CAPILLARY COLORING PROCESS IMPLEMENTING A COLORING STEP FROM A DYE, AND A TITANIUM SALT AND A REVELA

专利摘要:
The present invention relates to a method for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, comprising at least two stages in which said fibers are first treated with a cosmetic coloring composition Ci) comprising a) one or more dyes (s) preferably natural (s), b) one or more salt (s) of titanium and b1) optionally one or more particular carboxylic acids, then said fibers are treated with a cosmetic revealing composition Cii) comprising c) one or more alkaline agent (s) each having at most one amine function and d) optionally one or more chemical oxidizing agent (s); a cosmetic composition comprising the ingredients a), b), b1), c) and d) as defined above; and a multi-compartment device comprising ingredients a), b), b1), c) and d).
公开号:FR3037237A1
申请号:FR1555384
申请日:2015-06-12
公开日:2016-12-16
发明作者:Boris Lalleman；Alain Lagrange
申请人:LOreal SA；
IPC主号:

专利说明:

[0001] A method for hair dyeing using a dyeing step from a dye, and a titanium salt and a revelation step from an alkaline agent comprising at most one amine function The present invention relates to a process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, comprising at least two stages in which said fibers are first treated with a cosmetic coloring composition Ci) comprising a) one or more dyes which are preferably natural ( s), b) one or more titanium salts and b1) optionally one or more particular carboxylic acids, then said fibers are treated with a cosmetic revealing composition Cii) comprising c) one or more alkaline agent (s) (s) ) each having at most one amine function and d) optionally one or more chemical oxidizing agent (s); a cosmetic composition comprising the ingredients a), b), 131), c) and d) as defined above; and a multi-compartment device comprising ingredients a), b), 131), c) and d). It is known to obtain so-called "permanent" dyes with dyeing compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols and compounds. heterocyclic. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained can be varied by combining these oxidation bases with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indole compounds. This oxidation dyeing process consists in applying to the keratinous fibers, bases or a mixture of bases and couplers with hydrogen peroxide (H 2 O 2 or hydrogen peroxide) as an oxidizing agent, to be allowed to diffuse, then to rinse the fibers. The resulting colorations are permanent, strong, and resistant to external agents, including light, weather, washing, perspiration and friction. Nevertheless, it is still desired to increase the effectiveness of the oxidation dyes used during this dyeing process in order to improve their rise on the keratin fibers. In fact, such an improvement would make it possible in particular to reduce the content of the oxidation dyes present in the dyeing compositions, to reduce the exposure time on the keratinous fibers and / or to use other families of dyes having a low dyeing power. but which are able in particular to bring new shades or lead to more stubborn stains vis-à-vis external agents such as light or shampoos, we finally to lead to better quality of use as a less staining scalp, clothing, or even less coloration of the dye mixture (cleaner) during the application or the pause time Furthermore, it is known to dye keratinous fibers and in particular human hair, with dyeing compositions containing direct dyes. The standard dyes that are used are in particular nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine, triarylmethane or natural dyes. These dyes may be nonionic, anionic, cationic or amphoteric.
[0002] These dyes are colored molecules or dyes having an affinity for keratinous fibers. 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. The resulting colorings are particularly chromatic colorations which are, however, temporary or semi-permanent because the nature of the interactions which bind the direct dyes to the keratinous fiber and their desorption from the surface and / or the core of the fiber are responsible. their low dyeing power and their poor resistance to light, washing, or perspiration. There is therefore still some progress to be made in this field to provide powerful, resistant dyes which respect the nature of the hair from compositions containing, in particular, natural dyes. In the field of coloration from natural extract such as orthodiphenols (ODPs), it is also known to dye keratin materials such as hair or skin from ODPs in the presence of a metal salt, in particular of manganese (Mn) and / or zinc (Zn). In particular, the patent applications FR 2814943, FR 2814945, FR 2814946 and FR 2814947 provide compositions for coloring the skin or keratinous fibers, comprising a dye precursor which contains at least one orthodiphenol, salts and oxides of Mn. and / or Zn, alkalines of the hydrogencarbonate type in a particular ratio Mn, Zn / hydrogen carbonate and optionally an enzyme. According to these documents, it is possible to obtain dyes of keratin materials with oxygen from the air or any system generating oxygen. However, the colorations obtained from ODPs are insufficiently powerful, intense and / or are not very stubborn, especially in the case of hair fibers.
[0003] It is known to use acid-level metals for dyeing keratinous fibers in amounts similar to those used for dyes using an etching process, which involves preparing the fibers prior to dyeing to obtain stubborn hues (Ullmann's Encyclopedia "Metal and Dyes", 2005 § 5.1, p 8). However, this process generally has the drawback of not always respecting the cosmetics of the keratinous fiber. Other documents describe the use of ODPs associated with salts of Mn, Zn and other metal salts including titanium salts and a chemical oxidizing agent (FR297673, WO2011 / 086284, WO2011 / 086282, and FR2951374).
[0004] Nevertheless, improvements still need to be made in particular in terms of the tenacity of the color with regard to shampoos and sweat. There is therefore a real need to develop staining processes which make it possible to obtain more powerful and / or stubborn stains from dyes, in particular oxidation dyes, direct dyes of natural origin or otherwise, in particular ODPs, preferably from natural extracts rich in ODPs, less aggressive for keratin fibers, or requiring smaller quantities of dyes. More particularly, there is a need to obtain colorings which are satisfactorily resistant to external agents (light, weather, shampoos, sweat) which are stubborn and homogeneous, ie having low color selectivity between the root and the tip. , while remaining powerful and / or chromatic. In addition, it is necessary to obtain the satisfactory coloring performance that the product is stable. This (these) aim (s) is (are) achieved by the present invention which relates to a method for dyeing keratinous fibers. , in particular human keratinous fibers such as the hair, in which said fibers are treated, in several steps, by a coloring cosmetic composition Ci) containing a) one or more dyes, in particular chosen among the direct and natural dyes, preferably chosen from ortho-diphenols (ODPs); b) one or more salt (s) of titanium (Ti); in particular the Ti atom of the salt is of oxidation degree 2, 3 or 4 denoted Ti (I I), Ti (III) or Ti (IV), preferably Ti (IV); and b1) optionally one or more carboxylic acid (s) of formula (I) below; Formula (I) or a salt thereof in which: A represents a monovalent group when n is 0 or polyvalent when n is greater than or equal to 1, hydrocarbon comprising 1 to 50 carbon atoms, saturated or unsaturated, cyclic or non-cyclic, aromatic or nonaromatic, optionally interrupted by one or more heteroatoms and / or optionally substituted in particular with one or more hydroxyl groups; preferably A is a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted with one or more hydroxy groups; n represents an integer inclusive between 0 and 10, preferably n is between 0 and 5, such as between 0 and 2; then - a cosmetic revealing composition Cii) containing, c) one or more alkaline agent (s) comprising at most one amine function (-N H2); and d) optionally one or more chemical oxidizing agent (s) such as hydrogen peroxide or one or more hydrogen peroxide generator system (s); it being understood that when the composition Cii) contains several alkaline agents, then each of the alkaline agents comprises at most one amine function. said method preferably comprising between the application of Ci) and Cii) an intermediate rinsing step.
[0005] Preferably, the composition (s) used in the process of the invention is (are) aqueous. Another subject of the invention is a cosmetic composition, preferably aqueous, for the coloration of keratinous fibers containing ingredients a), b), 131), c), and d) as defined above and optionally an organic solvent such as as defined below. Another object of the present invention relates to a multi-compartment device comprising the ingredients a), b), c) and possibly d) distributed in several compartments. The multi-compartment device or "kit" is suitable for carrying out the coloring process according to the invention. The process according to the invention has the advantage of coloring human keratin fibers, with stubborn coloring results. In particular, the dyeing method according to the invention makes it possible to lead to colorings that are resistant to washing, perspiration, and light without altering the fibers. The perspiration resistance is particularly good. In addition, the coloring process used makes it possible to induce a "rise" and / or intensity (power) of the satisfactory coloration. Other objects, features, aspects and advantages of the present invention will become more apparent upon reading the description and examples which follow. A) the dye (s) According to the present invention, the process of the invention uses at least one composition Ci) comprising a) one or more dyes, in particular chosen from among the oxidation dyes, direct dyes, and dyes of natural origin, preferably selected from ortho-diphenols or ODPs. al) According to a first embodiment of the invention, the dye (s) is (are) chosen from oxidation dyes.
[0006] The oxidation dye precursors that can be used in the present invention are generally selected from oxidation bases, optionally combined with one or more couplers. The oxidation bases may preferably be chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Preferably, the oxidation base (s) of the invention are chosen from para-phenylenediamines and heterocyclic bases. 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-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N-bis (β-hydroxyethyl) paraphenylenediamine, 4-N, N-bis (β-hydroxyethyl) amino 2-methylaniline, 4-N, N-bis (β-hydroxyethyl) amino-2-chloroaniline, 2β-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (β-hydroxypropyl) ) paraphenylenediamine, 2 hydroxymethyl paraphenyl methnediamine, 2-methoxymethyl paraphenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl-1,3-hydroxyethyl) paraphenylenediamine, N- (3-yl-dihydroxypropyl) -paraphenylenediamine, N- (4 'aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 213-hydroxyethyloxy para-phenylenediamine, 2β-acetylaminoethyloxy para-phenylenediamine, N- (p-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, 213 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, 2β-hydroxyethyl paraphenylenediamine, 2β-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (3-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2 -3-acetylaminoethyloxy-para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine and their acid addition salts are particularly preferred.
[0007] 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; (N-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-diaminophenoxy) -3,6-dioxaoctane, and their addition salts. Among the para-aminophenols, para-amino phenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol and 4-amino-3-chlorophenol may be mentioned by way of example, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol 4-amino-2-fluoro phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid. Among the ortho-aminophenols, 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-amino are exemplified by way of example. phenol, and their addition salts. Among the heterocyclic bases, it is possible in particular to pyridine derivatives, pyrimidine derivatives and pyrazole derivatives. Among the pyridine derivatives, mention may be made of the compounds described, for example, in 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 [1,5a] -pyridines oxidation bases or their addition salts described for example in the patent application FR 2801308.
[0008] 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-Amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-aminopyrazolo [1,5-a] pyridin-5-yl) ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridine-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-aminopyrazolo [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; 2β-hydroxyethoxy-3-aminopyrazolo [1,5-a] pyridine; 2- (4-dimethylpiperazinium-1-yl) -3-amino-pyrazolo [1,5-a] pyridine; as well as their addition salts.
[0009] More particularly, the oxidation bases according to the invention are chosen from 3-aminopyrazolo- [1,5a] -pyridines preferably substituted in position 2 by: a) a (di) (C1-C6) (alkyl) group ) amino alkyl groups which may be substituted with one or more hydroxy, amino or imidazolium groups; B) a heterocycloalkyl group comprising from 5 to 7 chain members, and from 1 to 3 heteroatoms, cationic or otherwise, optionally substituted with one or more (C1-C6) alkyl groups such as di (C1-C4) alkylpiperazinium; c) a (C1-C6) alkoxy group optionally substituted with one or more hydroxyl groups such as p-hydroxyalkoxy and 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 VVO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4 dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their 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 VVO 94/08969, VVO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 diamino 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-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenyl pyrazole, 4-amino-1, 3-dimethyl-5-hydrazino pyrazole, 1-benzyl-4,5-diamino-3-methyl pyrazole, 4,5-diamino-3-tert-butyl-1-methyl pyrazole, 4,5 1-tert-butyl 3-methyl pyrazole, 4,5-diamino-1- (p-hydroxyethyl) -3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl pyrazole, 4, 5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-dia mino-3-methyl-1-isopropyl pyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl-3, 4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4- (3-hydroxyethyl) amino-1-methyl pyrazole, and their salts thereof; addition. Preferably the heterocyclic oxidation bases of the invention are selected from 4,5-diaminopyrazoles such as 4,5-diamino-1- (β-hydroxyethyl) pyrazole. 4-5-Diamino-1- (3-methoxyethyl) pyrazole can also be used.
[0010] Preferably, a 4,5-diaminopyrazole and even more preferably 4,5-diamino-1- (3-hydroxyethyl) pyrazole and / or a salt thereof will be used. As pyrazole derivatives, mention may also be made of diamino N, Ndihydropyrazolopyrazolones and especially those described in application FR-A-2 886 136 such as the following compounds and their addition salts: 2,3-diamino-6,7 1-Dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol 1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3- (pyrrolidin-1-yl) 6-a, 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- (pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one, 4-aminopropyl 5- (3-Diethylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2-dihydro-pyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro- 1H, 5H-pyrazolo [1,2-a] pyrazol-1-one. It will be preferred to use 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and / or a salt thereof. As heterocyclic bases, 4,5-diamino-1- (3-hydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2] will preferably be used. -a] pyrazol-1-one and / or a salt thereof. The oxidation base (s) used in the context of the invention are generally present in an amount ranging from 0.001 to 10% by weight approximately of the total weight of the dyeing composition, preferably ranging from 0.005 to 5%.
[0011] The additional couplers conventionally used for dyeing keratinous fibers are preferably chosen from 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 1-hydroxy-3-aminobenzene, 2-methyl-5-aminophenol, 3-amino- 2-chloro-6-methylphenol, 2-methyl-5-hydroxyethylaminophenol, 2,4-diamino-1- (11-hydroxyethyloxy) benzene, 2-amino-4- (11-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1 dimethylamino benzene, sesamol, thymol, 1-11-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- (11-hydroxyethyl) amino-3 4-methylene dioxybenzene, 2,6-bis (11-hydroxyethylamino) toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyra zole-5-one, 1-phenyl-3-methyl pyrazole-5-one, 2,6-dimethyl pyrazolo [1,5-13] -1,2,4-triazole, 2,6-dimethyl, 2-c] -1,2,4-triazole, 6-methyl pyrazolo [1,5-4-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 and sulphates. citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. In the context of the present invention, the coupler or couplers are generally present in a total amount ranging from 0.001 to 10% by weight of the total weight of the dyeing composition, preferably from 0.005 to 5% by weight relative to the total weight of the dye composition. a2) According to one embodiment of the invention, the dye (s) is (are) chosen from dyes of natural origin. The dyes of natural origin, may especially be selected from spinulosin, orceins, polyphenols or orthodiphenols (also called ODPs in the following description) and all extracts rich in ODPs, curcumin, derivatives of indole such as isatin or indole-2,3-dione, indigoides including indigo, phthalocyanines and porphyrins in particular complexed with a metal, glycosylated or non-glycosylated iridoids, chromenic dyes, anthraquinone dyes and benzoquinones such as that lawsone or henna, juglone, spinulosin, chromenic or chromanic dyes, such as neoflavanols and neoflavanones, flavanols, and indigoids such as indigo; and anthocyanidins. It is also possible to use the extracts or decoctions containing these natural dyes and in particular the poultices or plant extracts containing said dyes. The dye (s) of natural origin according to the invention can be salified (s) or not. They can also be in the form of aglygone (without bound sugar) or in the form of glycosylated compounds.
[0012] By "glycosyl" radical is meant a radical derived from a mono or polysaccharide. According to a particularly preferred embodiment of the invention the dye (s) are chosen from orthodiphenol (s): ODP (s) and polyphenols. By "ODP (s)" is meant one or more compounds comprising one or more aromatic rings of which at least one is a benzene ring is substituted by at least two hydroxy (OH) groups carried by two adjacent carbon atoms of said benzene group being present in the structure of the orthodiphenol (s). The aromatic ring is more particularly a condensed aryl or fused heteroaromatic ring, optionally containing one or more heteroatoms, such as benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, and the like. indole, isoindole, indoline, isoindoline, benzofuran, dihydrobenzofuran, chromane, isochromane, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic ring comprising at least two hydroxy groups carried by two adjacent carbon atoms of the aromatic ring. Preferably, the aromatic ring of the orthodiphenol derivatives according to the invention is a benzene ring. By "condensed ring" is meant that at least two saturated or unsaturated cycles, heterocyclic or otherwise, have a common bond, that is to say that at least one cycle is attached to another cycle.
[0013] More particularly, the dye (s) of the invention represents (s) an ODPs compound of formula (II), or one of its oligomers, tautomers, optical isomers, geometric isomers, as well as its salts or salts. its solvates such as hydrates: OH OH (II) formula (II) wherein: - R1 to R4, identical or different, represent: i) a hydrogen atom, ii) halogen, or a group selected from iii) hydroxy, iv) carboxy, v) carboxylate of (C1-C20) alkyl or (C1-C20) alkoxycarbonyl, vi) optionally substituted amino, vii) (C1-C20) linear or branched alkyl optionally substituted, viii) (C2 -C20) optionally substituted linear or branched alkenyl, ix) optionally substituted cycloalkyl, x) (C1-C20) alkoxy, x1) (C1-C20) alkoxy (C1-C20) alkyl, xii) C20) alkoxyaryl, xiii) aryl optionally substituted, xiv) aryl, xv) substituted aryl, xvi) heterocyclic, saturated or unsaturated, whether or not carrying a cationic charge or anion it is optionally substituted and / or optionally fused with an aromatic ring, preferably benzene, said aromatic ring being optionally substituted especially by one or more hydroxyl or glycosyloxy groups, xvii) a radical containing one or more silicon atoms; or two of the substituents carried by two adjacent carbon atoms R1-R2, R2-R3 or R3-R4 together with the carbon atoms carrying them a saturated or unsaturated ring, aromatic or otherwise, optionally containing one or more heteroatoms and optionally condensed with one or more saturated or unsaturated rings optionally containing one or more heteroatoms. In particular, the compound of formula (II) comprises from one to four rings.
[0014] A particular embodiment of the invention relates to one or more ODP (s) of formula (II) in which two adjacent substituents R1-R2, R2-R3 or R3-R4 can not form with the carbon atoms which carry them a pyrrolyl radical. According to a variant, R2 and R3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring bearing the two hydroxyls.
