaines, (C6-C8) alkylamidoalkyl betaines, (C6-C8) alkylamidoalkylsulfobetaines; these compounds comprising at least one alkyl chain comprising from 10 to 24 carbon atoms.

Preferably, the surfactants are nonionic, anionic or amphoteric and even more preferably nonionic. Usually, the surfactants represent from 0.01 to 50% by weight, preferably from 0.1 to 25% by weight relative to the weight of the composition.

The dye composition according to the invention may also comprise various adjuvants conventionally used in compositions for dyeing hair, such as, for example, cationic, anionic, nonionic, amphoteric or zwitterionic polymers other than the previously mentioned thickeners, or mixtures thereof; mineral thickeners such as clays; antioxidants such as for example ascorbic acid, erythorbic acid; reducing agents different from the aforementioned compounds (I) such as inter alia erythorbic acid, reducing sugars; penetrating agents, sequestering agents such as ethylenediamine tetraacetic or its salts; perfumes ; matting agents with, for example, titanium oxides; buffers; dispersants; film-forming agents; ceramides and preservatives. 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 composition. The composition according to the invention may also comprise a cosmetically acceptable medium. The cosmetically acceptable medium of the composition, which is a suitable medium for dyeing human keratin fibers, preferably comprises water and optionally one or more organic solvents different from the organic compounds (II) optionally present in the composition according to the invention. invention having a Hansen parameter value 8H of solubility of less than or equal to 16 MPa-2 and molecular weight of less than 250 g / mol, and different from the above-mentioned compounds (I) As examples of such organic solvents, mention may be made, for example, of linear or branched C2-C4 alkanols, such as ethanol and isopropanol, polyols and polyol ethers such as 2-butoxyethanol, hexylene glycol, propylene glycol and dipropylene glycol; glycerol and mixtures thereof This organic solvent or these organic solvents may be present in proportions ranging preferably from 1 to 40% by weight relative to total weight of the dye composition, and even more preferably from 5 to 30% by weight. The amount of water in the composition according to the invention is preferably greater than 10% by weight relative to the weight of the composition, and more preferably greater than or equal to 25% by weight. Preferably, the water content is between 25 and 98% by weight relative to the weight of the composition. The pH of the composition according to the invention may be between 2 and 12, inclusive. Preferably, the pH of the composition according to the invention is between 8 and 12, inclusive. It can be adjusted to the desired value by means of one or more acidifying agents or one or more additional alkalizing agents, different from the mineral bases according to the invention. 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 additional basifying agents, different from the inorganic bases according to the invention, mention may be made, for example, of alkanolamines such as mono-, di- and triethanolamines and their derivatives, hydroxides of sodium or of potassium and the compounds of the following formula:

Wherein W is a propylene residue optionally substituted with a hydroxyl group or a C1-C6 alkyl radical; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical. The composition according to the invention may also comprise one or more oxidizing agents. In particular, the composition with oxidant is obtained by extemporaneous mixing before the application of a previously described composition, 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 thus constituted by a process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, which consists in applying the composition according to the invention 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 include oxidation dye precursor (bases, couplers). According to a second embodiment, the composition is applied in the presence of at least one oxidizing agent. This embodiment can be implemented if the composition comprises, as dyestuffs, only direct dyes (dye (s)). hydrophobic character, and optionally one or more additional direct dyes) or even if the composition comprises one or more dyes with a hydrophobic nature, optionally one or more direct dyes synthetic and / or natural, combined with one or more dye precursors d oxidation (bases and couplers). According to a first variant of this second embodiment, the composition which has just been detailed and which is obtained by extemporaneous mixing before application, of a composition according to the invention devoid of an oxidizing agent with an oxidizing composition. According to a second variant of this second 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. These organic solvents can also be chosen from the organic compounds (II) present in the composition according to the invention having a Hansen parameter 8H value of solubility of less than or equal to 16 MPa.sup.-2 and a molecular weight of less than 250 g / mol. and different from the compounds (I) mentioned above 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.

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" for dyeing, in which a first compartment contains the dyeing composition according to the present invention as described above with the exception of the oxidizing agent (s), and a second compartment contains a composition comprising one or more oxidizing agents as described above. The following examples are intended to illustrate the invention without limiting its scope. In these examples, all the amounts are indicated in percent by weight of active material relative to the total weight of the composition, unless otherwise indicated.

EXAMPLE 1 The coloring compositions according to the invention are prepared, the formulations of which are given in Table 1 below.

