A CAPILLARY COLORING PROCESS USING AT LEAST ONE COLOR, AN ORGANIC TITANIUM SALT, AND A NON-CELLULOSI

专利摘要:
The present invention relates to a method for dyeing keratinous fibers, in particular human keratin fibers such as the hair, in which said fibers are treated from one or more cosmetic compositions comprising a) one or more dyes, b ) one or more salts of titanium and optionally b1) at least one carboxylic acid and c) one or more non-cellulosic polysaccharide (s), and d) optionally one or more chemical oxidizing agent (s) (s) ) such as hydrogen peroxide or one or more system (s) generator (s) of hydrogen peroxide.
公开号:FR3029409A1
申请号:FR1462064
申请日:2014-12-08
公开日:2016-06-10
发明作者:Boris Lalleman；Alain Lagrange；Francoise Albouy；Frederic Simonet
申请人:LOreal SA；
IPC主号:

专利说明:

[0001] The present invention relates to a process for the dyeing of keratinous fibers, in particular human keratinous fibers such as the hair, wherein said hair dyeing process uses at least one dye, an organic titanium salt and a non-cellulosic polysaccharide. fibers are processed from one or more cosmetic compositions comprising a) one or more dyes, b) one or more titanium salt (s) and b1) optionally one or more particular carboxylic acids; c) one or more non-cellulosic polysaccharide (s), d) optionally one or more chemical oxidizing agent (s) such as hydrogen peroxide or one or more system (s) ) generator (s) of hydrogen peroxide. 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 heterocyclic compounds. 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. It is nevertheless sought to increase the efficiency of the reaction of the oxidation dyes used during this process, in particular in terms of increasing the color on the keratin fibers. In fact, such an improvement would make it possible in particular to reduce the contents 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 to present a good toxicological profile. In addition it would bring new shades or lead to more stubborn stains vis-à-vis external agents such as light or shampoos, it finally leads to better quality of use as a less staining of scalp, clothing, or even less coloring dye mixture (cleaner) during application or break time 3029409 2 Furthermore, it is known to dye keratin fibers and in particular human hair, with compositions stain containing direct dyes. The standard dyes which 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. 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 keratin fibers for a time necessary to obtain the desired coloration, and then rinsed. The resulting dyes 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 of the surface and / or the core of the fiber are responsible for their low dyeing power and their poor resistance to light, washing, or perspiration. There is therefore still progress to be made in this field to provide powerful dyes, resistant and respecting the nature of the hair from compositions containing dyes including natural. In the field of staining from natural extract such as orthodiphenols (ODPs), it is also known to stain keratin materials such as hair or skin from ODPs in the presence of a metal salt, especially manganese (Mn) and / or zinc (Zn). In particular, 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, alkaloids of hydrogen carbonate type in a particular ratio Mn, Zn / hydrogencarbonate 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.
[0002] However, the colorations obtained from ODPs are insufficiently powerful, intense and / or are not very stubborn, especially in the case of hair fibers. It is known to use acid-level metals for dyeing keratinous fibers in amounts similar to those used for dyes by using an etching process, which consists of preparing the fibers before dyeing in order to obtain stubborn hues (Ullmann's Encyclopedia "Metal and Dyes", 2005 § 5.1, p 8). However, this process generally has the disadvantage of not always respecting the cosmetics of the keratin 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 40 (FR297673, WO2011 / 086284, WO2011 / 086282, and FR2951374) .
[0003] 3029409 3 However, improvements still need to be made, especially in terms of the color tenacity of 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 oxidation dyes, direct dyes and / or natural dyes, in particular from ODPs, in particular from from natural extracts rich in ODPs, less aggressive for keratinous fibers, or requiring smaller quantities of dyes. More particularly, there is a need to obtain stainings which are satisfactorily resistant to external agents (light, weather, shampoos, sweat) which are stubborn and homogeneous, ie with low selectivity of staining between the root and the tip. , while remaining powerful and / or chromatic. In addition, it is necessary to obtain the satisfactory coloration performance, that the product is stable and has suitable use qualities that is to say a sufficient rheology not to sink during the pause time. For this reason, it is preferable that the staining medium not interact with the staining process. This goal (s) is (are) achieved by the present invention which relates to a process for dyeing keratinous fibers, in particular human keratin fibers such as the hair, in which said fibers are treated, in one or more steps, by one or more cosmetic compositions containing, taken together or separately in the one or more compositions, the following ingredients: a) one or more dyes selected from the oxidation dyes and the synthetic direct dyes and dyes of natural origin, preferably selected from ODPs; B) one or more salt (s) of titanium; in particular the Ti atom of the salt is of oxidation state 2, 3 or 4 denoted Ti (I I), Ti (III) or Ti (IV), preferably Ti (IV); b1) optionally one or more carboxylic acid (s) of formula (I) below; A (I) n Formula (I) or a salt thereof wherein: -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 by one or more hydroxy groups; n represents an integer between 0 and 10, preferably n is between 0 and 5, such as between 0 and 2; c) one or more non-cellulosic polysaccharide (s); d) optionally one or more chemical oxidizing agent (s), especially chosen from hydrogen peroxide or one or more hydrogen peroxide generator system (s); preferably at least one of the compositions used in the dyeing process is at acidic pH, ie less than 7.0, preferably less than 5, particularly at a pH between 0 and 4 inclusive, more particularly between 0.5 and 3.5 and more preferably between 1 and 3. Preferably, the one or more compositions used in the process of the invention is (are) aqueous. Another subject of the invention is a cosmetic composition comprising the ingredients a), b), c) and optionally d) as defined above. Another object of the present invention is a multi-compartment device comprising ingredients a), b), c) and optionally d) distributed in a plurality of compartments. The multi-compartment device or "kit" is suitable for carrying out the coloring process according to the invention. The method according to the invention has the advantage of coloring the human keratinous fibers, with results of stubborn staining. In particular, the dyeing method according to the invention makes it possible to lead to colorings resistant to washing, transpiration, sebum and light without altering the fibers. The resistance to perspiration is particularly good. In addition, the coloring process used makes it possible to induce a "rise" and / or power of the satisfactory coloration.