[0015] Within the meaning of the present invention, and unless a different indication is given: the saturated or unsaturated rings, optionally condensed, may also be optionally substituted; the "alkyl" radicals are saturated, linear or branched hydrocarbon radicals, generally C 1 -C 20, particularly C 1 -C 10, preferably C 1 -C 6 alkyl radicals, such as methyl, ethyl or propyl, butyl, pentyl and hexyl, the "alkenyl" radicals are linear or branched, unsaturated hydrocarbon radicals at 02-020; preferably comprising at least one double bond such as ethylene, propylene, butylene, pentylene, methyl-2-propylene and decylene; the "aryl" radicals are mono- or polycyclic carbon radicals, condensed or not, preferably comprising from 6 to 30 carbon atoms and of which at least one ring is aromatic; preferentially chosen from the aryl radical is phenyl, biphenyl, naphthyl, indenyl, anthracenyl, and tetrahydronaphthyl; The "alkoxy" radicals are alkyl-oxy radicals with alkyl as defined above, preferably C 1 -C 10, such as methoxy, ethoxy, propoxy and butoxy; the "alkoxyalkyl" radicals are (C1-C20) alkoxy (C1-C20) alkyl radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, and the like; "Cycloalkyl" radicals are C 4 -C 8 cycloalkyl radicals, preferably cyclopentyl and cyclohexyl radicals; the cycloalkyl radicals may be substituted cycloalkyl radicals, in particular with alkyl, alkoxy, carboxylic acid, hydroxy, amine and ketone groups; the "alkyl" or "alkenyl" radicals, when they are "optionally substituted", may be substituted by at least one atom or group carried by at least one carbon atom, chosen from: i) halogen; ii) hydroxy; iii) (C1-C2) alkoxy; iv) (C1-C10) alkoxycarbonyl; v) (poly) hydroxy (C2-C4) alkoxy; vi) amino; vii) 5- or 6-membered heterocycloalkyl; viii) optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, and optionally substituted with a (C1-C4) alkyl radical, preferably methyl; ix) amino substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: a) a hydroxyl group, b) an amino group optionally substituted with one or two (C 1 -C 3) alkyl radicals optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated, optionally comprising at least one other heteroatom different from or different from nitrogen, c) a quaternary ammonium group - N + R'R "R-, M- for which R ', R", R-, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl group; and M- represents the counter-ion of the organic acid, mineral or of the corresponding halide, d) or a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C 1 -C 4) radical. ) alkyl, preferably methyl; x) acylamino (-N (R) -C (O) -R ') in which the radical R is a hydrogen atom, a (C1-C4) alkyl radical optionally carrying at least one hydroxyl group and the 3037237 R 'is a C 1 -C 2 alkyl radical; a carbamoyl radical ((R) 2N-O (O) -) in which the R radicals, which may be identical or different, represent a hydrogen atom, a (C 1 -C 4) alkyl radical optionally bearing at least one hydroxyl group; xi) alkylsulfonylamino (R'-S (O) 2 -N (R) -) in which the radical R represents a hydrogen atom, a radical (01-04) alkyl optionally bearing at least one hydroxyl group and the radical R 'represents a radical (01-04) alkyl, a phenyl radical; xii) aminosulphonyl ((R) 2N-S (O) 2-) in which the R radicals, which may be identical or different, represent a hydrogen atom, a (C 1 -C 4) alkyl radical optionally carrying at least one chosen group among a) hydroxy, b) carboxy-O (O) -OH in acidic or salified form (preferably with an alkali metal or ammonium, substituted or unsubstituted); xiii) cyano; xiv) nitro; xv) carboxy or glycosylcarbonyl; xvi) phenylcarbonyloxy optionally substituted with one or more hydroxy groups; xvii) glycosyloxy; and phenyl optionally substituted with one or more hydroxy groups; The "aryl" or "heterocyclic" radicals or the aryl or heterocyclic radical radicals when they are "optionally substituted" may be substituted by at least one atom or group borne by at least one carbon atom chosen from: 01-010) alkyl, preferably 01-08, optionally substituted with one or more radicals selected from hydroxy, (01-02) alkoxy, (poly) hydroxyalkoxy 02-04, acylamino, amino substituted by two C1-C4 alkyl radicals, which may be identical or different, may optionally carry at least one hydroxyl group, or the two radicals may form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 ring members, preferably 5 or 6 membered, optionally substituted saturated or unsaturated optionally comprising another heteroatom identical to or different from nitrogen; ii) halogen; iii) hydroxy; iv) alkoxy in 01-02; v) C1-C10 alkoxycarbonyl; vi) (poly) hydroxyalkoxy at 0204; vii) amino; viii) 5- or 6-membered heterocycloalkyl; ix) optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, and optionally substituted by a (C1-C4) alkyl radical, preferentially methyl; Amino substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally bearing at least: a) a hydroxy, b) amino group optionally substituted with one or two optionally substituted C 1 -C 3 alkyl radicals, said alkyl radicals which can form, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered heterocyclic ring, saturated or unsaturated optionally comprising at least one other heteroatom which is different from or different from nitrogen, c) a group quaternary ammonium - N + R'R "R", M- for which R ', R ", which may be identical or different, represent a hydrogen atom, or a C1-C4 alkyl group, and M- represents the counter-ion of the corresponding organic, mineral or halide acid, d) a 5- or 6-membered optionally cationic heteroaryl radical, preferably imidazolium, and optionally substituted with a (C1-C4) alkyl radical, preferably methyl xi) acylamino (-N (R) -C (O) -R ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'is a C 1 -C 2 alkyl radical; xii) carbamoyl ((R) 2 N-C (O) -) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; xiii) alkylsulphonylamino (R'S (O) 2 -N (R) -) in which the radical R represents a hydrogen atom, a C 1-4 alkyl radical optionally carrying at least one hydroxyl group and the radical R ' represents a C1-C4 alkyl radical, a phenyl radical; xiv) aminosulfonyl ((R) 2N-S (O) 2-) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group, xv) carboxy in acid or salified form (preferably with an alkali metal or ammonium, substituted or unsubstituted); (xvi) cyano; xvii) nitro; xviii) polyhaloalkyl, preferentially trifluoromethyl; xix) glycosylcarbonyl; xx) a phenylcarbonyloxy group optionally substituted with one or more hydroxyl groups; xxi) a glycosyloxy group; and xxii) phenyl optionally substituted with one or more hydroxy groups; By "glycosyl" radical is meant in the sense of the present invention a radical derived from a mono or polysaccharide; the radicals "containing one or more silicon atoms" are preferably poly-dimethylsiloxane, poly-diphenylsiloxane, poly-dimethylphenylsiloxane or stearoxydimethicone radicals; The "heterocyclic" radicals are radicals comprising, in at least one ring, one or more heteroatoms chosen in particular from 0, N and S, preferably 0 or N, optionally substituted with in particular one or more alkyl, alkoxy, carboxy or hydroxy groups; , amine or ketone. These rings may contain one or more oxo groups on the carbon atoms of the heterocycle; among the heterocyclic radicals which may be used, mention may be made especially of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl and thienyl groups; still more preferably, the heterocyclic groups are fused groups such as benzofuranyl, chromenyl, xanthenyl, indolyl, isoindolyl, quinolyl, isoquinolyl, chromannyl, isochromannyl, indolinyl, isoindolinyl, coumarinyl, isocoumarinyl, these groups may be substituted, in particular by one or more OH groups. Among the natural dyes according to the invention, compounds which can be present in nature and which are reproduced by (hemi) chemical synthesis are included.
[0016] The salts of the dyes of the invention may be salts of acids or bases. The acids can be mineral or organic. Preferably, the acid is hydrochloric acid which leads to chlorides. According to another preferred embodiment of the invention, the dyeing composition used in the process for dyeing keratinous fibers comprises, as dye, one or more natural dye (s). More particularly, the dye (s) of the invention a) (is) are chosen from: - flavanols such as catechin and epichatechin gallate, - flavonols such as quercetin, 10 - anthocyanidins such as cyanidin, delphinidin, petunidine, anthocyanins or anthocyanins such as myrtillin, orthohydroxybenzoates, for example salts of gallic acid, flavones such as luteolin, hydroxystilbenes, for example tetrahydroxy-3 , 3 ', 4,5'-stilbene, optionally oxylated (for example glucosylated), curcumin, indole derivatives, phthalocyanines and porphyrins in particular complexed with a metal, glycosylated or non-glycosylated iridoids glycosyls, 3,4-dihydroxyphenylalanine and its derivatives, 2,3-dihydroxyphenylalanine and its derivatives, 4,5-dihydroxyphenylalanine and its derivatives, dihydroxycinnamates such as caffeic acid and chlorogenic acid , - orthopolyhydroxycoumar ines, 25 - orthopolyhydroxyisocoumarins, - orthopolyhydroxycoumarones, - orthopolyhydroxyisocoumarones, - orthopolyhydroxychalcones, - orthopolyhydroxychromones, - (anthra) quinones, - hydroxyxanthones, - 1,2 dihydroxybenzene and its derivatives, - 1,2 , 4 trihydroxybenzene and its derivatives, 1,2,3-trihydroxybenzene and its derivatives, 2,4,5-trihydroxytoluene and its derivatives, proanthocyanidines and in particular proanthocyanidins Al, A2, Bi, B2, B3 and ci - Chromium and chromene compounds - proathocyanines, - tannic acid, - ellagic acid, - and mixtures of these compounds.
[0017] Particularly the dye (s) a) is (are) chosen from the following ODP (s): - flavanols such as catechin and epichatechin gallate, - flavonols such as quercetin, - anthocyanidins such as cyanidine , delphinidin, petunidine, anthocyanins or anthocyanins such as myrtillin, orthohydroxybenzoates, for example gallic acid salts, flavones such as luteolin, hydroxystilbenes, for example 3,3-tetrahydroxy 4,4'-dihydroxyphenylalanine and its derivatives, 2,3-dihydroxyphenylalanine and its derivatives, 4,5-dihydroxyphenylalanine and its derivatives - dihydroxycinnamates such as caffeic acid and chlorogenic acid, - orthopolyhydroxy (iso) coumarins, - orthopolyhydroxy (iso) coumarones, 20 - orthopolyhydroxychalcones, - orthopolyhydroxychromones, - quinones, - hydroxyxanthones, - the 1,2 dih ydroxybenzene and its derivatives, 1,2,4-trihydroxybenzene and its derivatives, 1,2,3-trihydroxybenzene and its derivatives, 2,4,5-trihydroxytoluene and its derivatives, proanthocyanidines and especially proanthocyanidines Al A2, Bi, B2, B3 and ci, chromanics, and chromenics, proanthocyanins, tannic acid, ellagic acid, and mixtures of the foregoing compounds; Preferably the ODP (s) is (are) selected from haematein, brasiline, gallic acid, tannic acid, hematoxylin and brasiline and mixtures thereof.
[0018] According to one particular embodiment of the invention, the dye or dyes of the invention are chosen from anthraquinone dyes, and preferably natural dyes, chosen from those of the following formulas (A1) and (A2): ## STR2 ## that their tautomeric and / or mesomeric forms, their stereoisomers, their addition salts with a cosmetically acceptable acid or base, and their solvates such as hydrates; formulas (A1) and (A2) in which: - R1 and R8, identical or different, represent a hydrogen atom, a hydroxy group, or alkyl such as methyl; R2 represents a hydrogen atom, a hydroxy group, carboxy -C (O) OH or carboxylate -C (O) O-, Q + with Q + representing an alkali metal or alkaline earth metal such as potassium or calcium; R3 represents a hydrogen atom, ii) a hydroxy group, or an optionally substituted (iii) aryl group, preferably a phenyl group optionally substituted with one or more groups selected from a) hydroxy, b) amino, c ) (C1-C6) alkyl optionally substituted by one or more groups selected from hydroxy, carboxy and (C1-C4) alkylcarbonylamino; - R4 represents a hydrogen atom, or a hydroxyl group; R 5 represents a hydrogen atom, or a hydroxy, carboxy or carboxylate group -C (O) O-, Q + with as defined previously; - R6 represents a hydrogen atom, a hydroxyl group, -O-, Q + with Q + as defined above, carboxy or carboxylate -C (O) O-, Q + with Q + as defined above; R7 represents a hydrogen atom or a glycosyl radical, preferably glucose; M represents a metal, preferably column IIIA of the periodic table of the elements, such as aluminum; and G represents a hydroxy group, a water molecule or a ligand such as alkoxy, (di) (alkyl) amino. Preferably, the dyes of the invention are of formula (A1) and in particular, taken together or separately: R1 represents a hydroxyl or (C1-C4) alkyl group; - R2, R4 and the, identical or different, represent a hydrogen atom or a hydroxyl group; R3 represents a hydrogen atom, a hydroxy group, or a substituted phenyl group optionally substituted with one or more groups chosen from hydroxy, carboxy and (C1-C4) alkylcarbonylamino such that: ## STR2 ## with Y represents a group chosen from: -CH (NH2) -C (O) OH, -CH2-OH, -NH-C (O) -CH3 and the point of attachment to the rest of the molecule. R5 and R6, which may be identical or different, represent a hydrogen atom or a hydroxyl, carboxy -C (O) OH group or carboxylate -C (O) O-, Q + with Q + representing an alkaline or alkaline-earth metal such as as potassium or calcium; and - R7 represents a hydrogen atom.
[0019] According to one embodiment, the dye (s) of the invention are of formula (A2) and in particular, taken together or separately, - R1 represents a (C1-C4) alkyl group; R2 represents a carboxyl or carboxylate group -C (O) O-, Q + with Q + representing an alkaline or alkaline earth metal such as potassium or calcium; R3 and the represent a hydroxy group; - R4 represents a hydrogen atom or a hydroxy group, preferably hydrogen; - R6, represents a hydroxyl group, -O-, Q + with Q + as defined above; and - R7 represents a glycosyl radical such as glucose.
[0020] More preferably, the dye (s) of the invention are chosen from the following anthraquinones and extracts: Garance (Rubia tinctorum or Rubia cordifolia); 1,3-dihydroxyanthraquinone (purpuroxanthine); 30 - 1,4-dihydroxyanthraquinone (quinizarin); 1,2,4-trihydroxy-anthraquinone (purpurin, veratinum, Smoke Brown G, C.I. 1037, C.I. 58205, C.I. 75410, C.I. Natural Red 16, C.I. Natural Red 8); 1,2-dihydroxyanthraquinone (alizarin); carmine (Crimson lake, cochineal, natural red 4, C.I. 75470 or E120), the aluminum salt of carminic acid; - laccaic acid A, B, C or D; and anthragallol or 1,2,3-trihydroxyanthraquinone. According to another particular embodiment of the invention, the dye (s) are chosen from benzoquinones and naphthoquinones, in particular juglone and lawsone. In particular those from shrub leaves of the genus Lawsonia of the family Lythraceae which is based on the principle of staining by the active Lawsone: 2-hydroxy-1,4-naphthoquinone henna. Lawone [83-72-7] (Cl Natural Orange 6; Cl 75420) also known as isojuglone may be found in Henna shrubs (Lawsonia alba, Lawsonia inermis). Preferably the henna is in powder form. The henna powder can be sieved to obtain particles of upper limit sizes corresponding to the orifices or mesh sizes of the sieve particularly between 35 and 80 mesh (US). According to one particular embodiment of the invention, the particle size of the henna powder is fine. According to the invention, more particularly is meant a particle size of less than or equal to 500 mm. Preferably, the powder consists of fine particles of size included between 50 and 300 mm and more particularly between 10 and 200 mm. It is understood that said henna particles preferentially have a moisture content of between 0 and 10% by weight, relative to the total weight of the powders.
[0021] According to another particular embodiment, the dye (s) are chosen from indole derivatives such as isatin or indole-2,3-dione and indigo, preferably isatin. In particular, the dyes are derived from plants Isatis tinctoria, Calanthe discolor or Couroupita guianensis.
[0022] According to a particular embodiment, the dye or dyes are curcumin or curcumin. It is a compound naturally present in curry which is a polyphenol of chemical name (1E, 6E) -1,7-bis (4-hydroxy-3-methoxyphenyl) -1,6-heptadiene-3,5 -dione as well as these tautomeric forms.
[0023] According to a particular embodiment, the dye (s) of the invention are chosen from natural phthalocyanines and porphyrins, in particular those complexed with a metal, in particular chlorophylline and in particular that complexed with copper or magnesium, preferably cupric chlorophyllin. .
[0024] According to one embodiment, the dye (s) are chosen from glycosylated or non-glycosylated iridoids. In particular, the dye (s) of the invention are chosen from the (seco) iridoide-glycoside or (nono) irido-glycosylated acid (also called aglycon), extracted from plants such as Rubiaceae, Euphorbiaceae, Valerianaceae, Cornaceae, Gentianaceae, Caprifoliaceae, Oleaceae, Ericaceae, Loganiaceae, etc. preferably Rubiaceae. More particularly, the dye (s) of the invention are derived from the following plant extracts: Veronica persica; Genipa americana; Apodytes dimidiata; Randia canthioides; Tarenna attenuata and preferably Genipa americana.
[0025] According to a particularly preferred embodiment of the invention, the dye (s) a) are chosen from chromenic or chromanic dyes. According to the invention, the term "chromenic or chromanic" dyes is understood to mean dyes which comprise in their structure at least one bicycle of the following formula (B): (B) the intracyclic bond representing a single carbon-carbon bond or a carbon-carbon double bond, as illustrated by the formula (B1) designating the chromene family and the formula (B2) designating the chroman family below: (B1) (B2) More particularly, the dye (s) of the invention a) are of formula (B) and preferably selected from neoflavanols and neoflavanones, particularly chosen from dyes of the following formulas:> formula (III), comprising in its structure the bicycle of formula (B2), O R4 H HO R 20 3 as well as its tautomeric and / or mesomeric forms, its stereoisomers, its addition salts with a cosmetically acceptable acid or base, and its solvates such as hydrates; Formula (III) wherein: - represents a single carbon-carbon bond or a carbon-carbon double bond, the linking of these bonds denotes two single carbon-carbon bonds and two carbon-carbon double bonds, said bonds being conjugated, - X represents a group: HO-C or O = C 5 -R1, R2, R3, R4, R5 and R6, which may be identical or different, represent a hydrogen atom, a hydroxy group or an alkyl group; optionally substituted, optionally substituted alkoxy, or an optionally substituted acyloxy group; and> formula (IV), comprising in its structure the bicycle of formula (B1): ## STR1 ## as well as its tautomeric and / or mesomeric forms, its stereoisomers, its addition salts with an acid or a cosmetically acceptable base , and its hydrates; Formula (IV) in which: R11, R12, R13, R16, R19 and R20, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical, and R14, R15, R17 and R18; identical or different, represent a hydrogen atom, a hydroxyl radical or a C1-C4 alkoxy radical. Regarding the dyes of formula (III) as defined above, these can be in two tautomeric forms noted (111a) and (111b): ## STR2 ## The alkyl radicals mentioned in the previous definitions substituents are hydrocarbon radicals, saturated, linear or branched, generally C 1 -C 20, particularly C 1 -C 10, preferably C 1 -C 6, such as methyl, ethyl, propyl, butyl, pentyl and hexyl. The alkoxy radicals are alkyl-oxy radicals with the alkyl radicals as defined above, and preferably the alkoxy radicals are C1-Cc, such as methoxy, ethoxy, propoxy and butoxy. The alkyl or alkoxy radicals, when substituted, may be substituted with at least one substituent carried by at least one carbon atom selected from i) a halogen atom; or a group ii) hydroxy, iii) C1-2 alkoxy, iv) C1-10 alkoxycarbonyl, v) (poly) hydroxyalkoxy 02-04, vi) amino, vii) 5- or 6-membered heterocycloalkyl, viii) heteroaryl 5- or 6-membered ring optionally cationic, preferably imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical, preferably methyl; ix) an amino radical substituted with one or two identical or different C1-C6 alkyl radicals optionally carrying at least: a) a hydroxyl group; b) an amino group optionally substituted by one or two C1-C6 alkyl radicals; 03 optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered heterocyclic ring, saturated or unsaturated, optionally substituted, optionally comprising at least one other heteroatom which may or may not be different from nitrogen; (c) a quaternary ammonium group - N + R'R "R", M- for which R ', R ", which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl group, and M- represents the counter-ion of the organic acid, mineral or of the corresponding halide, d) or a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted by a radical (01-04) alkyl le, preferably methyl; x) an acylamino radical (-N (R) -C (O) -R ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least a hydroxyl group and the radical R 'is a C 1 -C 2 alkyl radical; xi) a carbamoyl radical ((R) 2 N-C (O) -) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally carrying at least one group hydroxy; xii) an alkylsulphonylamino radical (R'-S (O) 2 -N (R) -) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C 1 -C 4 alkyl radical or a phenyl radical; xiii) an aminosulphonyl radical ((R) 2 N -SO 2 -) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; (xiv) a carboxylic radical in acid or salt form (preferably with an alkali metal or ammonium, substituted or unsubstituted); xv) a cyano group; (xvi) a nitro group; xvi) a carboxy or glycosylcarbonyl group; xvii) a phenylcarbonyloxy group optionally substituted by one or more hydroxyl groups; xviii) a glycosyloxy group; and xix) a phenyl group optionally substituted with one or more hydroxy groups. Preferably, the alkyl or alkoxy radicals of formula (III) are unsubstituted.