Table 1 ABCDE Indigo [1] 1g - - - - Isoindigo [2] - 1g - - - Tyr purple [3] - - 1g - - Thioindigo [4] - - - 1g - Oralith [5] - - - - 1g Benzyl alcohol 5g 5g 5g 5g 5g Ethanol 15g 15g 15g 15g 15g Acetoin 1g 1g 1g 1g 1g Carbonate 2g 2g 2g 2g 2g sodium Water qsp qsp qsp qsp 100g 100g 100g 100g 100g [1] Indigo, CAS = 482-89-3 , sold by Sigma Aldrich [2] Isoindigo [3] Tyr purple, 6,6'-dibromoindigo marketed by Kremer Pigmente [4] Thioindigo, CAS = 522-75-8, marketed by Sigma Aldrich [5] Oralith, CAS = 2379-74-0, marketed by Sigma Aldrich

The compositions are stirred under argon for 2H at 40 ° C.

Then, the pH is adjusted to 9.6 with 4 g of 25% ammonia in aqueous solution and 4 g of lactic acid at 90% in aqueous solution. Pairings of locks of hair with 90% natural and permed white hair are stained for 30 minutes at room temperature by these coloring compositions A to E, the locks are then dewatered, rinsed, shampooed and dried. Powerful and stubborn colorations are obtained.

Example 2

The coloring compositions according to the invention are prepared, the formulations of which are given in Table 2 below. Table 2 FGHIJ Indigo [1] 1g - - - - Isoindigo [2] - 1g - - - Tyr purple [3] - - 1g - - Thioindigo [4] - - - 1g - Oralith [5] - - - - 1g Benzyl Alcohol 5g 5g 5g 5g 5g Ethanol 15g 15g 15g 15g 15g Acetone 1g 1g 1g 1g Hydrogenocarbona 2g 2g - - - - Sodium Sodium Hydrogenocarbon - - 2g 2g 2g -te Potassium Water Qsp Qsp Qsp Qsp Qsp 100g 100g 100g 100g 100g [1] Indigo, CAS = 482-89-3, marketed by Sigma Aldrich [2] Isoindigo [3] Tyr purple, 6,6'-dibromo indigo marketed by Kremer Pigmente [4] Thioindigo, CAS = 522-75 -8, marketed by Sigma Aldrich [5] Oralith, CAS = 2379-74-0, marketed by Sigma Aldrich

The compositions are stirred under argon for 2H at 40 ° C. Then, the pH is adjusted to 9.6 with 4 g of 25% ammonia in aqueous solution and 4 g of lactic acid at 90% in aqueous solution. 46 Couples of locks of hair with 90% of natural and permed white hair are stained for 30 minutes at room temperature by these coloring compositions F to J, the locks are then dewatered, rinsed, shampooed and dried.

Powerful, stubborn colorations are achieved

Example 3

The coloring compositions according to the invention are prepared, the formulations of which are given in Table 3 below.

Table 3 KLM Indigo [1] 1g 1g 1g Glutaroin 1 g - - Dihydroxyacetone - 1 g - Benzoin - - 1 g Benzyl alcohol 5g 5g 5g Ethanol 15g 15g 15g Hydrogen carbonate 2g 2g 2g sodium Water qs 100g qs 100g qs 100g [1] Indigo, CAS = 482-89-3, marketed by Sigma Aldrich

The compositions are prepared and applied to pairs of natural and permed locks of hair with 90% white hair, under the same conditions as those of Example 2. Strong, stubborn blue colorings are obtained.

Example 4

The coloring compositions according to the invention are prepared, the formulations of which are given in Table 4 below.

Table 4 NOP Indigo [1] 0.5g 0.5g 0.5g Curcumin 0.5g 0.5g 0.5g Isatin 0.3g 0.3g 0.3g Orcein 0.3g 0.3g 0.3g Chlorophylline 0.15g 0.15g 0.15g Sorghum 0.02g 0.02g 0.02g Lactic Acid 0.01g 0.01g 0.01g Acetoin 1g 1g 1g Ethanol 15g 15g 15g Benzyl alcohol 5g 1g - 3-phenyl-1-propanol - 0, 5g - Decanol - - 5g CTAB [6] - - 2g Hydrogen carbonate 2g 2g 2g sodium Perfume qs qs qs Water qs 100g qs 100g qs 100g 10 [1] Indigo, CAS = 482-89-3, marketed by Sigma Aldrich [6] ] Cetyl trimethyl ammonium chloride

The compositions are prepared and applied to pairs of natural and permed locks of hair with 90% white hair, under the same conditions as those of Example 2. Strong, stubborn brown colorations are obtained. 48

Claims (15)