[0004] Other objects, features, aspects and advantages of the present invention will become more apparent upon reading the description and the examples which follow. a) The dye (s) According to the present invention, the dyeing process involves a) one or more dyes. The dye (s) used in the process according to the invention may be precursors of oxidation dyes and / or direct dyes of synthetic or natural origin.
[0005] The dye (s) of the invention may be present in one or more cosmetic composition (s) used during the dyeing process.
[0006] The oxidation dye precursors which can be used in the present invention are generally selected from oxidation bases, optionally combined with one or more couplers. The oxidation bases may 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 paraphenylenediamines, there may be mentioned, by way of 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 paraphenylenediamine, N, N-dimethyl paraphenylenediamine, N, N-diethyl paraphenylenediamine, N, N-dipropyl paraphenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N-bis - ((3-hydroxyethyl) paraphenylenediamine, 4-N, N-bis - ((3-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis - ((3-hydroxyethyl) amino 2-chloroaniline, 2- (3-hydroxyethyl) paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N - ((3-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, - (3-hydroxyethyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, (3-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, 2-hydroxyethylamino-5-amino-toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their salts. addition with an acid. Among the para-phenylenediamines mentioned above, para-phenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-hydroxy-3-hydroxyethyl paraphenylenediamine, 2-hydroxy-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis - ((3-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-13-acetylaminoethyloxy-para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine and acid addition salts thereof are particularly preferred. Among the bis-phenylalkylenediamines, for example, N, N'-bis- ((3-hydroxyethyl) N, N'-bis- (4) 1-aminophenyl) 1,3-diamino propanol, N, N'-bis - ((3-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-Aminophenyl) tetramethylenediamine, N, N'-bis - ((3-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethyl) thylenediamine, 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.
[0007] Among the para-aminophenols, para-amino phenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 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 - ((3-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid.On example, ortho-aminophenols include, by way of example, 2-amino phenol, 2-amino-5-methyl phenol, 2-amino-6-methyl phenol, 5-acetamido-2-amino phenol, and their addition salts, of which heterocyclic bases can be in particular pyridine derivatives, pyrimidine derivatives and pyrazole derivatives Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5 diamino pyridine,2- (4-methoxyphenyl) amino-3-amino-pyridine, 3,4-diamino pyridine, and their addition salts. Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-a] -pyridines oxidation bases or their addition salts described, for example, in FR 2801308. By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diaminopyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5a] 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 3029409; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-aminopyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridin-4-ol; 3-aminopyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol; 2- (3-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, more particularly the oxidation bases according to the invention are chosen from 3-aminopyrazolo- [1,5a] -pyridines preferably substituted in the 2-position by: a) a (di) group (C1-C6) (alkyl) amino the alkyl groups which may be substituted by one or more hydroxy, amino, or imidazolium groups; b) a heterocycloalkyl group comprising from 5 to 7 members, and from 1 to 3 heteroatoms, cationic or otherwise, optionally substituted by 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 hydroxy groups such as β-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 WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4 dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and tautomeric forms, when tautomeric equilibrium exists. Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 diamino 1-methyl pyrazole, 4,5-diamino-1 - ((3-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 5-diamino-1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenyl pyrazole, 4-amino-1 3-dimethyl-5-hydrazino pyrazole, 1-benzyl-4,5-diamino-3-methyl pyrazole, 4,5-diamino-3-tert-butyl-1-methyl pyrazole, 4,5-diamino-1-tert 3-methyl pyrazole, 4,5-diamino-1- (3-hydroxyethyl) -3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl pyrazole, 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-diam ino-3-methyl-1-isopropyl pyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl-3 4,5-Triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4 - ((3-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts. Preferably, the heterocyclic oxidation bases of the invention are chosen from 4,5-diaminopyrazoles such as 4,5-diamino-1 - ((3-hydroxyethyl) pyrazole, or 4-5-diamino. -1 - ((3-methoxyethyl) pyrazole.
[0008] Preferably, a 4,5-diaminopyrazole and even more preferably 4,5-diamino-1 - ((3-hydroxyethyl) pyrazole and / or one of its salts will be used as pyrazole derivatives. mention may also be made of diamino N, Ndihydropyrazolopyrazolones and in particular those described in Application FR-A-2,886,136, such as the following compounds and their addition salts: 2,3-diamino-6,7-dihydro-1H, 5H pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino 3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3- (pyrrolidin-1-yl) -6,7-dihydro-1H 5H-pyrazolo [1,2-a] pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2 diethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-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-o ne, 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one, 4-aminodo-1,2-diethyl-5- ( pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one, 4-amin-5- (3-di-methylamino-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 [1,2-2,5] is preferably 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 The additional couplers conventionally used for dyeing keratinous fibers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers, as well as their By way of example, mention may be made of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 1-hydroxybenzene and the like. 3-aminobenzene, 235 methyl-5-aminophenol, 3-amino-2-chloro-6-methyl phenol roxyethylaminophenol, 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-ureidoaniline, 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-diaminoinde 2,6-dimethoxypyridine, 1-N- (11-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis (11-hydroxyethylamino) toluene, 6-hydroxyindoline, 2,6-dihydroxy 4-methyl pyridine, 1-H-3-methyl pyrazol-5-one, 1-phenyl-3-methyl pyrazole 5-one, 2,6-dimethyl pyrazolo [1,5-b] -1 2,4-triazole, 2,6-dimethyl- [3,2-c] -1,2,4-triazole, 6-methyl pyrazolo [1,5-a] -benzimidazole, their addition salts with an acid, and mixtures thereof. In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. 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 dye composition, preferably from 0.005 to 5% by weight relative to the weight of the dye composition. total of the coloring composition. The direct dye (s) that can be used in the context of the invention may be anionic, cationic or neutral direct dyes, of natural or non-fluorescent origin or not. These direct dyes are in particular chosen from those conventionally used in direct dyeing all commonly used aromatic and / or nonaromatic dyes such as neutral neutral, acidic or cationic nitro benzene dyes, neutral azo direct dyes, acidic or cationic, natural direct dyes, quinone direct dyes and in particular neutral, acidic or cationic anthraquinone dyes, azine, polyarylmethane direct dyes such as triarylmethanics, indoamines, polymethines such as styryls, porphyrins, metalloporphyrins, phthalocyanines, methine cyanines .