[0026] According to one particular embodiment of the invention, the dyes of formula (III) comprise an R 6 radical representing a hydroxyl group. Another particular embodiment of the invention relates to the dye (s) of formula (III), for which the radical R 1 represents a hydrogen atom or a hydroxyl group. More particularly, the dye (s) of the invention (a) is (are) of formula (III) and chosen from hematoxylin, haematein, brazilin and braziléine; preferentially hematoxylin and brazilin: HO HO HO Hemeineine Braziléine HO HO OH HO HO Hematoxylin (Natural Black 1 - Braziline (Natural Red 24 - CAS 517-28-2) CAS 474-07-7) Braziléine is a conjugated form a chroman compound of formula (A2). The diagram below shows the tautomeric structures (111a) and (111b) illustrated above. Amongst the dyes of the invention of the hematoxylin / haematin and brazilin / braziline type, mention may be made, by way of example, of hematoxylin (Natural Black 1 according to the name I NCI) and braziline (Natural Red). 24 according to the name I NCI), dyes of the family of indochromanes, which are commercially available. These may exist in an oxidized form and be obtained by synthesis or by extraction of plants or plants known to be rich in these dyes.
[0027] The dye (s) of natural origin of the invention may be used in the form of extracts. The following plant extracts (genus and species) can be used: Haematoxylon campechianum, extract of oxidized wood (Haematoxylon 3037237 23 campechianum), brasiletto (Hematoxylum braziletto, rich in brazilin and protosappanin), Quebracho (schinopsis lorentsii) Caesalpinia echinata, Caesalpinia sappan , Caesalpinia spinosa, and Caesalpina Brasiliensis. The extracts are obtained by extracting various parts of plants, such as, for example, the root, the wood, the bark or the leaf. According to a particular embodiment of the invention, the dye (s) of natural origin are of formula (II) and are derived from woods of logwood, pernambuco wood, sappan wood and brazil wood. According to a particular embodiment of the invention, the dyes are of formula (IV), preferably those for which R 11 and R 13 represent an alkyl radical, preferably methyl. Preferably, R12, R16, R19 and R20 denote, independently of one another, a hydrogen atom or an alkyl radical, preferably methyl. Preferably, R 14 and R 17 denote, independently of one another, a hydrogen atom or an alkoxy radical, preferably methoxy. Preferably, R 18 and R 15 denote, independently of one another, a hydrogen atom, a hydroxyl radical or an alkoxy radical, preferably methoxy. A first particularly preferred family of naturally occurring dyes of the invention suitable for the present invention are those dyes of formula (IV) above wherein R12, R15, R16, R17, R19 and R20 each represent a hydrogen atom. R11 and R13 each represent a methyl radical and R14 represents a methoxy radical. Among the preferred dyes of the invention of this first family include those, for which R18 represents a methoxy (santaline B) or hydroxy (santaline A) radical.
[0028] A second particularly preferred family of dyes suitable for the present invention is that of the dyes of formula (IV) above for which: R 11 and R 13 are each methyl, R 17 is methoxy. A preferred dye of this second family is that for which, in addition, R19 represents a methyl radical, R20, R12, R14, R18 and R16 each represent a hydrogen atom, and R15 represents the hydroxyl radical (santarubin A). A second preferred dye of this second family is that for which R18, R20, R12, R14 and R16 represent a hydrogen atom, R15 represents a methoxy radical and R19 represents a methyl radical (Santarubine B).
[0029] A third family of preferred dyes of this second family is that for which R 20, R 12, R 14, R 15, R 16 and R 19 represent hydrogen and R 18 represents the hydroxyl radical (santarubine C).
[0030] The dye (s) of interest of this second family is that for which R 15 represents a methoxy radical, and R 18 and R 14 represent a hydrogen atom and R 20, R 12, R 16 and R 10 represent a methyl radical ( tetra-O-méthylcantarubine). The dye (s) of formula (IV) can be used in the form of extracts. Redwood plant extracts, generally comprising Asian and West African wood species of the genus Pterocarpus and the genus Baphia, may be used. These woods are, for example, Pterocarpus santalinus, Pterocarpus osun, Pterocarpus soyauxii, Pterocarpus erinaceus, Pterocarpus indicus or Baphia nitida. These woods can still be called padauk, sandalwood (sandalwood), narrawood, camwood or barwood. Thus, usable extracts containing dyes of formula (IV) in the present invention may for example be obtained from red sandalwood (Pterocarpus santalinus) by aqueous basic extraction, such as the product sold under the trade name Sandalwood Concentrate. SL 709C by the company COPIAA or 15 by means of a solvent extraction of sandalwood powder such as the product sold under the trade name Sandalwood Powder SL PP by the same company COPIAA. We can also mention the hydroalcoholic extract of Sandalwood powder red ALBAN MULLER company. Extracts also suitable for the present invention may be obtained from wood such as Camwood (Baphia nitida) or Barwood (Pterocarpus soyauxii, Pterocarpus erinaceus): the latter is thus fractionated and then ground: a conventional alcohol extraction or by percolation is then carried out on this ground to obtain a powdery extract particularly suitable for the implementation of the present invention.
[0031] The dye (s) of formula (III) and (IV) of the invention may be cosmetically acceptable acid or base salts. The acids can be mineral or organic. Preferably, the acid is hydrochloric acid leading to the chlorides. The bases can be mineral or organic. Especially the bases are alkali hydroxides, such as sodium hydroxide leading to sodium salts. According to a particular embodiment of the invention, the dye (s) are chosen from dihydroxyflavonoids, preferably of formula (V), and also their organic or inorganic acid or base salts, their optical, geometrical and tautomeric isomers. their solvates such as hydrates: ## STR2 ## wherein: represents a single bond or a double bond; R1, R2, R3, R4, R10, R11, R12, R13 and the same or different are hydrogen, halogen, or a group selected from i) hydroxy, ii) (C1-C6) alkyl, , iii) (C 1 -C 6) alkoxy, iv) (C 1 -C 6) alkylthio, v) carboxyl, vi) alkyl carboxylate or alkoxycarbonyl, vii) optionally substituted amino, viii) optionally substituted linear or branched alkenyl, ix) cycloalkyl optionally substituted, x) optionally substituted aryl, xi) a group containing one or more silicon atoms, xii) (di) ((hydroxy) (C1-C6) alkyl) amino, xiii) glucosyl, xiv) RZC (X) -Y- with R representing a hydrogen atom, a (C1-C6) alkyl or aryl group optionally substituted in particular by at least one hydroxyl group such as 3,4,5-trihydroxyphenyl; Y and Z, which may be identical or different, represent a bond, or an oxygen atom, sulfur atom or a group - N (R ') - with R' representing a hydrogen atom or a (C 1 -C 6) alkyl group, Y may also represent a (C1-C6) alkylene group; X represents an oxygen, sulfur, or N-R "atom with R" representing a hydrogen atom or a (C1-C6) alkyl group; R5, R6, R7, R8 and R9, which may be identical or different, represent a hydrogen atom, or a group chosen from a hydroxyl group, a (C1-C6) alkyl group, or a RZC (X) -Y group; - as defined above, - or else the unit (V) constitutes the polymeric unit of a polyphenol which will be connected to the other units of said polyphenol by positions 4, 6 or 8 of the chromane ring in which case R1, or R3 and R6 form a covalent bond with the other units of said polyphenol; Or R 5 with R 6 and / or R 7 together with R 8 together with the carbon atom carrying them an oxo group; or R8 and R9 together form a bond; it being understood that: when R5 with R6 and / or R7 with R8 together form an oxo group, or R8 with R9 together form a bond, then = represents a single bond; - when = is a double bond between the oxygen atom and the carbon atom in position 2 then R9 is absent and when = is a double bond between the carbon atoms in position 3 and 4 then R5 and R7 are absent ; When carried by the oxygen atom is a double bond, then the compound of formula (V) is cationic and it is associated with it an anionic counterion, organic or inorganic, such as halide. Preferably at least two radicals of the compounds of formula (V) selected from R1, R2, R3, R4, R10, R11, R12, R13 and contiguous represent a hydroxy group. Preferably the group R-Z-C (X) -Y- compounds of formula (V) is 3,4,5-trihydroxyphenyl-1-carbonyloxy (-O-gallate). Preferably, the radicals R 1, R 2, R 3, R 4, R 10, R 11, R 12, R 13 and R 14 are chosen from hydrogen, and hydroxy, glycosyloxy and alkoxy groups.
[0032] According to a particular embodiment, the dye or dyes of the invention are chosen from: i) flavanols of formula (Va) which contain at least two ortho hydroxy groups, such as catechin, pine bark extract, gallate epichatechin, and cocoa flavanols including epichatechin, flavanols, especially flavan-3-ol of green tea, and their oligomers and polymers called proanthocyanidols or condensed tannins such as theaflavin, theaflavin 3'-O- gallate, 3,3'-O-digallate theaflavin, Ai, A2, Bi, B2, B3 and Cl proanthocyanidins such as profisetinidine and procyanidin and mixtures of the foregoing compounds. R13 Flavan-3-ol or flavanol: (Va) as well as their acid or base salts, organic or inorganic, their optical, geometric isomers, tautomers and solvates such as hydrates; formula (Va) in which: R7, R8, which may be identical or different, represent a hydrogen atom, or a group chosen from hydroxy, (C1-C6) alkyl, or a group RZC (X) -Y- such that previously defined preferably 0-gallate being understood that at least one of the two groups; - R7 or R8 represents a hydroxy group or R-Z-C (X) -Y- as defined above; R 6 and R 6, which may be identical or different, represent a hydrogen atom or a hydroxyl group or R 6 and R 8 form a bond or the unit (Va) constitutes the polymeric unit which will be connected to the other units by the positions 4, 6; or 8 where R1, or R3 and R6 form a bond; the radicals R1, R2, R3, R4, R10, R11, R12, R13 and R14 being as defined above for the formula (V); Among the proanthocyanidin compounds, there may be mentioned, for example, profisetinidine and procyanidin, the formulas of which are represented; 5 - ii) flavonols of formula (Vb) which contain at least two ortho hydroxy groups such as quercetin, luteolin, myricetol, fisetin, and / or two hydroxy groups in meta such as the morine, their glycosides, their derivatives methoxylates such as rhamnetin (preferably having at least two hydroxy groups in ortho): R13 Flavonol: R4 0 (Vb) 3-hydroxy-2-phenylchromen-4-one and their acid or base salts, organic or mineral, their optical, geometric isomers, tautomers and their solvates such as hydrates; formula (Vb) in which the radicals R1, R2, R3, R4, R10, R11, R12, R13 and -14 are as previously defined in formula (V); iii) flavones of formula (Vc) which comprise at least two ortho-hydroxyl groups such as luteolin, their glycosides, such as luteolol 7-O-glucoside, baicalin, orientine: Flavone: (Vc) 0 2- phenylchromen-4-one as well as their acid or base salts, organic or inorganic, their optical isomers, geometric, tautomers and solvates such as hydrates; formula (Vc) wherein the radicals R 1, R 2, R 3, R 4, R 10, R 11, R 12, R 13 and 14 are as previously defined in formula (V); (Iv) dihydroflavonols or dihydroxyflavanonols of formula (Vd) which contain at least two orthohydroxy groups such as dihydroquercetol, and their glycosides such as dihydroquercetol 3-O-rhamoside: Dihydroflavonol or Flavanonol: 5 R4 0 (Vd) 3-hydroxy-2,3-dihydro-2-phenylchromen-4-one as well as their acid or base salts, organic or inorganic, their optical, geometric isomers, tautomers and solvates such as hydrates ; formula (Vd) in which the radicals R1, R2, R3, R4, R10, R11, R12, R13 and -14 are as previously defined in formula (V); v) flavanones of formula (Ve) which contain at least two ortho hydroxy groups such as eriodictyol; Flavanone: R 40 (Ve) 2,3-dihydro-2-phenylchromen-4-one as well as their acid or base salts, organic or inorganic, their optical isomers, geometric, tautomers and solvates such as hydrates ; wherein R1, R2, R3, R4, R10, R11, R12, R13 and -14 are as previously defined in formula (V); Vi) the flavan-3,4-diols or leucoanthocyanidines of formula (Vf) which contain at least two ortho hydroxy groups such as leucocyanidol (= procyanidol). Flavan-3,4-diol: (Vf) and their acid or base salts, organic or inorganic, their optical, geometrical isomers, tautomers and their solvates such as hydrates; Formula (Vf) wherein the radicals R 1, R 2, R 3, R 4, R 10, R 11, R 12, R 13 and 14 are as previously defined in formula (V); vii) anthocyanidins (or anthocyanidins, or anthocyanidins) of formula (Vg) which contain at least two hydroxyl groups ortho, such as cyanidol, delphinidin, aurantinidine, luteolinidine, their glycosides such as dihydroxyanthocyananes (or dihydroxyanthocyanosides) , or anthocyanins on the English model), their oligomers and polymers such as proanthocyanines, preferably anthocyanidins and in particular blueberry; R13 Anthocyanidol: Cation Flavylium According to another advantageous embodiment of the invention the dye (s) of the invention are compounds of formula (a), or one of its oligomers, in salified form or not: (a) wherein: - R represents a hydrogen atom or a hydroxyl group; Wherein R 'represents a hydroxy group or the following phenoxy group (a'): wherein: OH represents a divalent, trivalent or tetravalent group selected from (C1-C6) alkylene such as methylene; carbonyl -O (O) -, -CH =,> C <; R1, R2 and R3, which may be identical or different, represent a hydrogen atom, or a hydroxyl or (C1-C6) alkoxy group such as methoxy; R4 represents a hydrogen atom, a hydroxy group or -O-glycoside; or else the radicals R, Y and R 'form together with the carbon atoms which carry them a heterocyclic group condensed in the ring A, of formula (b), (g) or (g') as follows:, S, o, S ## STR2 ## R 5 represents a hydrogen atom, a hydroxy group or -O-glycoside; - R6 to R10, identical or different, represent a hydrogen atom or a hydroxyl group, preferably R6 and R10 represent a hydrogen atom, R7, R8 and R9, represent a hydrogen atom or a hydroxyl group; Z represents a hydrogen atom or the following group (d): It being understood that the compound of formula (a) has at least two hydroxyl groups in the ortho position of a phenyl radical. In a preferred variant, the dye (s) according to the invention are compounds of formula (a), and more particularly polyphenols such as tannic acid.
[0033] The dye (s) according to the invention may be in particular a mixture of proanthocyanidin derivatives such as profisetinidine and procyanidin and compounds of formula (a), and more particularly polyphenols such as tannic acid. Preferably, the dye (s) of the invention are derived from plant extracts. It is also possible to use mixtures of plant extracts.
[0034] The natural dye extracts according to the invention may be in the form of powders or liquids. Preferably, the extracts are in powder form. In particular, the dye or dyes of the invention are chosen from catechin, quercetin, brazilin, haematein, hematoxylin, chlorogenic, caffeic, gallic acids, catechol, gallic acid, L DOPA, pelargonidine, cyanidine, ( -) - Epicatechin, 15 (-) - Epigallocatechin, (-) - Epigallocatechin 3-gal late (EGCG), (+) - Catechin, I soquercetin, Pomiferin, esculetin, 6,7-Dihydroxy-3- (3-hydroxy) -2,4-dimethoxyphenyl) coumarin. Santalin AC, Mangiferine, Butein, Maritimetine, Sulfuretine, Robtein, Betanidine, Pericampylinone A, Theaflavin, Proanthocyanidin A2, Proanthocyanidin B2, Proanthocyanidin C1, Procyanidines DP 4-8, Tannic Acid, Purpurogalline, 5,6-Dihydroxy-2- methy1-1,4-naphthoquinone, Alizarin, VVelelactone, Variegatic acid, Gomphidic acid, Xerocomic acid, Carnosol, and natural extracts containing them. Preferably, the dye (s) of the invention are chromenic or chromanic and are chosen from haematein, hematoxylin, brasiline, brasiline and santaline A.
[0035] By "carboxylate" is meant carboxylic acid salt. When the dye precursors have D and L forms, both forms can be used in the compositions according to the invention, as well as the racemates. According to one embodiment, the natural dye (s) are derived from extracts of animals, bacteria, fungi, algae, plants and fruits used in whole or in part. In particular concerning the plants the extracts are from fruits including citrus fruits, vegetables, trees, shrubs. It is also possible to use mixtures of these extracts, rich in natural dyes, especially ortho-diphenols as defined above. Preferably, the natural dye (s) of the invention are derived from extracts of plants or parts of plants. For the purposes of the invention, these extracts will be assimilated as ingredient c). The extracts are obtained by extraction of various parts of plants such as for example root, wood, bark, leaf, flower, fruit, seed, pod, peel.
[0036] Among plant extracts, tea leaf extracts, especially Japanese green tea, rose. Among the fruit extracts, mention may be made of extracts of apple, grapes (in particular grape seeds), or extracts of beans and / or pods of cocoa.
[0037] Among the vegetable extracts, mention may be made of potato extracts and onion peels. Among the extracts of wood of trees include pine bark extracts, extracts of logwood, extracts of Quebracho. It is also possible to use mixtures of plant extracts.
[0038] According to a particular embodiment of the invention, the orthodiphenol derivative (s) are natural extracts rich in ODPs. According to a preferred embodiment, the dye (s) of the invention are only natural extracts. Preferably, the dye (s) according to the invention is (are) chosen from catechin, quercetin, haematein, hematoxylin, brasiline, brasiline, gallic acid, tannic acid. and natural extracts containing them selected from grape pomace, pine bark, green tea, onion, cocoa bean, logwood, red wood and gall-nut, sorghum or sorghum (dyer's sorghum) and quebracho wood.
[0039] The natural extracts according to the invention may be in the form of powders or liquids. Preferably, the extracts of the invention are in the form of powders. a3) According to another embodiment of the invention, the dye (s) is (are) chosen from among the direct dyes. The direct dye (s) that can be used in the context of the invention is (are) chosen from anionic direct dyes, cationic or neutral, synthetic or natural, fluorescent or not. According to one particular embodiment of the invention, the dye (s) are chosen from anionic or dye direct dyes commonly known as "acid" or "acid dyes" direct dyes for their affinity with alkaline substances. Anionic direct dyes are understood to mean any direct dye comprising in its structure at least one SO3- sulphonate group and / or at least one O (O) O- carboxylate group and optionally one or more G- with G- anionic groups, which may be identical or different. different, representing an anionic group selected from alkoxide O-, thiolate S-, carboxylate and thiocarboxylate: C (Q) Q'- with Q, Q 'identical or different representing an oxygen or sulfur atom; preferably G- represents a carboxylate i.e. Q and Q 'represents an oxygen atom.
[0040] More particularly, the dye (s) of the invention are chosen from the direct dyes of formula (VI): ColOrn (()) +, (VI) Formula (VI) in which: - Col °, represents the part anionic anionic direct dye or "acid" dye comprising in its structure at least one sulphonate group and / or at least one carboxylate group and comprising m anionic charge (s): - m and n, which are identical or different, represent a integer inclusive of between 1 and 10 - Q +, which may be identical or different, represents a cationic, organic or inorganic counterion, preferably chosen from alkali or alkaline earth metal cations such as Na + or K. In the formula (VI) of The radical Col (-) m represents the anionic part of the "acid dyes" or "acid dyes" or anionic direct dyes and preferably Col (-) m has in its structure: o at least one sulphonate group and at least one a (hetero) aryl group, it being understood that at least one sulphonate group is directly linked to a (hetero) aryl group, preferably an aryl group such as phenyl or benzo; and o optionally one or more anionic groups G- as defined above. According to another preferred embodiment of the invention, Col (-) m comprises in its structure: at least one carboxylate group and at least one (hetero) aryl group, it being understood that at least one carboxylate group is linked directly to a (hetero) aryl preferentially aryl group such as phenyl or benzo; and o optionally one or more anionic groups G- as defined above. According to yet another preferred embodiment of the invention, Col% contains in its structure: at least one carboxylate group, at least one carboxylate group and at least one (hetero) aryl group, it being understood that at least one group sulfonate or carboxylate is directly connected to a group (hetero) aryl preferentially aryl such as phenyl or benzo; and optionally, one or more anionic groups G- as defined above. According to a particular embodiment of the invention, the dyes of formula (VI) are such that m is equal to n.