REVENDICATIONS1. Dye composition comprising: one or more hydrophobic direct dyes of logP greater than or equal to 2, one or more mineral bases chosen from carbonates, hydrogenocarbonates and their mixtures, and one or more compounds (I) comprising in their structure a chaining: CH2) n \ X / O with n denoting an integer from 0 to 4, and where X denotes a grouping: C ùCH C Il O OH or or 2. Composition according to claim 1, characterized in that the hydrophobic direct dye or dyes are chosen from the following compounds: Disperse Red 17, Disperse Violet 1, HC Yellow 7, Disperse Blue 377, Disperse Red 13, Disperse Green 9, Solvent Black 3, Disperse Blue 148, Disperse Violet 63, Disperse Blue 60, Disperse 20 Blue 14, Solvent Orange 15, Solvent Orange 7, Solvent Blue 14, Disperse Yellow 82, Indigo Dyes, and mixtures thereof. 3. Composition according to Claim 2, characterized in that the hydrophobic direct dye or dyes are chosen from indigo dyes. 25 4. Composition according to claim 2 or 3, characterized in that the indigo dyes are chosen from indigo, isoindigo, indirubine, isoindirubin, 4,4'-dibromoindigo, 6,6'- dibromoindigo, 5,5'-dibromoindigo, cis -6,6'-dibromoindigo, 5,5 ', 7,7'-tetrabromoindigo, 4,4', 7,7'-tetrachloroindigo, 3H-indol-3-one, 1,2-dihydro-2- (3-oxobenzo [b] thien-2- (3H) -ylidene), OHthioindigo, Vat Red 1, cis-thioindigo, 6,6'-dichloro-4,4'-dimethylthioindigo, 5,5'-dichloro-7,7'-dimethylthioindigo, 4,4'-7,7'-tetramethylthioindigo, thioindigo Scarlet R, 2H- indol-2-one, 1,3-dihydro-3- (3-oxobenzo [b] thien-2 (3H) -ylidene) -, (3E) -, thioindirubin, 2H-indol-2-one, 1 3-dihydro-3- (2-oxobenzo [b] thiophen-3 (2H) -ylidene), benzo [b] thiophen-2 (3H) -one, 3- (2-oxobenzo [b] thiophen-3 (2H) -ylidene. 5. Composition according to any one of the preceding claims, characterized in that the hydrophobic direct dye or dyes represent from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, better still from 0.1 to 5% by weight of the total weight of the cosmetic composition. 6. Composition according to any one of the preceding claims characterized in that the compound (s) (I) have in their structure a sequence CùCH C = C Il I I OH (A) or OH OH (B). 7. Composition according to any one of the preceding claims, characterized in that the compound or compounds (I) are chosen from hydroxyacetone, acetoin, glutaroin, adipoin, dihydroxyacetone, glycol aldehyde and benzoin. 2,3-dihydroxyacrylaldehyde, cyclopentanedione, acetone acetone, acetyl acetone, diacetyl, dipropionyl, 2-ketoglutaric acid, 3-ketoglutaric acid, pyruvic acid, levulinic acid, acetoacetic acid, propionylacetic acid, acetonylmalonic acid, acetomethyl acetate, acetoethyl acetate, acetopyruvic acid, cyclohexanedione. 8. Composition according to any one of the preceding claims, characterized in that the compound or compounds (I) represent from 0.01 to 20% by weight, preferably from 0.05 to 10% by weight, better still from 0.1. at 5% by weight of the total weight of the cosmetic composition. 9. Composition according to any one of the preceding claims, characterized in that the mineral base (s) are chosen from alkali metal carbonates, alkali metal hydrogen carbonates, and mixtures thereof; and preferably from sodium carbonate, potassium carbonate, sodium hydocarbonate, potassium hydrogencarbonate, and mixtures thereof. 10. Composition according to any one of the preceding claims, characterized in that said one or more mineral bases represent from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, and more preferably from 1 to 5. % by weight, relative to the total weight of the composition. 11. Composition according to any one of the preceding claims, characterized in that it also contains one or more organic compounds (II) having a Hansen solubility parameter value 8H of less than or equal to 16, preferably less than 16, plus preferably between 5 and 15.8 MPa "2 and even more preferably between 8 and 15.8 MPa" 2, and with a molecular weight of less than 250 g / mol, this or these compounds being present at a content ranging from 0.1 at 20%, preferably 1 to 5% by weight, of the total weight of the composition. 12. Composition according to the preceding claim, characterized in that the organic compound (s) (II) are chosen from alkanols, aliphatic esters, ethers, aromatic alcohols, alkylaryl alcohols, aromatic acids, aliphatic acids, alkylene carbonates, lactones, and mixtures thereof, and preferably from alkanols, aliphatic esters, ethers, aromatic alcohols, alkylaryl alcohols, aromatic acids, aliphatic acids, and mixtures thereof. 13. Composition according to any one of the preceding claims, characterized in that the composition comprises one or more additional dyes different from hydrophobic dyes of logP greater than or equal to 2, chosen from natural dyes and non-natural direct dyes, precursors. oxidation dye, or combinations thereof. 14. Composition according to any one of the preceding claims, characterized in that it also comprises one or more oxidizing agents, preferably hydrogen peroxide. 15. Coloring process consisting in applying to the keratinous fibers, in particular human keratinous fibers such as the hair, a composition as defined in any one of the preceding claims.