[0009] Among the natural direct dyes are lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidine, orceins, polyphenols or ortho-diphenols (ODPs) and all extracts. rich in ODPs. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular the poultices or extracts based on henna and / or indigo. According to a particularly preferred embodiment of the invention, the dye (s) are chosen from orthodiphenol (s) or ODP (s). The invention relates to one or more ODP (s) or mixtures of compounds comprising one or more aromatic rings of which at least one is a benzene ring substituted by at least two hydroxy groups (OH) carried by two adjacent carbon atoms of said benzene group being present in the structure of the orthodiphenol (s).
[0010] 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, chroman, isochromane, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic ring having at least minus two hydroxy groups carried by two adjacent carbon atoms of the aromatic ring. Preferably, the aromatic ring of orthodiphenol derivatives according to the invention is a benzene ring. By "condensed ring" is meant that at least two saturated or unsaturated, heterocyclic or non-heterocyclic rings have a common bond, i.e. at least one ring is attached to another ring. The ODP (s) according to the invention may be salified or not. They can also be in the form of aglygone (without bound sugar) or in the form of glycosylated compounds.
[0011] More particularly, the ODP (s) a) represents a compound of formula (II), or one of its oligomers, tautomers, optical isomers, geometric isomers, as well as its salts or solvates such as hydrates: OH formula (II) wherein: R 1 to R 4, identical or different, represent: i) a hydrogen atom, ii) halogen, or a group selected from iii) hydroxy, iv) carboxy, carboxylate ( Ci-C20) alkyl or (C1-C20) alkoxycarbonyl, vi) optionally substituted amino, vii) C20) optionally substituted linear or branched alkyl, viii) (C2-C20) optionally substituted linear or branched alkenyl, ix) optionally substituted cycloalkyl, x) C20) alkoxy, xi) (C1-C20) alkoxy (C1-C20) alkyl, xii) (C1-C20) alkoxyaryl, xiii) optionally substituted aryl, xiv) aryl, xv) substituted aryl, xvi ) heterocyclic, saturated or not, with or without a cationic or anionic charge, optionally substituted and / or optionally condensed with an aromatic ring, preferably benzene, said aromatic ring being optionally substituted especially by one or more hydroxy 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 form together with the carbon atoms bearing 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. 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 pyrrolyl radical. According to a variant, R2 and R3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring bearing the two hydroxyls. For the purposes 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, generally C 1 -C 20, particularly C 1 -C 10, hydrocarbon radicals, preferably C 1 -C 6 alkyl radicals, such as methyl, ethyl, propyl or butyl, pentyl and hexyl; the "alkenyl" radicals are hydrocarbon radicals, linear or branched, unsaturated C 2 -C 20; 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 C1-C10, 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; the "cycloalkyl" radicals are C 4 -C 8 cycloalkyl radicals, preferably the cyclopentyl and cyclohexyl radicals; the cycloalkyl radicals can be substituted cycloalkyl radicals, in particular with alkyl, alkoxy, carboxylic acid, hydroxy, amine and ketone groups; the radicals "alkyl" or "alkenyl" 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 (ClC4) 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 hydroxy group, b) an amino group optionally substituted by one or two radicals (C 1 -C 3) optionally substituted alkyl, 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 ", 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) alkyl radical, preferentially m ethyl; x) acylamino (-N (R) -C (O) -R ') in which the radical R is a hydrogen atom, a (C1-C4) alkyl radical optionally bearing at least one hydroxyl group and the radical R 'is a C1-C2 alkyl radical; a carbamoyl radical ((R) 2 N-C (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) alkylsulphonylamino (R'-S (O) 2 -N (R) -) in which the radical R represents a hydrogen atom, a (C1-C4) alkyl radical optionally carrying at least one hydroxyl group and the radical R 'represents a (C1-C4) alkyl radical, a phenyl radical; xii) aminosulphonyl ((R) 2N-S (O) 2-) in which the radicals R, which may be identical or different, represent a hydrogen atom, a (C 1 -C 4) alkyl radical optionally carrying at least one group selected from a) hydroxy, b) carboxy-O (O) -OH in acid 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: (C1-C10) alkyl, preferably C1-C8, optionally substituted with one or more radicals selected from hydroxy, (C1-C2) alkoxy, (poly) hydroxyalkoxy C2-04, acylamino, amino; substituted with two identical or different C 1 -C 4 alkyl radicals, optionally bearing at least one hydroxyl group, or the two radicals being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7; 5-membered, preferably 5 or 6-membered, optionally substituted saturated or unsaturated linkages optionally comprising another heteroatom identical to or different from nitrogen; ii) halogen; iii) hydroxy; iv) C 1 -C 2 alkoxy; v) C1-C10 alkoxycarbonyl; vi) (poly) hydroxyalkoxy C2-04; 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, preferably methyl; x) amino substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: a) a hydroxy, b) amino group optionally substituted by one or two optionally substituted C 1 -C 3 alkyl radicals, said alkyl radicals being capable of forming, with the nitrogen atom to which they are attached, an optionally substituted 5 to 7-membered saturated or unsaturated heterocycle optionally comprising at least one other non-nitrogen heteroatom or another, 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 C1-C4 alkyl group, and M- represents the counter-group; ion of the organic acid, mineral or of the corresponding halide, d) a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C1-C4) alkyl radical, preferably methyl; acylamino (-N (R) -C (O) -R ') in which the radical R is a hydrogen atom, a C1-C4 alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a C1-C2 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 -C 4 alkyl radical optionally bearing 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 carrying at least one hydroxyl group; (xv) carboxy in acidic 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, stearoxydimethicone radicals; the "heterocyclic" radicals are radicals comprising in at least one ring one or more heteroatoms particularly chosen from O, N and S, preferably O 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.