[0041] An advantageous variant of the invention relates to the dyestuffs of formula (VI) for which m and n are 1, 2 or 3. The preferred anionic dyes of formula (VI) of the invention are chosen from acidic direct nitro dyes. acid azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, indigoids and acidic natural dyes; each of these dyes having at least one cationic counterionic sulfonate or carboxylate group as defined above; preferentially alkali metal, alkaline earth metal or ammonium sulphonate or carboxylate.
[0042] As dyestuffs according to the invention, mention may be made of the dyes of formulas (VII), (VII '), (VIII), (VIII'), (IX), (IX '), (X), (X' ), (XI), (XII), (XIII) and (XIV): a3a) diaryl anionic azo dyes of formula (VII) or (VII '): R'7 R'10 R'8 (VII') In which: R7, R8, R9, R10, R'7, R'9 and R'10, which may be identical or different, represent a hydrogen atom or a chosen group; among: i) alkyl, ii) alkoxy, iii) alkylthio, iv) hydroxy, v) mercapto, vi) nitro, vii) R ° -C (X) -X'-, R ° -X'-C (X) Embedded image wherein R 0 represents a hydrogen atom, an alkyl or aryl group, X, X 'and X ", which may be identical or different, representing an atom of oxygen, sulfur or NR with R representing a hydrogen atom or an alkyl group; viii) (0) 2S (0 -) -, W with W as previously defined for M or represents a cationic counter ion as defined above; ix) (0) C0--, W with W as previously defined; x) R "-S (O) 2-, with R" representing a hydrogen atom, an alkyl group, an aryl group, (di) (alkyl) amino, aryl (alkyl) amino; preferentially a phenylamino or phenyl group; xi) R - S (O) 2 -X'- with R "representing an alkyl group, optionally substituted aryl, X 'as defined above; xii) (di) (alkyl) amino; xiii) aryl (alkyl) amino optionally substituted with one or more groups selected from nitro; nitroso; (O) 2S (O -) -, W and alkoxy with W as defined above; xiv) optionally substituted heteroaryl; preferably benzothiazolyl; xv) cycloalkyl; cyclohexyl, xvi) Ar-N = N- with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted by one or more alkyl groups, (0) 2S (O -) -, W or phenylamino; two contiguous groups R7 with R8 OR R8 with R9 OR R9 with R10 together form a fused group benzo A 'and R'7 with R'8 OR R'8 with R'9 OR R'9 with 5 R'10 together a fused benzo B 'group with A' and B 'optionally substituted with one or more groups selected from i) nitro; ii nitroso; iii) (0) 2S (0 -) -, W; iv) hydroxy; (v) mercapto; vi) (di) (alkyl) amino; vii) R ° -C (X) -X'-; viii) R ° -X'-C (X) -; ix) R °-X'-C (X) -X "-; x) Ar-N = N- and xi) aryl (alkyl) amino optionally substituted, with W, R °, X, X ', X" and Ar as defined previously; W represents a sigma bond, an oxygen or sulfur atom, or a divalent radical i) -N (R) - with R as defined above, or ii) methylene -C (Ra) (Rb) - with Ra and Rb identical or different, representing a hydrogen atom or an aryl group, or else Ra and Rb together with the carbon atom carrying them a cycloalkyl spiro; preferentially W represents a sulfur atom or Ra and Rb together form a cyclohexyl; it being understood that the formulas (VII) and (VII ') comprise at least one (O) 2S (O -) -, Q + or carboxylate (0) C (O -) -, Q + sulphonate radical on one of the rings A, A ', B, B' or C with R2R3R4 as previously defined; preferentially alkali metal, alkaline earth metal or ammonium sulphonate or carboxylate; Examples of dyestuffs of formula (VII) which may be mentioned are: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Red Acid Red 73, Red Acid Red 73, Red Acid Red 135, Red Acid Red 138, Food Red 1, Food Red 1 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2; and by way of example of dyes of formula (VII ') that may be mentioned: Acid Red 111, Acid Red 134, Acid yellow 38; A3b) the azo anionic pyrrazolone dyes of formula (VIII) and (VIII '): R16 R17 R17 R13 (VIII) R15 F20 R18 R19 19 1 1 (V1 1 1) R13 R1 formulas (VIII) and (VIII in which: R 11, R 12 and R 13, which may be identical or different, represent a hydrogen atom, a halogen atom, an alkyl group or - (O) 2 S (O-), W with W as defined above; R14 represents a hydrogen atom, an alkyl group or a C (O) O- group, W with W as defined above; - R15 represents a hydrogen atom; - R16 represents an oxo group in which case R'16 is absent, or else R15 with R16 together form a double bond; R 17 and R 18, which are identical or different, represent a hydrogen atom, or a group chosen from: - (O) 2 S (O -) -, W with W as defined previously; - Ar-O-S (O) 2- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted with one or more alkyl groups; - R10 and R20 together form either a double bond or a benzo group D ', optionally substituted; - R'16, R'16 and R'20, identical or different, represent a hydrogen atom or an alkyl group, or hydroxy; R21 represents a hydrogen atom, an alkyl group, or alkoxy; - R. and Rb, identical or different, are as defined above, preferably Ra represents a hydrogen atom and Rb represents an aryl group; - Y represents either a hydroxyl group or an oxo group; - represents a single bond when Y is oxo group; and represents a double bond when Y represents a hydroxy group; it being understood that the formulas (VIII) and (VIII ') comprise at least one sulfonate group (O) 2S (O -) -, Q + on one of the rings D or E, or the formulas (VIII) and (VIII') comprise at least minus a carboxylate group (O) C (O -) -, Q + with Q + as previously defined; preferably comprise at least one sulfonate group (O) 2S (O -) -, Q + on one of the rings D or E and more particularly sulphonate; By way of example of dyes of formula (VIII) mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and by way of example of dyes of formula (VIII '), mention may be made of 'Acid Yellow 17; R11 36 R21 R21 - 4 FjJ N -R14 R11 3037237 37 a3c) anthraquinone dyes of formula (IX) and (IX '): R22 formulas (IX) and (IX') in which: - R22, R23, R24, R25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom, or a group chosen from: i) alkyl, ii) hydroxy, iii) mercapto, iv) alkoxy, v) alkylthio, vi) aryloxy or optionally substituted arylthio, preferably substituted by one or more groups selected from alkyl and (0) 2S (O -) -, W with W as defined above, vii) aryl (alkyl) amino optionally substituted with one or more groups selected from alkyl and (0) 2S (O-) -, W with W as defined above, viii) (di) (alkyl) amino, ix) (di) (hydroxyalkyl) amino, x) (O) 2S (O-) -, W with W as defined previously; Z 'represents a hydrogen atom or a group NR28R29 with R28 and R29, identical or different, represent a hydrogen atom or a group chosen from i) alkyl, ii) polyhydroxyalkyl such as hydroxyethyl, iii) aryl optionally substituted by one or more particularly alkyl groups such as methyl, n-dodecyl, n-butyl; (0) 2S (0 -) -, W with W as previously defined; R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X "- with R °, X, X 'and X" such as defined above, preferably R ° represents an alkyl group, iv) cycloalkyl; especially cyclohexyl; - Z, represents a group selected from hydroxy and NR'28R'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined above; it being understood that formulas (IX) and (IX ') comprise at least one sulfonate group (O) 2S (O -) -, Q +; By way of example of dyes of formula (IX), mention may be made of Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140 and Acid Blue 251, Acid Green. 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; and by way of example of dyes of formula (IX ') mention may be made of Acid Black 48; A3d) nitro dyes of formula (X), and (X '): W-ALK-SO 3 (R 30) q (X) NO 2 (R 30) p (X) (X') formulas (V) and (V ') in which: R30, R31 and R32, which are identical or different, represent a hydrogen or halogen atom, or a group chosen from: i) alkyl, ii) alkoxy optionally substituted with one or more hydroxyl groups (iii) alkylthio optionally substituted by one or more hydroxyl groups, iv) hydroxy, mercapto, v) nitro, nitroso, vi) (poly) haloalkyl, vii) R ° -C (X) -X'-, R ° - X'-C (X) -, R °-X'-C (X) -X "- with R °; X, X 'and X" as previously defined, viii) (0) 2S (0 -) - , W with W as defined above, ix) (O) CO, W with W as previously defined, x) (di) (alkyl) amino, xi) (di) (hydroxyalkyl) amino, xii) heterocycloalkyl such that piperidino, piperazino or morpholino especially R 30, R 31 and R 32 represent a hydrogen atom; - R, and Rd, identical or different, represent a hydrogen atom or an alkyl group; - W is as defined previously; W is particularly -NH-15 -AlK is a divalent linear or branched C 1 -C 6 alkylene group; especially ALK is -CH2-CI-12-; n is 1 or 2; - p represents an integer inclusive between 1 and 5; Q represents an integer inclusive between 1 and 4; u is 0 or 1; when n is 1, J represents a nitro or nitroso group; especially nitro; when n is 2, J represents an oxygen or sulfur atom, or a divalent radical - S (O), - with m representing an integer 1 or 2; preferentially J represents a -SO2- radical; M 'is as defined previously for W; present or absent represents a benzo group optionally substituted with one or more R30 groups as defined above; It being understood that formulas (X) and (X ') comprise at least one sulfonate group (O) 2S (O -) -, Q + or carboxylate (O) C (O -) -, Q +; By way of example of dyes of formula (X), mention may be made of: Acid Brown 13; Orange Acid 3; by way of example of dyes of formula (X '), mention may be made of: Acid Yellow 1, 2,4-dinitro-1-naphthol-7-sulfonic acid sodium salt, 2-piperidino 5-nitro benzene acid sulfonic acid, 2 (4'-N, N (2 "-hydroxyethyl) amino-2'-nitro) aniline ethanesulphonic acid, 4β-hydroxyethylamino-3-nitrobenzene sulfonic acid, a3e) triarylmethane dyes of formula (XI): (XI) wherein R33, R34, R35 and R36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; benzyl optionally substituted with a group (O), S (O -) -, W with W and m as defined above; - R37, R38, R30, R40, R41, R42, R43 and Raa, which are identical or different, represent a hydrogen atom or a group selected from: i) alkyl; ii) alkoxy, alkylthio; iii) (di) (alkyl) amino; iv) hydroxy, mercapto; y) nitro, nitroso; vii) R ° -C (X) -X'-, R °-X'-C (X) -, R °-X'-C (X) -X "- with R ° representing a hydrogen atom, an alkyl or aryl group; X, X 'and X ", which may be identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; viii) 20 (0) 25 (0 -) -, W with W representing a hydrogen atom or a cationic counterion, ix) (O) C0--, W with W as previously defined, - or two contiguous groups R41 with R42 OR R42 with R43 OR R43 with R44 forming together a benzo fused group with the optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (0) 25 (O -) -, W; iv) hydroxy; mercapto; vi) (di) (alkyl) amino; vii) R ° -C (X) -X'-; viii) R ° -X'-C (X) -; ix) R ° -X'-C (X) -X "-; with W, R 0, X, X ', X "as defined previously, especially R 37 to R a represent a hydrogen atom, and R 41 to R 44, which are identical or different, represent a hydroxyl group or (0) (0) -, W, and when R43 with R44 together form a benzo group, it is preferably substituted by a group (0) (0 -) - with the proviso that at least one of the rings G, H, I or comprise at least one sulfonate group (O) (O -) -, Q + or carboxylate (O) C (O -) -, Q +; 3037237 40 By way of example of dyes of formula (XI), mention may be made of: Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid Green 50, a3f) the xanthene dyes of formula (XII): R 45 R 47 R51 R51 R51 R51 R49 R49 which: R 45, R 46, R 47 and R 48, which are identical or different, represent a hydrogen atom or a halogen atom; R 46, R 50, R 51 and R 52, which are identical or different, represent a hydrogen atom, 10 halogen, or a chosen group among i) alkyl, ii) alkoxy, alkylthio; iii) hydroxy, mercapto; iv) nitro, nitroso; v) (0) 2S (0 -) -, W with W representing a hydrogen atom or a cationic counterion; vi) (0) 00--, W with W as previously defined; especially R53 R54, R55 and R48 represent a hydrogen or halogen atom; G represents an oxygen atom, sulfur atom or a NR group, with R e as defined above; especially G represents an oxygen atom; L represents an alcoholate O-, W; a thioalkoxide S-, W or a group NRf, with Rf representing a hydrogen atom or an alkyl group, and W as defined above; W is particularly Na + or K +; L 'represents an oxygen atom, sulfur atom or an ammonium group: N + RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an optionally substituted alkyl or aryl group; L 'is particularly an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (0), S (0 -) -, W with m and W as defined above; Q and Q ', which may be identical or different, represent an oxygen or sulfur atom; particularly Q and Q 'represent an oxygen atom; - W is as defined previously; it being understood that the formula (XII) comprises at least one sulfonate group (O) 2S (O -) -, Q + or carboxylate (O) C (O -) -, Q + with Q + as defined previously; By way of example of dyes of formula (VII), mention may be made of ammonium salts derived from: Acid Yellow 73; Acid Red 51; Acid Red 87; Acid Red 92; Acid Red 95; Purple Acid 9; The indigo dyes of formula (XIII): (XIII) formula (XIII) in which: R53, R54, R55, R56, R57, R58, R59 and R60, which may be identical or different, represent an atom of hydrogen or a group selected from i) alkyl; ii) alkoxy, alkylthio; iii) hydroxy, mercapto; iv) nitro, nitroso; v) R ° -C (X) -X'-, R °-X'-C (X) -, R °-X'-C (X) -X "- with R ° representing a hydrogen atom, an alkyl or aryl group X, X 'and X ", which may be identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; vi) (0) 2S (0 -) -, W with W as previously defined; vii) (0) C0--, W with W as previously defined; - G represents an oxygen atom, sulfur or a group N Re with Re as defined above; especially G represents an oxygen atom; - R, and Rh, identical or different, represent a hydrogen atom or an alkyl group; It being understood that formula (XIII) comprises at least one sulfonate group (O) 2S (O -) -, Q + or carboxylate (O) C (O -) -, Q + with Q + as defined above; By way of example of dyes of formula (XIII) mention may be made of Acid Blue 74 and indigo carmine (or indigotin I, blue C1 # 1) is a blue dye (E132 number) extracted from natural indigo worker; 20 a3h) quinoline-derived dyes of formula (XIV): R 'R 61 6 HO (XIV) -R61 represents a hydrogen atom, a halogen atom or an alkyl group; - R62, R63, and R64, identical or different, represent a hydrogen atom or a group (0) 2S (0 -) -, W with W as defined above; or else R61 with R62, or R61 with R64, together form a benzo group optionally substituted with one or more (0) 2S (0 -) - groups, W with W representing a hydrogen atom or a cationic counterion; it being understood that formula (IX) comprises at least one sulfonate group (O) 2S (O -) -, Q + with Q + as defined above. By way of example of dyes of formula (IX), mention may be made of ammonium salts derived from: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.
[0043] More particularly, the dyes of formula (VII) to (XIV) useful for the invention are chosen from the following salts: (CI 45380) Acid Red 87 (XIV) (CI 10316) ammonium salts of acid 2, 4-dinitro-1-naphthol-7-sulfonic acid (X ') (CI 10383) Acid Orange 3 (XII) (CI 13015) Acid Yellow 9 / Food Yellow 2 (VII) (CI 14780) / Direct Red 45 / Food Red 13 (VII) (Cl 13711) Acid Black 52 (VII) (Cl 13065) Acid Yellow 36 (VII) (Cl 14700) ammonium salt of 1-hydroxy-2- (2 ', 4'-xylyl) -5- sufonatoazo) -naphthalene-4-sulfonic acid / Food Red 1 (VII) (CI 14720) Red Acid 14 / Food Red 3 / Blue Mordant 79 (VII) (CI 14805) 4-Ammonium salt hydroxy-3 - [(2-methoxy-5- (nitrophenyl) diaza] -6- (phenylamino) naphthalene-2-sulfonic acid / Acid Brown 4 (VII) (CI 15510) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 (VII) (IC 15985) Food Yellow 3 / Pigment Yellow 104 (VII) (Cl 16185) Acid Red 27 / Food Red 9 (VII) (Cl 16230) Acid Orange 10 / Food Orange 4 (VII) (Cl 162 50) Acid Red 44 (VII) (C.I. 17200) Acid Red 33 / Food Red 12 (VII) (Cl 15685) Acid Red 184 (VII) (0.1.19125) Acid Violet 3 (VII) (Cl 18055) Ammonium salt of 1-hydroxy-2-acid - (4'-Acetamido phenylazo) -8-acetamido-naphthalene-3,6-disulfonic acid / Acid Violet 7 / Food Red 11 (VII) (Cl 18130) Acid Red 135 (VII) (Cl 19130) Acid Yellow 27 (VIII ) (CI 19140) Acid Yellow 23 / Food Yellow 4 (VIII) (CI 20170) 4 '- (Sulfonato-2 ", 4" -dimethyl) -bis- (2,6-phenylazo) -1,3-dihydroxybenzene / Acid Orange 24 (VII) (CI 20470) ammonium salt of 1-amino-2- (4'-nitrophenylazo) -7-phenylazo-8-hydroxy-naphthalene-3,6-disulfonic acid / Acid Black 1 (VII) (Cl 23266) (4 - ((4-methylphenyl) sulfonyloxy) phenylazo) 2,2'-dimethyl-4 - ((2-hydroxy-5,8-disulfonato) naphthylazo) biphenyl / Acid Red 111 (VII ') (CI 27755) Food Black 2 (VII) (CI 25440) 1- (4'-sulfonatophenylazo) -4 - ((2 "-hydroxy-3" -acetylamino-6 ", 8" -disulfonato) naphthylazo ) -6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1 (VII) (CI 42090) Acid Bl 9 (XI) (C.I. 60730) Acid Violet 43 (IX) (C.I. 61570) Acid Green 25 (IX) (Cl 62045) ammonium salt of 1-amino-4-cyclohexylamino-9,10-anthraquinone 2-sulfonic acid / Acid Blue 62 (IX) (Cl 62105) Acid Blue 78 (IX) (CI 14710) 4-hydroxy-3 ((2-methoxyphenyl) azo) -1-naphthalenesulfonic acid / Acid Red 4 (VII) ammonium salt 2-piperidino-5-nitro benzene acid Sulfonic acid (X ') 2 (4'-N, N (2 "-hydroxyethyl) amino-2'-nitro) aniline ethane sulfonic acid (X') 4β-hydroxyethylamino-3-nitrobenzene sulfonic acid (X ') ( 0.1 42640) Acid Blue 49 (XII) (0.142080) Acid Blue 7 (XI) (0.1.580O5) 1,2-dihydroxy-3-sulfo-anthraquinone / Mordant Red 3 (IX) (0.1.62055) acid 1-amino-9,10-dihydro-9,10-dioxo-4- (phenylamino) -2-anthracenesulfonic acid / Acid Blue (IX) (0.1.1710) 4-hydroxy-3 - ((2-methoxyphenyl) acid -azo) -1-naphthalenesulfonic acid / Acid Red 4 (VII) Most of these dyes are described in particular in the Color Index published by The Society of Dyers and Colorists, PO Box 244, Perkin Hous 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England. The more particularly preferred anionic dyes designated in the Color Index under the code CI 58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulphonic acid), CI 60730 (monosodium salt of the acid 2- [(9,10-dihydro-4-hydroxy-9,10-dioxo-1-anthracenyl) -amino] -5-methyl-benzenesulfonic acid), CI 15510 (monosodium salt of 4 - [( 2-hydroxy-1-naphthalenyl) azo] benzenesulfonic acid), CI 15985 (disodium salt of 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid), CI 17200 ( disodium salt of 5-amino-4-hydroxy-3 (phenylazo) -2,7-naphthalene disulfonic acid), CI 20470 (disodium salt of 1-amino-2- (4'-nitrophenylazo) 7-phenylazo-8-hydroxy-3,6-naphthalene disulfonic acid), CI 42090 (disodium salt of N-ethyl-N444 [44ethyl [3-sulphophenyl) methyl] amino] phenyl] (2-sulphophenyl) methylene] -2,5-cyclohexadien-1-ylidene] -3-sulfobenzenemethanaminium hydroxide, internal salt), CI 61570 (Disodium salt of 2,2'-acid) [(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl) -diimino] -bis [5-methyl] -benzene sulfonic acid. It is also possible to use compounds corresponding to the mesomeric, tautomeric forms of structures (VII) to (XIV). More particularly, the dye (s) according to the invention are chosen from those of formula (VII), (IX) and (XIII), preferably of formula (XIII). According to another particular embodiment of the invention, the dye (s) are chosen from cationic or dye direct dyes commonly known as "basic" or "basic dyes" direct dyes for their affinity with acidic substances. The cationic dyes are preferably chosen from hydrazono, (poly) azo, polymethine dyes such as styryl and (poly) arylmethane dyes. More preferentially, the cationic dye (s) of the invention are chosen from the hydrazono dyes of formula (XVa) and (XV'a), the azo compounds (XVIa) and (XVI'a) and the following diazo compounds (XVIla): Het + - C (Ra) = NN (Rb) -Ar, Q-Het + -N (Ra) -N = C (Rb) -Ar, Q-Het + -N = N-Ar, Q- (XVa) (XV'a) (XVIa) Ar + -N = N-Ar ", Q- and Het + -N = N-Ar'-N = N-Ar, Q-3037237 44 (XVI'a) (XVIla) formulas (XVa), (XV ') a), (XVIa), (XVI'a) and (XVIla) with: - Het + representing a cationic heteroaryl radical, preferably with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally substituted preferentially by one or more groups (C1 -C8) alkyl such as methyl; -Ar + representing an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge preferentially ammonium especially tri (C1-C8) alkylammonium such as trimethylammonium; -Ar represents an aryl group, especially phenyl, optionally substituted, 1 Preferably by one or more electron donor groups such as i) C8) optionally substituted alkyl, ii) (C1-C8) optionally substituted alkoxy, iii) (di) (C1-C8) (alkyl) amino optionally substituted on the group or groups alkyl by a hydroxyl group, iv) optionally substituted aryl (C1-C8) alkylamino, v) N- (C1-C8) alkyl-N-aryl (C1C8) alkylamino or Ar represents a julolidine group; Ar 'is an optionally substituted divalent (hetero) arylene group such as phenylene, especially para-phenylene, or naphthalene, optionally substituted, preferably with one or more (C1-C8) alkyl, hydroxyl or (C1-C8) alkoxy groups; Ar - is an optionally substituted (hetero) aryl group such as optionally substituted phenyl or pyrazolyl, preferentially with one or more (C1-C8) alkyl, hydroxyl, (di) (C1-C8) (alkyl) amino groups, C1-C8) alkoxy or phenyl; - Ra and Rb, identical or different, representing a hydrogen atom or a (C1-C8) alkyl group optionally substituted, preferably with a hydroxyl group, or the substituent Ra with a substituent of Hee and / or Rb with a substituent of Ar and / or Ra with Rb together with the atoms which carry them a (hetero) cycloalkyl particularly Ra and Rb, representing a hydrogen atom or a group (Ci-C4) alkyl optionally substituted by a hydroxyl group; -Q- represents anionic counterion as defined above. According to a preferred variant of the invention, the cationic dyes are chosen from polymethine dyes of formulas (XVIlla) and (XVIll'a) VV * - [C (Rc) = C (Rd)], ', - Ar', Q- Ar- [C (Rd) = C (Rc)] ,,, - VV ' +, Q- (XVIlla) (VIll'a) 35 formulas (XVIlla) or (XVIll'a) with: 3037237 - VV + representing a heterocyclic or cationic heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more groups (C1 -C8) alkyl optionally substituted in particular with one or more hydroxyl groups; 5 - VV + representing a heterocyclic or heteroaryl as defined for VV +; Ar represents a (hetero) aryl group such as phenyl or naphthyl, optionally substituted preferentially by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (C1-C8) alkyl groups, preferably C1-C4 groups such as methyl; iii) one or more hydroxyl groups; iv) one or more (C1-C8) alkoxy groups such as methoxy; v) one or more hydroxy groups (C1-C8) alkyl such as hydroxyethyl, vi) one or more amino or (di) (C1-C8) alkylamino groups, preferably with the C1-4 alkyl part optionally substituted with one or several hydroxyl such as (di) hydroxyethylamino, vii) with one or more acylamino groups; viii) one or more heterocycloalkyl groups such as 5- or 6-membered piperazinyl, piperidinyl or heteroaryl such as pyrrolidinyl, pyridinyl and imidazolinyl; Ar 'is a (hetero) aryl radical as defined for Ar; - m 'represents an integer inclusive between 1 and 4, particularly m is 1 or 2; more preferably 1; Rc, Rd, which may be identical or different, represent a hydrogen atom or an optionally substituted (C1-C8) alkyl group, preferentially C1-C4, or else Rc contiguous with VV + or VV + and / or Rd contiguous with Ar or Ar 'and / or Rc and Rd contiguous form with the atoms forming with (hetero) cycloalkyl, especially Rc is contiguous with VV + or VV + and form a (hetero) cycloalkyl such as cyclohexyl; As defined above, preferably represents a halide or a mesylate. Mention may more particularly be made of azo and hydrazono endocyclic cationic charge dyes of formula (XVa), (XV'a), (XVIa) and (XVI'a) as defined above. More particularly those of formula (XVa), (XV'a) and (XVIa) from the dyes described in patent applications VVO 95/15144, VVO 95/01772 and EP-714954. Preferentially, the cationic dyes comprise an endocyclic cationic charge and are particularly of the following formula: ## STR2 ## R.sub.1 R.sub.1 R.sub.2 R.sub.1 R.sub.1 R.sub.1 R.sub.1 R.sub.1 (XVa-1) (X (XVI)) a-1) 3037237 46 formulas (XVa-1) and (XVIa-1) with: - R1 representing a group (C1-C4) alkyl such as methyl; R2 and R3, identical or different, represent a hydrogen atom; or a (C 1 -C 4) alkyl group such as methyl, and R 4 represents a hydrogen atom or an electron-donor group such as (C 1 -C 8) alkyl optionally substituted, (C 1 -C 8) alkoxy optionally substituted, (di) (C1C8) (alkyl) amino optionally substituted on the alkyl group (s) with a hydroxyl group, especially R4 is a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferentially CH, 10-Q-such as defined above, preferably represents a halide or a mesylate, especially the dyes of the inv. ention are selected from those of formula (XVIa-1) and (XVa-1) is selected from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives: NN, c1-13 NcH3 H3c N + _ + H3N NH2 Q-N-CH3 H3C Q-Basic Red 51 Basic Orange 31 Basic Yellow 87 With Cr as defined above, preferably represents a halide or mesylate. In the context of the present invention, the dye (s) are present in a total amount ranging from 0.001% to 20% by weight relative to the total weight of the dye composition, in particular ranging from 0.005% to 10% by weight relative to the total weight of the dye composition. Preferably from 0.01 to 5% by weight relative to the total weight of the dye composition. As regards pure natural dyes, in particular pure ODPs, the content in the composition (s) containing them is preferably between 0.001 and 5% by weight of each of the compositions containing them.
[0044] With regard to the extracts, the content in the composition (s) containing the extract (s) as (s) such (s) which (s) is (s) is preferably between 0.1 and 20% by weight of each of these compositions. b) the titanium salt (s): The titanium salt (s) of the invention may be one or more organic (s) or inorganic (s) salt (s) of titanium. For the purposes of the present invention, the term "organic titanium salt" is intended to mean the actual salts resulting from the action of at least one organic acid on Ti. By "organic acid" is meant an acid ie a compound capable of releasing a cation or H + proton, or H30 + in aqueous media, which comprises at least one hydrocarbon chain C-020, optionally unsaturated, linear or branched, a group (hetero ) cycloalkyl, or (hetero) aryl and at least one acidic chemical function being in particular selected from carboxy COOH, sulfuric SO3H, SO2H, and phosphoric PO31-12, PO4H2. In particular, the organic acid (s) is (are) to form the organic titanium salt (s) of the invention is (are) chosen from carboxylic acids (s) of formula (1) as defined above and preferably is or are an alpha hydroxy acid such as lactic, glycolic, tartaric or citric acids.
[0045] Preferably, the organic titanium salt resulting from the action of one or more organic acid (s) as defined above, preferably carboxylic acid (s) of formula (I). ) as defined above, is an optionally charged complex (in particular negatively) which is complexed with one or more carboxylate group (s) of carboxylic acid (s).
[0046] Preferably, the titanium organic salt (s) of the invention is (are) chosen from those of formula (I-A) below: ## STR5 ## Formula (I-A) in which: A is identical to that of formula (I): n, n 'and n ", which are identical or different, are 1,2,3 or 4 with n' + n" equal to 6; M1 and M2, which may be identical or different, represent a cationic counterion, chosen in particular from alkali metal cations such as Na, or K, alkaline earth metal such as Ca or organic such as ammonium, preferably ammonium or a hydrogen atom. ; TiY denoting Ti (01-1), r, or Ti (O) 12, or Ti (01-1) ,, 1 (O) ,, 2 with m1 + m2 = n ", preferably the radical A of the compound ( 1-A) as defined above represents a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted by one or more hydroxyl groups, and n represents an integer from 0 to 5 inclusive, such between 0 and 2, especially the carboxylic acid or acids used to form the organic titanium salt (s) of the invention are chosen from α-hydroxy acids, preferably the acid is chosen from citric acid and lactic acid; , tartaric acid, and glycolic acid, preferably from lactic and glycolic acid, the at least one organic titanium salt (s) of the invention is (are) chosen from among those of formula (IB): Formula (IB) wherein: - L 'and L ", identical or different, represent a divalent group (hetero) arylene, C6) a lkylene, (C2-C6) alkenylene, said alkylene and arylene groups being optionally substituted with one or more atoms or groups selected from halo, (C1-C4) alkyl, hydroxy, thiol, and (di) (C1-C4) (alkyl) ) amino, carboxy, and / or optionally interrupted by one or more heteroatoms such as oxygen; Preferably L 'and L "are identical and represent a methylene or ethylene group optionally substituted with a (C1-C4) alkyl group; X' and X", which may be identical or different, represent a heteroatom such as oxygen, sulfur or amino; Rc-N with Rc representing a hydrogen atom or a (CiC4) alkyl group, preferably X 'and X "are identical and represent an oxygen atom; Y and Y', which are identical or different, are such that defined for X 'and X ", preferably Y and Y' are the same and represent an oxygen atom; - Ra and Rb, identical or different, represent a hydrogen atom, or a (C 1 -C 6) alkyl, (C 2 -C 6) alkenyl, or (hetero) aryl; particularly Ra and Rb, identical represent a hydrogen atom or a (C1-C4) alkyl group, preferably hydrogen; M +, identical or different, represents a cationic counter ion such as alkali (Na, K), alkaline earth (Ca) or organic metal cation such as ammonium, preferably ammonium. Preferably, the organic titanium salt (s) of the dyeing process is the dihydroxybis (lactato) titanium IV salt such as those of the following formula: ## STR2 ## M + (IB) The staining process may use one or more organic acids b1) of formula (I) as defined above.
[0047] According to an advantageous variant, the dyeing method also uses b1) one or more carboxylic acid (s) of formula (I) as defined above. More preferentially, the carboxylic acid or acids b1) are different from the carboxylic acids complexed with the Ti salts. For example, if the carboxylic acid complexed with the titanium salt b) is lactic acid or its carboxylate salt (lactate), the second acid b1) other than lactic acid or lactate, and may be for example the acid glycolic. For the purposes of the present invention, the term "inorganic titanium salt" means the salts themselves, derived from the action of an inorganic acid on Ti. By "inorganic acid" is meant an acid which does not have carbon atoms other than carbonic acid. Inorganic salts of titanium are preferably selected from titanium halides, titanium sulfates and titanium phosphates. The titanium salts are preferably inorganic salts of Ti (II), Ti (III) or Ti (IV), more particularly Ti (III) or Ti (IV). Preferably, the titanium salt (s) is (are) organic titanium salts, and more preferably organic Ti (IV) salts. According to an advantageous embodiment of the invention, the organic salt of Ti consists of a Ti (IV) atom and from 2 to 3 molar equivalents of at least one carboxylic acid of formula (I). The salt (s) of titanium (b) is (are) present in the cosmetic composition (s) used in the process according to the invention in a content ranging from 0.001 to % to 20% by weight relative to the total weight of the composition or compositions containing them. In particular, the organic titanium salt (s) and the inorganic titanium salts according to the invention are soluble in water in a proportion of at least 0.0001 g / l, more preferably at least 1 g / l.
[0048] According to a particular embodiment, the pKai of the carboxylic acid (s) b1) is less than 3. c) the alkaline agent (s) The dyeing method of the invention uses a revelation composition Comprising one or more alkaline agent (s) c) which has at most one amine function, it being understood that when the composition Cii) comprises several alkaline agents, then each of the alkaline agents comprises at most one amine function. It is a compound (s) for increasing the pH of the composition (s) containing it (s).
[0049] The alkaline agent is a Bronsted, Lowry or Lewis base. It can be mineral or organic and when it is organic it does not have more than one NH 2 amine function. In particular, said alkaline agent is chosen from i) (bi) carbonates, ii) ammonia, iii) alkanolamines comprising only one amine function such as monoethanolamine; monopropanolamine iv) oxyalkylenated alkanolamines comprising only one amine function and in particular oxyethylenated aclanolamines such as oxyethylenated and / or oxypropylenated ethyleneamines, v) inorganic or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) amino acids comprising only one amine function, basic preferences such as histidine.
[0050] The inorganic or organic hydroxides are preferably selected from a) the hydroxides of an alkali metal, b) the hydroxides of an alkaline earth metal, such as hydroxides of sodium or potassium, c) the hydroxides of a transition metal, such as hydroxides of Group III, IV, V and VI metals, d) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides.
[0051] By (bi) carbonates i) is understood to mean: a) alkali metal carbonates (Met +2, CO32-), alkaline earth metal (Met2 +, CO32-) ammonium ((R "4N +) 2 , CO32-) or phosphonium ((R "4P +) 2, CO32- with Met 'representing an alkaline earth metal and Met representing an alkali metal, and R", which may be identical or different, represent a hydrogen atom, a grouping (C1-C6) optionally substituted alkyl such as hydroxyethyl), and b) bicarbonates, also called hydrogenocarbonates, of the following formulas: HCO3- with R 'representing a hydrogen atom, an alkali metal, an ammonium group R "4N + - or phosphonium R "4P + - where R", identical or different, represent a hydrogen atom, an optionally substituted (C1-C6) alkyl group such as hydroxyethyl and when R 'represents a hydrogen atom the hydrogencarbonate is then called dihydrogen carbonate (CO2, H 2 O); and Met '2+ (1-1CO3-) 2 with Met' representing an alkaline earth metal. More particularly, the alkaline agent is selected from alkali or alkaline earth metal (bi) carbonates and amino acids comprising at most one amine function such as hystidine; preferentially alkali metal (bi) carbonates and amino acids comprising at most one amine function.
[0052] According to one particular embodiment of the invention, the alkaline agent (s) is (are) chosen from a mixture of 2 alkaline agents chosen from families i) to vii) as defined. previously. Particularly the alkaline agent (s) c) is (are) selected from the following mixtures: 1) carbonates + bicarbonates; 2) amino acids + (bi) carbonates; 3) alkanolamines + (bi) carbonates; 4) oxyalkylenated alkanolamines + (bi) carbonates; 5) inorganic or organic hydroxides + (bi) carbonates; 6) alkali metal silicates + (bi) carbonates; amino acids and alkanolamines oxyalkylenated or not comprising at most one amine function; more particularly the weight ratio between 1) carbonates and bicarbonates or between the first alkaline agents (amino acids, alkanolamines, oxyalkylenated alkanolamines, mineral or organic hydroxides or alkali metal silicates) according to 2) to 6) and the (bi) carbonates is greater than or equal to 2, preferably is greater than or equal to 4, more preferably is greater than or equal to 6, still more preferably greater than or equal to 8 better than or equal to 10 and in particular is included between 2 and 16 inclusive. preferably, it is between 10 and 14 inclusive. According to a particularly advantageous embodiment, the alkaline agent (s) c) is (are) chosen from among i) alkali metal or alkaline-earth metal carbonates, ii) alkali metal or alkaline earth bicarbonates and iii) amino acids having at most one amine function such as histidine, alone or in mixtures. They are preferably found together during the coloring process. The composition Cii) preferably comprises a mixture of at least one alkali metal or alkaline earth metal carbonate i) and at least one alkali metal or alkaline earth metal bicarbonate ii According to a preferred embodiment of the invention, the alkaline agent (s) c) is (are) chosen from a mixture of carbonates and bicarbonates as defined above with a carbonate weight ratio. bicarbonates greater than 2, preferably greater than or equal to 4, more preferably greater than or equal to 6, even more preferably greater than or equal to 8 better than or equal to 10 and in particular is inclusive between 2 and 16, preferentially 35 is included between 10 and 14. Among the carbonates and bicarbonates suitable for the present invention, there may be mentioned carbonates and bicarbonates (also called hydrates). rocarbonates) of Na, K, Mg, Ca and mixtures thereof, and in particular Na carbonate and bicarbonate. These bicarbonates may come from natural water, for example spring water from the Vichy basin, from La Roche Posay, Badoit water (see patent for example FR 2 814 943). Particularly mention may be made of sodium carbonate [497-19-8] = Na2003, sodium hydrogencarbonate or sodium bicarbonate [144-55-8] = NaHCO3, and sodium dihydrogen carbonate = Na (HCO3) 2.
[0053] According to a particularly advantageous embodiment of the invention, the composition Cii) comprises at least one alkaline agent chosen from alkali metal carbonate alone such as sodium carbonate alone, or a mixture of alkali metal carbonate and alkali metal bi carbonate. such that the mixture of sodium carbonate and sodium bicarbonate with preferably a weight ratio of carbonates / bicarbonates greater than 2, preferably greater than or equal to 4, more preferably greater than or equal to 6, even more preferably greater than or equal to 8 is preferably greater than or equal to 10 and in particular is between 2 and 16 inclusively, preferably between 10 and 14 inclusive. Preferably, the pKa or pKa of each alkaline agent is included between 6 and 11.5, plus particularly between 9.5 and 11, at room temperature, said alkaline agent may have several pKa when it comprises Several basic functions can be mentioned for example sodium bicarbonate which has two pKa (pKa1 = 6.33 and pKa2 = 10.33). Thus preferably each alkaline agent c) alone or in mixture has one or more pKa which are inclusive between 6 and 11.5, or better between 9.5 and 11 ie each pKa should preferably be between 6 and 11.5, or better between 9.5 and 11. The alkaline agent (s) (s) c) as defined above preferably represent a total amount greater than 1% by total weight relative to the total weight of the composition Cii). More particularly, the total amount of alkaline agent (s) according to the invention is between 1% and 15% inclusive, preferably between 2% and 10% and more preferably between 5.1 and 9% by weight. d) the chemical oxidizing agent (s) According to one particular embodiment of the invention, the dyeing method also uses one or more oxidizing agent (s). (s) chemical (s). By chemical oxidizing agent is meant an oxidizing agent different from the oxygen of the air. More particularly, the dyeing process employs one or more chemical oxidizing agent (s) selected from: i) hydrogen peroxide; ii) urea peroxide; iii) polymer complexes which can release hydrogen peroxide, such as polyvinylpyrrolidone / H 2 O 2, in particular being in the form of powders and the other polymer complexes described in US Pat. No. 5,008,093; US 3,376,110; US 3037237 53 5,183,901; iv) oxidases in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase); y) metal peroxides generating hydrogen peroxide in water such as calcium peroxide, magnesium peroxide; vi) perborates; and / or vii) percarborates.
[0054] According to a preferred embodiment of the invention, the composition Cii) contains one or more chemical oxidizing agent (s) chosen from: i) urea peroxide, ii) polymeric complexes capable of releasing hydrogen peroxide selected from polyvinylpyrrolidone / H 2 O 2; iii) oxidases; iv) perborates and y) percarborates. According to another particular embodiment of the invention, the composition Ci) contains one or more chemical oxidizing agent (s) chosen from: i) urea peroxide, ii) complexes polymers capable of releasing hydrogen peroxide selected from polyvinylpyrrolidone / H 2 O 2; iii) oxidases; iv) perborates and y) percarborates.
[0055] In particular, the dyeing process uses hydrogen peroxide. Furthermore, the composition or compositions comprising hydrogen peroxide or hydrogen peroxide generating system may also contain various adjuvants conventionally used in compositions for dyeing keratinous fibers as defined below.
[0056] According to one particular embodiment of the invention, the chemical oxidizing agent (s) used represent (s) from 0.001% to 12% by weight of chemical oxidizing agents (of hydrogen peroxide) relative to the total weight of the composition containing them. and preferably from 0.2% to 5%, more preferably from 0.1 to 3% by weight of the composition containing them.
[0057] Water: According to one embodiment of the invention, water is preferably included in the process of the invention. It may come from the wetting of the keratinous fibers and / or the composition or compositions comprising the compounds a) to d) as defined above or from one or more other compositions. Preferably, the water comes from at least one composition comprising at least one compound chosen from a) to d) as defined above.
[0058] Compositions: The compositions according to the invention generally comprise water or a mixture of water and one or more organic solvents or a mixture of organic solvents.
[0059] By organic solvent is meant an organic substance capable of dissolving or dispersing another substance without chemically modifying it. Organic solvents: According to a particular embodiment, at least one of the cosmetic compositions of the invention further comprises an organic solvent. According to one variant, the compositions Ci) and Cii) comprise at least one organic solvent. According to an advantageous variant only the composition Ci) comprises at least one organic solvent.