[0012] The ODP (s) useful in the process of the invention can be natural or synthetic. Natural ODPs include compounds that may be present in nature and are reproduced by (hemi) chemical synthesis. The salts of the ODPs 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. By "basifying agents" is meant the bases as defined for e) may be mineral or organic. Especially the bases are alkali hydroxides such as sodium hydroxide which leads to sodium salts. According to a particular embodiment of the invention, the composition comprises as ingredient a) one or more synthetic ODP (s) which do not exist in nature. According to another preferred embodiment of the invention, the composition that is useful in the process for staining keratinous fibers comprises as ingredient a) one or more natural ODP (s).
[0013] More particularly, the ODP (s) usable in the process of the invention according to a) (is) are in particular: flavanols such as catechin and epichatechin gallate, 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 tetrahydroxy-3,3 ', 4,5'-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, o polyhydroxycyclones, orthopolyhydroxychromones, 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 especially proanthocyanidins Al, A2, B1, B2, B3 and C1, chromium and chromene compounds, proathocyanins, tannic acid, ellagic acid; and mixtures of the foregoing compounds. According to the invention, "chromenic or chromanic" ODP compounds are understood to mean ODPs which comprise in their structure at least one bicycle of the following formula (A): (A) the intracyclic bond representing a single carbon-carbon bond or else a carbon-carbon double bond, as illustrated by the formula (A1) denoting the family of chromenes and the formula (A2) denoting the chroman family below: ## STR2 ## ODPs of the invention are of formula (A) and preferably chosen from the dyes of the following formulas: - formula (III), comprising in its structure the bicycle of formula (A2), R4 OH and its tautomeric forms and / or mesomers, its stereoisomers, its addition salts with a cosmetically acceptable acid or base, and its 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: HO-C or O = C 15 -R1, R2, R3, R4, R5 and R6, 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 (A1): ## STR2 ## 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. With regard to the orthodiphenols of formula (III) as defined above, these may be in two tautomeric forms noted (IIIa) and (IIIb): ## STR1 ## The alkyl radicals mentioned above in the preceding definitions of the substituents are hydrocarbon radicals, saturated, linear or branched, generally C 1 -C 20, especially 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-C10, 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) (C 1 -C 2) alkoxy, (iv) C 10 -C 20 alkoxycarbonyl, (poly) -hydroxyalkoxy O 2-04, vi) amino, vii) 5- or 6-membered heterocycloalkyl, viii) 5-membered heteroaryl, or 6-membered optionally cationic, preferably imidazolium, and optionally substituted with a (C1-C4) alkyl radical, preferably methyl; ix) an amino radical 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 5 alkyl radicals -C3 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 or 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 with a (C1-C4) alkyl radical le, preferably methyl; x) an acylamino radical (-NR-COR ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group and the radical R is a C1-C2 alkyl radical; xi) a carbamoyl radical ((R) 2N-CO-) 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; xii) an alkylsulphonylamino radical (R'SO 2 -NR-) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally carrying at least one hydroxyl group and the radical R 'represents a radical; C1-C4 alkyl, a phenyl radical; xiii) an aminosulphonyl radical ((R) 2 N -SO 2 -) 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; (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. By glycosyl radical is meant a radical derived from a mono or polysaccharide. Preferably, the alkyl or alkoxy radicals of formula (III) are unsubstituted. According to a particular embodiment of the invention, the dyes of formula (III) include a radical R 6 representing a hydroxyl group. Another particular embodiment of the invention relates to the ODPs of formula (III), for which the radical R1 represents a hydrogen atom or a hydroxyl group. More particularly, the composition according to the invention may comprise one or more ODP (s) of formula (III) chosen from hematoxylin, haematein, brazilin and braziline. HO HO HO Hemeinine Braziléine HO HO OH HO Hematoxylin (Natural Black 1 - Braziline (Natural Red 24 - CAS 517-28-2) CAS 474-07-7) BRAZILINE is a conjugated form of a chroman compound of formula ( A2). The diagram below shows the tautomeric structures (111a) and (111b) illustrated above. Among the hematoxylin / haematin and brazilin / braziline type ODPs, there may be mentioned by way of example hematoxylin (Natural Black 1 according to the INCI name) and braziline (Natural Red 24 according to the INCI name). ), 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.
[0014] The ODPs of formula (III) can be used in the form of extracts. The following plant extracts (genus and species) may be used: Haematoxylon campechianum, Haematoxylon brasiletto, 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.
[0015] According to a particular embodiment of the invention, the ODP or ODPs are of formula (I) natural and are derived from logwood wood, pernambuco wood, sappan wood and brazil wood. According to a particular embodiment of the invention the ODPs are of formula (IV), preferably those for which R11 and R13 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 particularly preferred first family of ODPs suitable for the present invention are those dyes of formula (II) 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 ODPs of this first family include those, for which R18 represents a methoxy (santaline B) or hydroxy (santaline A) radical. A second particularly preferred family of ODPs 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 is methyl, R20, R12, R14, R18 and R16 are each hydrogen, and R15 is hydroxy (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). A third family of preferred ODPs of this second family is that for which R20, R12, R14, R15, R16 and R19 are hydrogen and R18 is hydroxy (santarubine C). The preferred ODP or ODPs of this second family is that for which R15 represents a methoxy radical, and R18 and R14 represent a hydrogen atom and R20, R12, R16 and R19 represent a methyl radical (tetra-O-methylcantarubine).
[0016] The ODP (s) of formula (IV) may be used in the form of extracts. Redwood plant extracts can be used, generally including Asian and West African redwood species of the genus Pterocarpus and the genus Baphia. These woods are for example Pterocarpus santalinus, Pterocarpus osun, Pterocarpus soyauxii, Pterocarpus erinaceus, Pterocarpus indicus or 40 Baphia nitida. These woods can still be called padauk, sandalwood, narrawood, camwood or barwood. Thus, usable extracts containing ODPs of formula (11) 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. SL 709C concentrate by the company COPIAA or else 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.
[0017] Extracts also suitable for the present invention may be obtained from woods 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 material in order to collect a pulverulent extract particularly suitable for the implementation of the present invention. The ODP salts 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.
[0018] The bases can be mineral or organic. Especially the bases are alkali hydroxides, such as sodium hydroxide leading to sodium salts. Preferably, the ODP or ODPs of formula (III) and (IV) included in the composition according to the invention are derived from plant extracts. It is also possible to use mixtures of plant extracts.
[0019] The natural extracts of ODPs according to the invention may be in the form of powders or liquids. Preferably, the extracts are in powder form. Particularly the ODPs of the invention are comprised of catechin, quercetin, brazilin, haematein, hematoxylin, chlorogenic acids, caffeic, gallic, catechol, gallic acid, L DOPA, pelargonidine, cyanidine, (-) -Epicatechin, 30 (-) - Epigallocatechin, (-) - Epigallocatechin 3-gallate (EGCG), (+) - Catechin, Isoquercetin, Pomiferin, esculetin, 6,7-Dihydroxy-3- (3-hydroxy-2,4-hydroxy) - dimethoxyphenyl) coumarin. Santalin AC, Mangiferine, Butein, Maritimetine, Sulfuretine, Robtein, Betanidine, Pericampylinone A., Theaflavin, Proanthocyanidin A2, Proanthocyanidin B2, ProanthocyanidinCl, Procyanidins DP 4-8, Tannic Acid, Purpurogalline, 5,6-Dihydroxy-2-methyl 1,4-naphthoquinone, Alizarin, VVelelactone, Variegatic acid, Gomphidic acid, Xerocomic acid, Carnosol, and natural extracts containing them. Preferably, the ODPs of the invention are chromenic or chromanic and are chosen from haematein, hematoxylin, brasiline, brasiline, santaline A.
[0020] By "carboxylate" is meant carboxylic acid salt.
[0021] 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 ODPs 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 ODPs as defined above. Preferably, the natural ODP or ODPs of the invention are derived from extracts of plants or parts of plants.
[0022] Within the meaning of the invention, these extracts will be assimilated as compounds a). The extracts are obtained by extraction of various parts of plants such as for example root, wood, bark, leaf, flower, fruit, seed, pod, peel. Among the plant extracts, there may be mentioned the extracts of tea leaves, rose.
[0023] Among the fruit extracts, mention may be made of extracts of apple, grapes (in particular grape seeds), or extracts of beans and / or cocoa pods. Among the vegetable extracts, there may be mentioned potato extracts, onion peels. Among the extracts of wood of trees, mention may be made of pine bark extracts, extracts of logwood wood. It is also possible to use mixtures of plant extracts. 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. More preferably, the ODP (s) of the invention is (are) chosen from: - haematein, brazile, gallic acid, tannic acid, when the dyeing process does not no use of chemical oxidizing agent; or else - haematoxylin, brasiline, gallic acid, tannic acid, when the dyeing process uses a chemical oxidizing agent 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.
[0024] According to one particular embodiment of the invention, the dye or dyes are chosen from anionic direct dyes or dyes commonly known as "acid" direct dyes or "acid dyes" for their affinity with alkaline substances. By direct anionic dyes is meant any direct dye comprising in its structure at least one CO2R or SO3R substituent with R denoting a hydrogen atom or a cation derived from a metal or an amine, or an ammonium ion. The anionic dyes may be selected from acidic nitro dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes, indigoids and acidic natural dyes. 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 dyes, polymethine such as styryl and (poly) arylmethane dyes. More preferentially, the cationic dye (s) of the invention are chosen from the hydrazono dyes of formula (Va) and (V'a), the azo compounds (Via) and (VI'a) and the following diazo compounds (Vila): Het + - C (Ra) = NN (Rb) -Ar, Q-Het + -N (Ra) -N = C (Rb) -Ar, Q-Het + -N = N-Ar, Q- (Va) (V'a) (Via) Ar + -N = N-Ar ", Q- and Het + -N = N-Ar'-N = N-Ar, Q- (VI'a) (Vila), formulas (Va), (V'a) ), (Via), (VI'a) and (Vila) with: - Het + representing a cationic heteroaryl radical, preferably with endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally substituted preferentially with one or more groups (CiC8) alkyl, such as methyl, Ar + representing an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge preferably ammonium, particularly tri (C 1 -C 8) alkylammonium such as trimethylammonium, Ar represents an aryl group, in particular phenyl, which is optionally substituted, preferentially by one or more electron donor groups such as i) (C1-C8) optionally substituted alkyl, ii) (C1-C8) optionally substituted alkoxy, iii) (di) (C1-C8) (alkyl) amino optionally substituted on the one or more alkyl groups by a hydroxyl group, iv) optionally substituted aryl (C1-C8) alkylamino, v) N- (C1-C8) alkylN-aryl (C1-C8) 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 with one or more (C1-C8) alkyl, hydroxyl or (C1-C8) groups; alkoxy; Ar "is an optionally substituted (hetero) aryl group such as phenyl or pyrazolyl optionally substituted, preferably with one or more (C1-C8) alkyl, hydroxyl, (di) (C1-C8) (alkyl) amino groups, ( C1-C8) alkoxy or phenyl, Ra and Rb, which may be identical or different, representing a hydrogen atom or an optionally substituted (C1-C8) alkyl group, preferably with a hydroxyl group, or the substituent Ra with a substituent of Het + and / or Rb with a substituent of Ar and / or Ra with Rb together with the atoms carrying them a (hetero) cycloalkyl, especially Ra and Rb, representing a hydrogen atom or a group (C1-C4) alkyl, optionally