[0060] As an organic solvent, there may be mentioned, for example, C1-C4 lower alkanols, 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, hexylene glycol, and aromatic alcohols such as benzyl alcohol or phenoxyethanol. Preferably, the dye composition comprising the dye (s), in particular the ODPs, of the invention comprises at least one organic solvent as defined above and particularly an organic solvent chosen from aromatic alcohols such as benzyl alcohol. The organic solvents are present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and still more preferably between 5 and 30% by weight approximately. Adjuvants: The composition (s) of the dyeing method according to the invention may also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, nonionic surfactants, amphoteric, zwitterionic or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetrating 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, preservatives, opacifying agents. The dyeing process of the invention may also carry out in addition to compounds a), b), c) and optionally d) at least one other particular carboxylic acid 3037237 of formula (I) as defined above. More particularly, the carboxylic acid or acids of formula (I) are such that A represents a monovalent (CiC6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted by one or more hydroxyl groups, and n represents an integer inclusive between 0 and 5, such as between 0 and 2. More particularly, the carboxylic acid or acids of the invention are chosen from the acids of formula (I) having a solubility in water greater than or equal to 1% by weight relative to ° C and at atmospheric pressure. Preferably the acids of formula (I) comprise at least one hydroxy group in their structure. Even more preferentially, the acid is chosen from α-hydroxy acids. The preferred acids of the invention are selected from glycolic acid, lactic acid, tartaric acid and citric acid. The salts of the acids of formula (I) can be organic or inorganic base salts such as sodium hydroxide, ammonia, or potassium hydroxide or organic amine salts such as alkanolamines. The acids of formula (I) or their salts are present in the composition or compositions containing them in a content ranging from 0.1 to 20% by weight. Said adjuvants are preferably selected from surfactants such as anionic, nonionic surfactants or mixtures thereof and inorganic or organic thickeners. The adjuvants above are generally present in an amount for each of them between 0.01 and 40% by weight relative to the weight of the composition, preferably between 0.1 and 20% by weight relative to the weight of the composition. Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition or to the composition (s) useful in the dyeing process according to the invention do not not, or not substantially, impaired by the addition or additions envisaged. The cosmetic composition (s) of the invention may be in various galenical forms, such as a powder, a lotion, a mousse, a cream, a gel or in any other form suitable for producing a dyeing of keratinous fibers. They can also be packaged in a pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam. PH of the compositions: According to a preferred embodiment of the invention, the pH of the cosmetic composition Ci) comprising at least one of the ingredients a), b), or b1) is acidic, ie less than 7.0, preferably less than 5.0, especially at a pH inclusive between 0 and 4, more preferably between 0.5 and 3.5, preferably between 1 and 3.5. According to one embodiment, the pH of the cosmetic composition Cii) containing one or more alkaline agents as defined above is alkaline, that is greater than 7.5, preferably between 8 and 12 inclusive, and more particularly between 8.5 and 11, preferentially inclusive between 9.5 and 10.5. The pH of these compositions may be adjusted to the desired value by means of alkaline agents as defined previously in c) or from acidifying agents normally used for dyeing keratin fibers or else using buffer systems classics. Among the acidifying agents of the compositions used in the invention, 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, sulfonic acids. By "carboxylic acid" is meant a compound comprising at least one carboxylic acid group -C (O) -OH, preferably of formula (I) as defined above, preferably comprising between 1 and 4 carboxylic acid groups such as 1 or 2; or chosen from: i) (C 1 -C 10) alkyl- [C (O) -OH] and ii) het- [C (O) -OH], with n an integer inclusive of between 1 and 4, preferably between 1 and 2, hetero-cyclic group such as pyrrolidone, the alkyl group or hét may be optionally substituted by one or more groups, especially selected from OH, and (di) (C1C6) (alkyl) amino.
[0061] Multi-step dyeing process According to a particular embodiment, the process for dyeing keratinous fibers in several steps consists in applying to said fibers a first dyeing cosmetic composition Ci) comprising: a) one or more dyes as defined previously, preferably ODP (s) as defined previously; b) one or more titanium salt (s); optionally b1) one or more carboxylic acid (s) of formula (I) as defined above; then a second cosmetic revealing composition Cii) comprising: c) one or more alkaline agent (s) each comprising at most one amine function as defined previously; preferably the alkaline agent (s) c) is (are) chosen from 1) a mixture of carbonates and bicarbonates as defined above with in particular a ratio by weight of carbonates / bicarbonates greater than 2, preferably is greater than or equal to 4, more preferably greater than or equal to 6, even more preferably greater than or equal to 8 better than or equal to 10 and in particular is inclusive between 2 and 16, preferably is inclusive of between 10 and 14; and d) optionally one or more chemical oxidizing agent (s), in particular chosen from hydrogen peroxide or one or more hydrogen peroxide generator system (s) such as ) as defined previously; preferably the composition Ci) is at acidic pH, ie less than 7, preferably less than 5, particularly at a pH between 0 and 4, more preferably between 0.5 and 3.5, better still between 1 and 3. According to a particularly advantageous embodiment of the invention between the step of applying the composition Ci) and Cii) is carried out, in the method according to the invention, at least one step of intermediate rinsing said fibers preferably to the water.
[0062] According to a particular embodiment of the invention, the coloring process is characterized in that the titanium salt (s) is (are) chosen from organic or inorganic titanium salts, preferably from organic titanium salts, and in which (s) titanium is in particular of oxidation state 2, 3 or 4 preferably of oxidation degree 4.
[0063] According to a particular embodiment of the invention, the dyeing process is carried out in at least two steps which comprises a first step in which the keratinous fibers are treated with a cosmetic composition Ci) comprising a) one or more dyes (s) ), preferably one or more ODP (s) such as defined previously, b) one or more salt (s) of titanium and optionally b1) one or more carboxylic acid (s) such (s) defined previously followed by a second step in which the keratinous fibers are treated with a cosmetic composition Cii) comprising c) one or more alkaline agent (s) as defined previously (s) whose pH is greater than 7, and preferably between 8 and 12, especially between 9 and 10.5, and which optionally comprises d) one or more chemical oxidizing agent (s) such as defined (s) previously. Preferably the composition Ci) comprising a) + b) and optionally b1) is at acidic pH, ie less than 7, preferably less than 5, particularly at a pH inclusive of between 1 and 3. Preferentially the cosmetic composition Cii) applied on the keratinous fibers 35 during the second step further comprises d) one or more chemical oxidizing agent (s), in particular chosen from hydrogen peroxide or one or more generator systems (s) ( s) hydrogen peroxide, preferably hydrogen peroxide. According to a particular embodiment, the dyeing process according to the invention is carried out in several stages by application to the keratinous fibers in a first step of a cosmetic composition Ci) comprising: a) one or more ODP (s), as defined above, in particular chosen from 5 - haematein, brasiline, gallic acid, tannic acid, when the dyeing process does not use an oxidizing agent chemical d); or else - hematoxylin brasiline, when the dyeing process uses a chemical oxidizing agent d); B) one or more organic titanium salt (s) as defined previously; advantageously, ingredient b) is chosen from the salts or complexes of Ti (IV); b1) optionally one or more carboxylic acid (s) of formula (I) as defined above; then in a second step of a cosmetic composition Cii) comprising c) one or more alkaline agent (s) such as defined previously; preferably, the alkaline agent (s) is (are) chosen from 1) a mixture of carbonates and bicarbonates as defined above with in particular a weight ratio of carbonates / bicarbonates greater than 2, preferably greater than or equal to 4, more preferably greater than or equal to 6, still more preferably greater than or equal to 8 more preferably greater than or equal to 10, and in particular is inclusive between 2 and 16, preferably between 10 and 14 inclusively; and d) optionally one or more chemical oxidizing agent (s) chosen from hydrogen peroxide or one or more hydrogen peroxide generator system (s) as defined previously; it being understood that: - preferably the composition Ci) is at acidic pH, i.e. less than 7, preferably less than 5, particularly at a pH inclusive of between 1 and 3; and the composition Cii) is at alkaline pH, preferably between 8 and 12, and more particularly between 9 and 10.5. The pause time after application of composition Ci) comprising the dye (s), in particular ODP (s) as defined above, is generally set between 3 and 120 minutes and preferably between 10 and 60 minutes and more preferably between 15 and 45 minutes.
[0064] Preferably the two compositions Ci) and Cii) used in the dyeing process of the invention are aqueous. For the coloring process, the pause time after application of Ci) for the first step is generally set between 3 and 120 minutes and preferably between 10 and 60 minutes and more preferably between 15 and 45 minutes. The application time of the composition Cii) comprising ingredient c) during the second step is generally set between 3 and 120 minutes and preferably between 3 and 60 minutes and more preferably between 5 and 30 minutes. According to another embodiment, the process for dyeing keratinous fibers takes place in two or three steps. According to this embodiment, the method for dyeing keratinous fibers is carried out by application to the keratinous fibers in a first step of a cosmetic composition Ci) comprising: a) one or more dyes, in particular one or more ODP (s) , in particular chosen from: - haematein, brazilein, gallic acid, tannic acid, when the dyeing process does not use chemical oxidizing agent d); or else - hematoxylin brasiline, when the dyeing process uses a chemical oxidizing agent d); b) one or more titanium salt (s) as defined above and b1) optionally one or more carboxylic acid (s) of formula (1) as defined previously with A representing a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted by one or more hydroxyl groups, and n representing an integer inclusive of between 0 and 5, such as between 0 and 2, more particularly the carboxylic acid or acids of the invention are chosen from citric acid, lactic acid, glycolic acid and tartaric acid; then in a second step the application on said fibers of a cosmetic composition comprising: d) optionally one or more chemical oxidizing agent (s) chosen from hydrogen peroxide or one or several system (s) generator (s) of hydrogen peroxide; then in a third step the application on said fibers of a cosmetic composition Cii) comprising: c) one or more alkaline agent (s) as defined above; preferably the alkaline agent (s) c) is (are) chosen from 1) a mixture of carbonates and bicarbonates with in particular a weight ratio of carbonates / bicarbonates greater than 2, preferably greater than 2; or equal to 4, more preferably is greater than or equal to 6, even more preferably is greater than or equal to 8 better than or equal to 10 and in particular is between 2 35 and 16 inclusively, preferably between 10 and 14 being inclusive; understood that: - preferentially the composition Ci) is at acidic pH, ie less than 7, preferably less than 5, particularly at a pH inclusive of between 1 and 3; and - the composition Cii) comprising the alkaline agent (s) is at alkaline pH, preferably between 8 and 12, and more particularly between 8.5 and 11, better still between 9.5 and 10.5. The invention is carried out in at least two stages, in the first step the ingredients a), b) and optionally b1) are applied together on the keratin fibers, in particular the hair, then in the second stage the ingredients c) and optionally d) are applied together on said fibers. Whatever the mode of application, the application temperature is generally between ambient temperature (15 to 25 ° C.) and 220 ° C. and more particularly between 15 and 45 ° C. Thus, it is advantageous, after applying the composition Ci) and / or Cii) according to the invention, to subject the hair to heat treatment by heating at a temperature of between 30 and 60 ° C. In practice, this operation can be conducted by means of a hairdressing helmet, an infra-red heat helmet (such as Climazon), a hair dryer, an infrared ray dispenser and other conventional heaters. Both heating and smoothing of the hair can be used as a heating iron at a temperature of between 60 and 220 ° C and preferably between 120 and 200 ° C. Whatever the mode of application, it is possible to perform a mechanical rinsing or wiping and / or a drying of the keratinous fibers between each step, in particular before carrying out the last step comprising the application of the composition Cii) containing the ingredient. c). The mechanical wiping and intermediate drying steps are also referred to as "non-rinsed mastered" to differentiate from "conventional high-water rinsing" and "non-rinsing". By "mechanical wiping" of the fibers is meant the rubbing of an absorbent object on the fibers and the physical removal by the absorbent object of the surplus ingredient (s) that has not penetrated the fibers. The absorbent object may be a piece of cloth such as a particularly sponge towel, a cloth, absorbent paper such as paper towels.
[0065] According to a particularly advantageous method of the invention, the mechanical wiping is carried out without total drying of the fiber, leaving the fiber wet. By "drying" is meant the action of evaporating organic solvents and / or water contained in one or more compositions used in the process of the invention, comprising or not one or more ingredients a) to e) as defined previously. The drying can be done by thermal source (convection, conduction or radiation) by sending for example a hot gas stream such as the air necessary for the evaporation of the solvent or solvents. As a thermal source there may be mentioned a hair dryer, hair helmets, a hair straightener, an infrared dispenser and other conventional heating devices.
[0066] A particular embodiment of the invention relates to a coloring process which is carried out at ambient temperature (25 ° C.). In all the particular modes and variants of the processes described above, the compositions mentioned are ready-to-use compositions which may result from the extemporaneous mixing of two or more compositions, and in particular of compositions present in dyeing kits. Dyeing device or "kit" Another object of the invention is a multi-compartment device or "kit" of dyeing. Advantageously, this kit comprises from 2 to 5 compartments containing from 2 to 5 compositions in which are distributed the ingredients a) to d) as defined previously can be aqueous or powder, with particularly at least one of said compositions being aqueous.
[0067] According to a first variant, the kit comprises 5 compartments, the first 4 compartments respectively comprising the ingredients, optionally in powders a), b), and optionally b1) and c) as defined above and in the 5th compartment containing an oxidizing composition aqueous such as water comprising d) as defined above.
[0068] In this embodiment, at least one of the four compositions is aqueous and the dye (s), particularly the ODP (s) may be in powder form. In another variant of the kit, the latter comprises two compartments, in which the first composition contained in the first compartment comprises a), b) and optionally b1) the second compartment comprises c) and optionally d) in the form of powder or aqueous medium, preferably the second composition is aqueous. In another variant of the kit, the latter comprises three compartments, in which the first composition contained in the first compartment comprises a) and b) and optionally b1) and the second compartment comprises d) in the form of a powder or in an aqueous medium preferably the second composition is aqueous and the third compartment comprises c). According to one variant, the device according to the invention further comprises an additional composition comprising one or more treatment agents. The compositions of the device according to the invention are packaged in separate compartments, possibly accompanied by appropriate, identical or different application means, such as brushes, brushes or sponges. The device mentioned above can also be equipped with means for delivering the desired mixture onto the hair, for example such as the devices described in patent FR 2586913.
[0069] The invention also relates to the use of said dye cosmetic composition for dyeing keratinous fibers. The invention also relates to a cosmetic composition for the dyeing of keratinous fibers containing compounds a), b), optionally 131), c), and optionally d) as defined above. For the purposes of the present invention, the term "rise" of the color of the keratinous fibers is understood to mean the variation in color between strands of unstained white hair and strands of colored hair. The following examples serve to illustrate the invention without being limiting in nature.
[0070] EXAMPLES: Example 1: a) Preparation of the compositions and application to keratinous fibers The following compositions were prepared from the ingredients in the proportions indicated in grams per 100 g of composition according to the following tables: Coloring Composition 1: Ingredients quantity Logwood wood 76% hematoxylin a) 4 Dihydroxybis (ammonium lactate) titanium (IV) 50% by weight b) 10.3 Glycolic acid b1) 15 Ethanol 15 Benzyl alcohol 5 Water qs 100 pH agent Qsp pH Relative compositions A to D: Ingredients ABCD comparative invention 1) Comparative 2) comparative 3) arginine - 5.25 7 7 pKa1 = 2.0-pKa2 = 9, pKa3 = 12.1 sodium bicarbonate, pKa1 = 6.33-pKa2 = 10.33 Sodium carbonate, pKai = 10.33 5.25 - - - pH agent (soda pKa = 14) - - - Qsp pH = 10 , 3 Hydrogen peroxide (at 50%) 1.7 1.7 1.7 1.7 Water qs 100 qs 100 qs 100 qs 100 pH pH 10.3 pH 10.3 pH 9.4 pH 10.3 The coloring composition 1 was applied on natural Chinese hair with 100% white hair, left for 45 minutes at 40 ° C and then rinsed with tap water until color disappeared in the rinse water.
[0071] Then each of the developer compositions a aD was applied in the same amount and allowed to stand for 15 minutes at 40 ° C.
[0072] At the end of these exposure times, the locks are washed with Elsève multi-vitamin shampoo, rinsed and then dried with a helmet. b) Visual and colorimetric evaluations It has been found that the locks treated by the process of the invention are very intensely colored which has been corroborated with the colorimetric measurements below. In addition, it appeared that the coloration was visually homogeneous and tenacious with respect to successive shampoos.
[0073] The color of the locks was then evaluated in the CIE L * a * b * system using a Minolta Spectrophotometer CM3600D colorimeter. In this system L * a * b *, the three parameters denote respectively the intensity of the color (L *), a * indicates the green / red color axis and b * the blue / yellow color axis. Rise in color: The color change between strands of Chinese hair at 90% white permed before and after treatment or staining is defined by (3.E *) according to the following equation: 4E * = V (L * In this equation, L *, a * and b * represent the values measured on hair strands after staining and Lo. *, ao * and bo * represent the values measured on strands of unstained virgin hair. The higher the value of A.E *, the better the color rise. The results L, a, b of rise in color are listed in the table below: Process (Invention vs. Comparative) * A * Composition 1 + Composition A (Invention) 20.66 62.83 Composition 1 + Composition B (Comparative 1) 24.49 58.47 Composition 1 + Composition C (Comparative 2) 23.21 59.61 Composition 1 + Composition D (Comparative 3) 26.3 56.01 25 It appears that the process according to the invention which used the revealing composition A resulted in a significantly more intense staining, with a significantly greater increase than when the staining method employed a comparative developer composition containing an alkaline agent comprising 2 amine functions such that arginine (comparative compositions B to D). Example 2: 3037237 a) Preparation of the compositions and application on keratin fibers The following compositions were prepared from the ingredients in the proportions indicated in grams per 100 g of composition according to the following tables: Coloring composition 1: was prepared according to the same quantities as the previous example. -F revealing compositions according to the invention: Ingredients Sodium bicarbonate, pKa1 = 6.33 pKa2 = 10.33 0.42 - - Sodium carbonate, pKai = 10.33 5.25 5.25 12 Oxygenated water (at 50%) 2, 2.4 2.4 Water qs 100 qs 100 qs 100 pH pH 10.3 pH 10.8 pH 10.8 The coloring composition 1 was applied as defined in Example 1. Then each of the EaG then applied, and left for 15 minutes at 40 ° C. At the end of these exposure times, the locks were washed with Elsève multi-vitamin shampoo, rinsed and then dried with a helmet. Highly efficient colorations (intensity, homogeneity of color) were visually observed, regardless of the applied developer composition E to G. After the keratin fibers were treated with the compositions 1 and the developer compositions E to G, strands obtained were of a very powerful black, and intense. This is confirmed by spectrocolorimetric measurements with low L * values and high 4E rise values: Process according to the invention * a * * A * Composition 1 + Composition E 20.71 -0.02 -0.5 62, Composition 1 + Composition F 21 0.03 -0.13 62.28 Composition 1 + Composition G 21.43 -0.13 -0.31 61.96 20