substituted by a hydroxyl group; C 2 -C 2 represents anionic counterion as defined above. According to one preferred variant of the invention, the cationic dyes are chosen from polymethine dyes of formula (Villa) and (Vlll'a) VV + 4C (Rc) = C (Rd)], ', - Ar', Q Ar- [C (Rd) = C (Rc)] ,,, - W '+, ( (VIIa) formulas (VIIa) or (VIIIa) with: - W + representing a heterocyclic or cationic heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more optionally substituted (C1-C8) alkyl groups in particular by one or more hydroxyl groups; - representing a heterocyclic or heteroaryl as defined for W - Ar representing 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, 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 (C1-C8) alkyl groups such as hydroxyethyl, vi) one or more amino or (di) (C1-C8) alkylamino groups, preferably with the C1-C4 alkyl part optionally substituted by a or more 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, pyperidinyl 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, identical or different, represent a hydrogen atom or a group (C1-C8) alkyl optionally substituted, preferably C1-C4, or Rc adjacent to VV * or Ve and / or Rd contiguous to Ar or Ar 'and / or Rc and Rd contiguous form with the atoms forming with the atoms which carry them a (hetero) cycloalkyl, especially Rc is contiguous with VV * or Ve and forms a (hetero) cycloalkyl such as cyclohexyl; - C2- 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 (Va), (V'a), (Via) and (VI'a) as defined above. More particularly those of formula (Va), (V'a) and (Via) from the dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferentially, the cationic dyes comprise an endocyclic cationic charge and of the following formula: ## STR2 ## formulas (Va-1) and (Via-1) with: R 1 representing a (C1-C4) alkyl group such as methyl; - R2 and R3, identical or different, represent a hydrogen atom or a group (C1-C4) alkyl such as methyl; and R 4 represents a hydrogen atom or an electron-donor group such as optionally substituted (C1-C8) alkyl, (C1-C8) alkoxy optionally substituted, (di) (C1-C8) (alkyl) amino optionally substituted on the or the alkyl groups by a hydroxyl group; in particular, R 4 is a hydrogen atom; Z represents a CH group or a nitrogen atom, preferably CH 2 -CO 2 as defined above, and preferably represents a halide or a mesylate.
[0025] Particularly the dyes of the invention are chosen from those of formula (IIIa-1) and (IVa-1) is chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives: 3029409 H, c'N ## STR2 ## with Q - as defined above, preferably represents a halogenide or a halogenide. a mesylate. According to the invention, the synthetic dye (s), natural (s), and / or the natural extract (s) used as ingredient (a) in one or more composition (s) cosmetic (s) useful (s) in the process according to the invention is (are) preferably from 0.001% to 20% by weight of the total weight of the composition or compositions containing them .. As for the Pure dyes, especially pure ODPs, the content in the composition or compositions containing them is preferably between 0.001 and 5% by weight of each of the compositions containing them. With regard to the extracts, the content in the composition or compositions containing the extracts as such is preferably between 0.1 and 20% by weight of each of these compositions, and better still between 0.5 and 10% by weight of the compositions containing them. b) titanium salt (s): The titanium salt (s) of the invention may be one or more organic (s) or inorganic (s) salt (s) of titanium.
[0026] For the purposes of the present invention, the term "organic titanium salt" means the salts themselves, derived 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 proton H +, or H30 + in aqueous media, which comprises at least one C1-C20 hydrocarbon chain, optionally unsaturated, linear or branched, a group ( hetero) cycloalkyl, or (hetero) aryl and at least one acidic chemical function being in particular chosen from carboxy COOH, sulfuric SO3H, 502H, 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 (I) as defined above and preferably is or are a hydroxy acid alpha such as lactic, glycolic, tartaric or citric acids. Preferentially, the organic titanium salt resulting from the action of one or more organic acid (s) as defined previously, 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). Preferably, the organic titanium salt (s) of the invention is (are) chosen from those of the following formula (IA): ## STR2 ## Formula (IA) in which: - A is identical to that of the formula (I) - n, n 'and n "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, in particular chosen from alkali metal cations such as Na, or K, alkaline earth such as Ca or organic such as ammonium, preferably ammonium or an atom. hydrogen; - designating Ti (01-1), r, or Ti (0), r / 2, or Ti (01-1) ,, i (0) ,, 2 with m1 + m2 = n ", preferably the radical A of the compound (IA) 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 inclusive between 0 and 5, such as between 0 and 2, especially the carboxylic acid (s) used to form the organic titanium salt (s) of the invention are chosen from α-hydroxy acids, and preferably the acid is chosen from citric acid and lactic acid, tartaric acid, and glycolic acid, preferably from lactic and glycolic acid, and preferably the organic titanium salt (s) of the invention is (are) chosen from those of formula (IB): Ra Y ON1 / 0 Ti X "yi (IB) 2- M + M + Formula (IB) in which: - L 'and L", identical or different, represent a group divalent (hetero) arylene, C6) alkylene, (C2-C6) alkenylene, said alkylene and arylene groups being optionally substituted by 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 by a (C1-C4) alkyl group; 10 - 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 as defined for X 'and X ", preferably Y and Y' are the same and represent an oxygen atom; Ra and Rb, which may be identical or different, represent a hydrogen atom, or a (C 1 -C 6) alkyl, (C 2 -C 6) alkenyl or (hetero) aryl group; 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 titanium organic salt (s) of the dyeing process is the dihydroxybis (lactato) titaniumlV salt such as those of the following formula: ## STR2 ## The staining method may use one or more organic acids b1) of formula (I) as defined above. According to an advantageous variant, the dyeing process also employs 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 has no 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).