权利要求:
Claims (22)
[0001]
REVENDICATIONS1. Process for the dyeing of keratinous fibers, in particular human keratinous fibers such as the hair, in which said fibers are treated, in several steps, by a dyescent cosmetic composition Ci) containing: a) one or more dyes, in selected from the direct and natural dyes, preferably selected from ortho-diphenols (ODPs); b) one or more salt (s) of titanium (Ti); in particular the Ti atom of the salt is of oxidation state 2, 3 or 4 denoted Ti (II), Ti (III) or Ti (IV), preferably Ti (IV); and b1) optionally one or more carboxylic acid (s) of formula (I) below; OH A (I) 0 Formula (I) or a salt thereof in which: -A represents a monovalent group when n is 0 or polyvalent when n is greater than or equal to 1, hydrocarbon comprising 1 to 50 carbon atoms, saturated or unsaturated, cyclic or non-cyclic, aromatic or nonaromatic, optionally interrupted by one or more heteroatoms and / or optionally substituted in particular with one or more hydroxyl groups; preferably A represents a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted with one or more hydroxyl groups; n represents an integer inclusive between 0 and 10, preferably n is between 0 and 5, such as between 0 and 2; then - by a cosmetic revealing composition Cii) containing: c) one or more alkaline agent (s) comprising at most one amine function; and d) optionally one or more chemical oxidizing agent (s) such as hydrogen peroxide or one or more hydrogen peroxide generator system (s); it being understood that when the composition Cii) contains several alkaline agents, then each of the alkaline agents comprises at most one amine function; said method preferably comprising between the application of Ci) and Cii) an intermediate rinsing step.
[0002]
2. A dyeing method according to claim 1, wherein the composition Ci) is at acidic pH, ie less than 7.0, preferably less than 5.0, particularly at a pH of between 0 and 4 inclusive, more particularly between 0.5 and 3.5, preferably between 1 and 3.5; and / or the pH of the composition Cii) containing one or more alkaline agents is alkaline, ie greater than 7, preferably between 8 and 12 inclusive, and more particularly between 8.5 and 11, preferably inclusive of between 9.5 and 10.5. 5
[0003]
3. Method according to any one of the preceding claims wherein the dye (s) a) of the dye composition Ci) is (are) chosen from dyes of natural origin; selected from among spinulosin, orceins, polyphenols or ODPs and all extracts rich in ODPs, curcumin, indole derivatives such as isatin or indole-2,3-dione, indigoids of which indigo, phthalocyanines and porphyrins, in particular complexed with a metal, glycosylated or non-glycosylated iridoids, chromenic dyes, anthraquinone and benzoquinone dyes such as lawsone or henna, juglone, spinulosin, chromenic or chromanic dyes such as neoflavanols and neoflavanones, flavanols, indigoids such as indigo; and anthocyanidins. 15
[0004]
4. Coloring method according to any one of the preceding claims, wherein the dye (s) a) of the dye composition Ci) is (are) chosen from ODPs of the following formula (II) or one of its oligomers, tautomers, optical isomers, geometric isomers, as well as its salts or solvates such as the hydrates: OH formula (II) in which: R1 to R4, identical or different, represent: i) an atom hydrogen, ii) halogen, or a group selected from iii) hydroxy, iv) carboxy, v) (C1-C20) alkyl carboxylate or (C1-C20) alkoxycarbonyl, vi) optionally substituted amino, vii) (C1-C20) optionally substituted linear or branched alkyl, viii) (C2-C20) optionally substituted linear or branched alkenyl, ix) optionally substituted cycloalkyl, x) (C1-C20) alkoxy, x1) (C1-C20) alkoxy ( C1-C20) alkyl, xii) (C1-C20) alkoxyaryl, xiii) aryl optionally substituted, xiv) aryl, xv) aryl substituted ue, xvi) heterocyclic, saturated or unsaturated, optionally bearing a cationic or anionic charge, optionally substituted and / or optionally fused with an aromatic ring, preferably benzene, said aromatic ring being optionally substituted especially by one or more hydroxyl groups; or glycosyloxy, xvii) a radical containing one or more silicon atoms; or two of the substituents carried by two adjacent carbon atoms R1 - R2, R2- R3 or R3-R4 together with the carbon atoms carrying them a saturated or unsaturated ring, aromatic or otherwise, optionally containing one or more heteroatoms and optionally condensed with one or more saturated or unsaturated rings optionally containing one or more heteroatoms; particularly, R 1 to R 4 together form from one to four rings; more particularly, R2 and R3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring carrying the two hydroxy; especially the ODP (s) a) is (are) chosen from: - flavanols such as catechin and epichatechin gallate, 10 - flavonols such as quercetin, - anthocyanidins such as cyanidine, delphinidin , petunidine, anthocyanins or anthocyanins such as myrtilline, orthohydroxybenzoates, for example gallic acid salts, flavones such as luteolin, hydroxystilbenes, for example 3,3'-tetrahydroxy, 5'-stilbene, optionally oxylated (for example glucosylated), 3,4-dihydroxyphenylalanine and its derivatives, 2,3-dihydroxyphenylalanine and its derivatives, 4,5-dihydroxyphenylalanine and its derivatives, dihydroxycinnamates such as caffeic acid and chlorogenic acid, orthopolyhydroxycoumarines, orthopolyhydroxyisocoumarines, orthopolyhydroxycoumarones, orthopolyhydroxyisocoumarones, orthopolyhydroxychalcones, orthopolyhydroxychromones, nes, - hydroxyxanthones, 1,2-dihydroxybenzene and its derivatives, 1,2,4-trihydroxybenzene and its derivatives, 1,2,3-trihydroxybenzene and its derivatives, 2,4,5-trihydroxytoluene and its derivatives, - proanthocyanidins and in particular proanthocyanidins Al, A2, Bi, B2, B3 and Cl, 35 - chromanics, and chromenics, - proanthocyanins, - tannic acid, - ellagic acid, - and mixtures of the foregoing compounds; Preferably, the ortho-diphenol (s) are chosen from haematein, brasiline, gallic acid, tannic acid, hematoxylin, brasiline and mixtures thereof.
[0005]
5. A dyeing method according to any one of the preceding claims, wherein the dye (s) a) of the dye composition Ci) is (are) selected from the chromium or chromanic ODPs dyes and particularly selected among neoflavanols and neoflavanones, more particularly chosen from dyes of the following formulas:> formula (III), comprising in its structure the bicycle of formula (B2), and its tautomeric and / or mesomeric forms its stereoisomers, its addition salts with a cosmetically acceptable acid or base, and its solvates such as hydrates; Formula (III) in which: - represents a single carbon-carbon bond or a carbon-carbon double bond, the linking of these bonds denotes two single carbon-carbon bonds and two carbon-carbon double bonds, said bonds being conjugated X represents a group: ## STR2 ## wherein R 1, R 2, R 3, R 4, R 5 and R 6, which may be identical or different, represent a hydrogen atom, a hydroxyl group or an optionally substituted alkyl group; optionally substituted alkoxy, or an optionally substituted acyloxy group; and> formula (IV), comprising in its structure the bicycle of formula (B1): R18 (IV) as well as its tautomeric and / or mesomeric forms, its stereoisomers, its addition salts with an acid or a base cosmetically acceptable, and its hydrates; Formula (IV) in which: - R11, R12, R13, R16, R19 and R20, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical, and - R14, R15, R17 and R18, identical or different, represent a hydrogen atom, a hydroxyl radical or a C 1 -C 4 alkoxy radical; in particular, the dye (s) a) is (are) of formula (III) and more particularly chosen from hematoxylin, haematein, brazilin and braziléine; preferentially hematoxylin and brazilin: HO HO HO Hemeineine Braziléine HO HO OH HO HO Hematoxylin Braziline
[0006]
6. A dyeing method according to any one of the preceding claims, wherein the dye (s) a) of the dye composition Ci) are chosen from the natural dyes and is (are) chosen among extracts of animals, bacteria, fungi, algae, plants and fruits.
[0007]
The method of dyeing according to any one of the preceding claims, wherein the acid (s) bl) of the dye composition Ci) is (are) of the formula (I) with A representing a monovalent group (C1). -C6) alkyl or polyvalent (C1-C6) alkylene optionally substituted by one or more hydroxyl groups, and n representing an integer inclusive of between 0 and 5, such as 0, 1 or 2, especially the carboxylic acid or acids of the invention are selected from α-hydroxy acids; Preferentially the acid is selected from citric acid, lactic acid, tartaric acid, and glycolic acid; more preferably the acid (s) b1) of formula (I) or their salts, is (are) present (s) in a content ranging from 0.1 to 20% by weight relative to the total weight of the composition Ci ). 10
[0008]
8. A method of coloring according to any one of the preceding claims, wherein the salt (s) of titanium b) of the dye composition Ci) is (are) chosen from organic or inorganic titanium salts, preferably from organic titanium salts, and in which titanium is in particular of oxidation state 2, 3 or 4, preferably of oxidation degree 4.
[0009]
9. The method of dyeing according to the preceding claim, wherein the organic salt (s) of titanium b) of the dye composition Ci) is (are) from (s) the acid reaction (s) organic (s) on titanium, wherein the organic acid (s) is (are) selected from organic acids which comprise: a) at least one C1-C20 hydrocarbon chain, optionally unsaturated, linear or branched, (hetero) cycloalkyl, or (hetero) aryl, and b) at least one acidic chemical function being in particular selected from carboxy COOH, sulfuric SO3H, SO2H, and phosphoric PO3H2, PO41-12; preferably the organic acid (s) is (are) chosen from carboxylic acids (s) of formula (I) as defined in claim 1 or 7, more preferably from citric acids, lactic, tartaric and glycolic and more particularly lactic and glycolic acids.
[0010]
10. A dyeing method according to any one of the preceding claims, wherein the acid (s) b1) of the dye composition Ci) is (are) of formula (I) as defined (s) in claim 1 or 7 and the latter is (are) different from the organic acid (s) of the titanium salt as defined in claim 8 or 9.
[0011]
11. Coloring method according to any one of the preceding claims, in which the titanium organic salt (s) b) of the dye composition Ci) is (are) chosen from those of formula (IA) wherein (A) is as defined in claim 1 or 6; n, n 'and n ", identical or different, are 1, 2, 3, or 4 with n' + n" = 6; M1 and M2, which are identical or different, represent a cationic counterion such as an alkali metal cation such as Na, or K, alkaline earth such as Ca or organic such as ammonium, preferably ammonium or a hydrogen atom; - TiY ',, represents Ti (01-1), r, or Ti (0) 12, or T (OH) mi (0), 2 with m1 + m2 = n ", preferably, the salt (s) The titanium organic (s) of the staining process is the dihydroxybis (lactato) titanium IV salt such as those of the following formula: ## STR2 ##
[0012]
12. A dyeing process according to any preceding claim wherein the alkaline agent (s) c) of the revealing composition Cii) is (are) selected from i) the (bi) carbonates ii) ammonia, iii) alkanolamines comprising only one amine function such as monoethanolamine; monopropanolamine iv) oxyalkylenated alkanolamines comprising only one amine function and in particular oxyethylenated aclanolamines such as oxyethylenated and / or oxypropylenated ethyleneamines, y) inorganic or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) amino acids comprising only one amine function, basic preferences such as histidine; more particularly, the alkaline agent is chosen from alkali metal or alkaline earth metal (bi) carbonates and amino acids comprising only one amine function such as hystidine; preferentially, the alkaline agent (s) c) of the revealing composition Cii) is (are) chosen from alkali metal (bi) carbonates and the amino acids comprising only one function amine.
[0013]
13. A dyeing process according to any one of the preceding claims wherein the alkaline agent (s) c) of the revealing composition Cii) is (are) selected from a mixture of 2 alkaline agents. ) to vii) as defined in the preceding claim; particularly the alkaline agent (s) c) is (are) chosen from among the following mixtures: 1) carbonates + bicarbonates; 2) amino acids + (bi) carbonates; 3) alkanolamines + (bi) carbonates; 4) oxyalkylenated alkanolamines + (bi) carbonates; 5) inorganic or organic hydroxides + (bi) carbonates; 6) alkali metal silicates + (bi) carbonates; oxyalkylenated or non-alkylene amino acids and alkanolamines comprising at most one amine function; more particularly the weight ratio between carbonates and bicarbonates according to 1) or between the first alkaline agents: amino acids, alkanolamines, alkylene oxyalkylenated alkanes, inorganic or organic hydroxides, alkali metal silicates and the (bi) carbonates according to 2) to 6) is greater than or equal to 2, preferably greater than or equal to 4, more preferably greater than or equal to 6, even more preferably greater than or equal to 8 better than or equal to 10 and in particular being between 2 and 16 inclusive, preferentially is included inclusively between 10 and
[0014]
14. The method of dyeing according to the preceding claim wherein the agent (s) alkali (s) c) of the revealing composition Cii) is (are) selected from a mixture of carbonates and bicarbonates with a ratio by weight of carbonates / bicarbonates greater than 2, preferably greater than or equal to 4, more preferably greater than or equal to 6, even more preferably greater than or equal to 8 better than or equal to 10 and in particular is included inclusively between 2 and 16, preferably is between 10 and 14 inclusively, advantageously the composition Cii) comprises at least one alkaline agent chosen from alkali metal carbonate alone such as sodium carbonate alone or a mixture of alkali metal carbonate and bi alkali metal carbonate such as the mixture of sodium carbonate and sodium bicarbonate with preferably a weight ratio of carbonates / bicarbonates greater than 2, preferably is greater than or equal to 4, more preferably greater than or equal to 6, even more preferably greater than or equal to 8 more preferably greater than or equal to 10, and in particular is inclusive from 2 to 16, preferentially being included inclusively. between 10 and 14.
[0015]
15. The method of dyeing according to any preceding claim wherein the agent (s) alkali (s) c) of the composition Cii) has (s) one or more pKa inclusive between 6 and 11.5, more particularly between 9.5 and 11 at room temperature.
[0016]
16. A dyeing process according to any one of the preceding claims wherein the carboxylic acid (s) b1 has (s) a pKai of less than 3.
[0017]
17. A dyeing process according to any preceding claim wherein the agent (s) alkali (s) c) of the composition Cii) represents (s) a total amount greater than 1% by total weight relative to the total weight of the composition Cii), particularly preferably between 1% and 15 (:) / 0, more particularly between 2% and 10 (:) / 0, preferably between 5.1 and 9% by weight of the composition Cii).
[0018]
18. A dyeing process according to any one of the preceding claims, wherein the composition Cii) comprises one or more chemical oxidizing agent (s) d) selected from hydrogen peroxide or one or more system (s) generator (s) of hydrogen peroxide; in particular, chosen from hydrogen peroxide or urea peroxide, preferably hydrogen peroxide. 20
[0019]
19. The method of dyeing according to any one of the preceding claims, wherein the composition Ci) and / or the composition Cii), preferably the composition Ci) comprises one or more organic solvent (s) , especially chosen from C1-C4 lower alkanols, 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, hexylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, preferably aromatic alcohols such as benzyl alcohol.
[0020]
20. A method of dyeing according to any one of the preceding claims which comprises firstly the application to the keratinous fibers of a cosmetic composition Ci) comprising: a) one or more ODP (s), as (s) defined (s) in any one of claims 3 to 6, in particular chosen from: - haematein, brasiline, gallic acid, tannic acid, when the dyeing process does not involve chemical oxidizing agent d) as defined in claim 1 or 18; or else - hematoxylin, brasiline, when the dyeing process uses a chemical oxidizing agent d) as defined in claim 1 or 18; B) one or more organic titanium salt (s) as defined as defined in any one of claims 1, 8 to 11; b1) optionally one or more carboxylic acid (s) of formula (I) as defined in any one of claims 1, 7 and 16; then secondly applying a cosmetic composition Cii) comprising c) one or more alkaline agent (s) as defined in any one of claims 1, 13 to 15 and 17; and d) optionally one or more chemical oxidizing agent (s) selected from hydrogen peroxide or one or more hydrogen peroxide generator system (s) as defined previously; it being understood that: the composition Ci) is at acidic pH, i.e. less than 7, preferably less than 5, particularly at a pH ranging between 1 and 3; and - the composition Cii) is at alkaline pH, preferably between 8 and 12 and more particularly between 9 and 10.5.
[0021]
21. Cosmetic composition containing the ingredients a), b), optionally b1), c), and optionally d) as defined according to any one of claims 1 to 18 and optionally an organic solvent as defined in claim 19. 20
[0022]
22. A multi-compartment device comprising 2 to 5 compartments containing from 2 to 5 compositions, in which are distributed the ingredients a), b), b1), c), and d) as defined according to any one of the claims. 1 to 18, said compositions being aqueous or powdery, with at least one of these compositions being aqueous.

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公开号 | 公开日

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FR3037237B1|2018-11-30|

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WO2016198656A1|2016-12-15|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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US20080233068A1|2005-04-06|2008-09-25|The Boots Company Plc|Oxidative Hair Dyes and Related Topical Compositions|

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WO2011086284A1|2009-12-23|2011-07-21|L'oreal|Composition for dyeing keratin fibers, including at least one ortho-diphenol derivative, one chemical oxidizing agent, and one alkalinizing agent|

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FR2976793A1|2011-06-23|2012-12-28|Oreal|Dyeing keratin fibers, preferably hair, comprises treating fibers with compositions containing ortho-diphenol derivatives, manganese or zinc salts, hydrogen peroxide, carbonates, basifying agents and titanium salts to keratin fibers|

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FR2976797A1|2011-06-23|2012-12-28|Oreal|Dyeing keratin fibers, preferably hair, comprises applying compositions containing e.g. dihydroxyflavone derivatives, manganese salts, different basifying agents or bicarbonates, and metal salt e.g. scandium and titanium, to the fibers|WO2019122332A1|2017-12-22|2019-06-27|L'oreal|Multi-step process for dyeing keratin fibres using indigo-producing plant powder, and for alkaline dye treatment|

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WO2019121504A2|2017-12-22|2019-06-27|L'oreal|Multiple-compartment device comprising at least one internal frangible seal|

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WO2019121503A2|2017-12-22|2019-06-27|L'oreal|Multiple-compartment device comprising at least one internal frangible seal|

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WO2019163497A1|2018-02-20|2019-08-29|株式会社Ｎｉｌ|Hairdye|

法律状态:
2016-05-16| PLFP| Fee payment|Year of fee payment: 2 |

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2016-12-16| PLSC| Search report ready|Effective date: 20161216 |

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2018-05-11| PLFP| Fee payment|Year of fee payment: 4 |

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2020-05-12| PLFP| Fee payment|Year of fee payment: 6 |

优先权:

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申请号 | 申请日 | 专利标题

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FR1555384|2015-06-12|

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FR1555384A|FR3037237B1|2015-06-12|2015-06-12|CAPILLARY COLORING PROCESS IMPLEMENTING A COLORING STEP FROM A DYE, AND A TITANIUM SALT AND A REVELATION STEP FROM ALKALINE AGENT COMPRISING AT LEAST ONE AMINO FUNCTION|FR1555384A| FR3037237B1|2015-06-12|2015-06-12|CAPILLARY COLORING PROCESS IMPLEMENTING A COLORING STEP FROM A DYE, AND A TITANIUM SALT AND A REVELATION STEP FROM ALKALINE AGENT COMPRISING AT LEAST ONE AMINO FUNCTION|

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PCT/EP2016/063380| WO2016198656A1|2015-06-12|2016-06-10|Hair dyeing process involving a dyeing step using a dye and a titanium salt, and a revealing step using an alkaline agent comprising not more than one amine function|