[0027] 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).
[0028] 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 20% by weight relative to the total weight of the composition or compositions containing them. In particular, the titanium organic 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. . c) the non-cellulosic polysaccharide (s) According to the present invention, the dyeing process uses c) one or more non-cellulosic polysaccharide (s) ie a polysaccharide polymer (s) not cellulosic (s), which preferably is (are) thickener (s). The non-cellulosic polysaccharide (s) according to the invention may be of natural or synthetic origin, they may be modified chemically or otherwise, associative or not.
[0029] The non-cellulosic polysaccharide (s) of the invention is (are) chosen in particular from glucans, modified or non-modified starches (such as those derived, for example, from cereals such as wheat, corn or rice, vegetables such as sweet pea, tubers such as potatoes or cassava), amylose, amylopectin, glycogen, dextrans, mannans, xylans, arabans, galactans , galacturonans, chitin, chitosans, glucoronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acids and pectins, arabinogalactans, carrageenans, agars, gum arabic, tragacanth gums, gums Ghatti, Karaya gums, locust bean gums, galactomannans such as guar gums and their nonionic derivatives (hydroxypropyl guar), and mixtures thereof. In general, the compounds of this type which can be used in the present invention are chosen from those described in particular in "Encyclopedia of Chemical Technology, Kirk-Othmer, Third Edition, 1982, Volume 3, pp. 896- 900, and Vol 15, pp 439-458 ", in" Polymers in Nature, by EA MacGREGOR and CT GREENWOOD, Editions John Wiley & Sons, Chapter 6, pp 240-328, 1980 "and_ in the Industrial Gums - Polysaccharides and their Derivatives, Edited by Roy L. WHISTLER, Second Edition, Academic Press Publishing Inc. "According to a particular embodiment of the invention, where the non-cellulosic polysaccharide (s) is (are) selected ) among homopolysaccharides, consisting of the same monosaccharide, such as for example fructans, glucans, galactans or mannans.
[0030] According to another embodiment of the invention the non-cellulosic polysaccharide (s) is (are) chosen from heteropolysaccharides, consisting of different monosaccharides. More particularly, the non-cellulosic polysaccharide (s) may be chosen from the bioheteropolysaccharides. For the purposes of the present invention, the term "bio heteropolysaccharides" is intended to mean substances synthesized by fermentation of sugars by microorganisms. In particular, bioheteropolysaccharides often have units selected from the mannose, glucose and glucuronic acid or galacturonic acid units in their chain, these units optionally being acylated. In particular, xanthan gums produced by the bacterium xanthomonas campestri and the mutants and variants thereof can be mentioned. Mention may also be made of scleroglucan gums produced by Sclerotium rolfsii, gellan gums produced by Pseudomonas elodea or Sphingomonias, pullulan gums produced by Aureobacidium pullulens, Curdlar gums produced by faecalis-like alkaligenic Faecalis, dextran gums produced by many organisms including Leuconostoc mesenteroides and Leuconostoc dextrantum, grifolane gums produced by Grifola frondera, lentinan gums produced by Lentinus e dodes, Schizophyllane gums produced by Schizophyllum commine, Spirulin sybsyla spirulinum gums and krestine gums produced by Coriates versicolor.
[0031] The non-cellulosic polysaccharide (s) of the invention may be chemically modified or not.
[0032] According to a particular embodiment of the invention the non-cellulosic polysaccharide (s) is (are) modified (s). Mention may in particular be made of nonionic guar gums modified with (C 1 -C 6) (poly) hydroxyalkyl groups. Among the hydroxyalkyl groups, there may be mentioned by way of example, the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl groups. These guar gums are well known in the state of the art and may, for example, be prepared by reacting corresponding alkene oxides, such as, for example, propylene oxides, with guar gum so as to obtain guar gum modified with hydroxypropyl groups.
[0033] The level of (poly) hydroxyalkylation, which corresponds to the number of alkylene oxide molecules consumed by the number of free hydroxyl functions present on the guar gum, preferably ranges from 0.4 to 1.2. Such nonionic guar gums optionally modified with hydroxyalkyl groups are for example sold under the trade names Jaguar HP8, Jaguar HP60 and Jaguar HP120, Jaguar DC 293 and Jaguar HP 105 by the company Rhodia Chimie or under the name GALACTASOL 4H4FD2 by the company AQUALON. Non-cellulosic polysaccharides also include non-cellulosic associative polysaccharides well known to those skilled in the art and in particular of nonionic, anionic, cationic or amphoteric nature. It is recalled that the "associative polysaccharides" are polymers capable, in an aqueous medium, to associate reversibly with each other or with other molecules. Their chemical structure more particularly comprises at least one hydrophilic zone and at least one hydrophobic zone. By "hydrophobic group" is meant a linear or branched, saturated or unsaturated hydrocarbon-based radical or polymer comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 atoms. carbon and more preferably from 18 to 30 carbon atoms. Preferably, the hydrocarbon group comes from a monofunctional compound. By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It can also denote a hydrocarbon polymer such as for example polybutadiene. According to a particular embodiment of the invention, the non-cellulosic polysaccharide (s) of the invention is (are) chosen from the anionic or neutral associative polymer (s). ) as follows: - (a) which comprise at least one hydrophilic unit, and at least one fatty-chain allyl ether unit, more particularly those whose hydrophilic unit consists of an unsaturated anionic monomer; ethylene, more particularly with a vinyl carboxylic acid and most preferably with acrylic acid or methacrylic acid or mixtures thereof. (b) which comprise i) at least one hydrophilic unit of olefinic unsaturated carboxylic acid type, and ii) at least one hydrophobic unit of unsaturated carboxylic acid alkyl (010-030) ester type. Alkyl esters (010-030) of unsaturated carboxylic acids useful in the invention include, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate, dodecyl acrylate, and corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate, and dodecyl methacrylate. Anionic polymers of this type are for example described and prepared according to US Pat. Nos. 3,915,921 and 4,509,949. (C) which comprise at least one ethylenically unsaturated monomer containing a sulphonic group, in free form or partially or completely neutralized and comprising at least one hydrophobic part. (d) which comprise at least one hydroxy (C1-C6) alkyl guar group such as associative guar derivatives such as hydroxypropyl guars modified with a fatty chain such as the product ESAFLOR HM 22 (modified with an alkyl chain at 022) sold by LAMBERTI; the product MIRACARE XC 95-3 (modified with a C14 alkyl chain) and the product RE 205-146 (modified with an alkyl chain at 020) sold by RHODIA CHIMIE, e) which comprise alkyl or polyalkyl esters of dextrin or of inulin.
[0034] It may be in particular a mono-or poly-ester of dextrin and of at least one fatty acid and in particular having the following formula (IX): CH2OR, O OR2O n (IX) OR3 Formula (IX ) in which: n is an integer ranging from 3 to 200, in particular ranging from 20 to 150, and in particular ranging from 25 to 50; R 1, R 2 and R 3, which are identical or different, are chosen from hydrogen; or an acyl group (RC (O) -) in which the radical R is a hydrocarbon group, linear or branched, saturated or unsaturated, having from 7 to 29, in particular from 7 to 21, in particular from 11 to 19, more particularly 13 to 17 or even 15 carbon atoms, provided that at least one of said radicals R1, R2 or R3 is different from hydrogen.
[0035] In particular, R 1, R 2 and R 3 may represent hydrogen or an acyl group (RC (O) -) in which R is a hydrocarbon radical as defined above, with the proviso that at least two of said radicals R 1, R 2 or R3 are identical and different from hydrogen. All of the radicals R1, R2 and R3 may be an acyl group (R-C (O)) identical or different, and in particular identical. In particular, n previously exposed advantageously varies from 25 to 50, in particular is equal to 38 in the general formula of the saccharide ester that can be used in the present invention. In particular, when the radicals R 1, R 2 and / or R 3, identical or different, are an acyl group (RC (O)), these may be chosen from caprylic, capric, lauric, myristic, palmitic, stearic and arachic radicals. behenic, isobutyric, isovaleric, 2-ethylbutyric, ethylmethylacetic, isoheptanoic, 2-ethylhexanoic, isononanoic, isodecanoic, isotridecanoic, isomyristic, isopalmitic, isostearic, isoaracic, isohexanoic, decenoic, dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic , elaidic, asclepine, gondoleic, eicosenoic, sorbic, linoleic, linolenic, punicic, stearidonic, arachidonic, stearic, and mixtures thereof. Preferably, at least one dextrin palmitate is used as dextrin ester and fatty acid (s). This can be used alone or mixed with other esters.
[0036] Advantageously, the dextrin and fatty acid ester has a degree of substitution less than or equal to 2.5 on the basis of a glucose unit, in particular ranging from 1.5 to 2.5, preferably from 2 to 2,5. The weight average molecular weight of the dextrin ester may be in particular from 10,000 to 150,000, especially from 12,000 to 100,000 and even from 15,000 to 80,000.
[0037] Dextrin esters, in particular dextrin palmitates, are commercially available under the name RHEOPEARL TL or RHEOPEARL KL from Chiba Flour. Preferably, the non-cellulosic polysaccharide (s) of the invention are not chemically modified. More preferably, the xanthan and scleroglucan gums are used. Even more preferentially, the scleroglucan gums are used. Scleroglucan gums are nonionic natural water-soluble polymers that are produced by many filamentous fungi, such as, for example, Sclerotium rolfisii. For the purposes of the invention, the term "scleroglucan" means a hydrophilic colloid in the form of a D-glucopyranose polymer, generally of microbial origin, in particular of fungal origin, which is known to stabilize and thicken aqueous systems by increasing their viscosity. On an industrial scale, scleroglucans are obtained by submerged aerobic culture of selected strains of microorganisms, in particular selected fungal strains. In particular, scleroglucan can be obtained in a known manner by an aerobic fermentation process of a Sclerotium fungus. Scleroglucans consist of a sequence of f3-1,3-glucose units with a basic sequence of three units of f3-1,3-glucose comprising a side chain of f3-1,6-glucose. Scleroglucans are compounds of the following formula (X): (X) Formula (X) wherein n is an integer from 500 to 1600. The integer "n" materializes the degree of polymerization of said scleroglucan. In some embodiments, the scleroglucan has an average molecular weight ranging from 1x106 to 12x106, which includes 2x106 to 10x1e. Preferentially, the molecular weight of a scleroglucan is determined according to the Taudinger index ("Staudinger Index") using the following Mark-Houwink equation (A): MW = hi / 4x45x10-11 / 149. The scleroglucans according to the invention include the products marketed under the name Actigum CSTM by Sanofi Bio Industries, such as the product marketed under the reference Actigum CS 11TM. The scleroglucans according to the invention include the products sold under the name Amigel Tm by Alban Muller International. Also encompassed are other scleroglucans such as the glyoxal-treated one described in French Patent Application No. FR2633940. Preferably the non-cellulosic polysaccharide (s) of the invention is (are) of natural origin, not chemically modified, and non-associative (s). Preferably, the molecular weight (MW) of the non-cellulosic polysaccharide (s) of the invention is between 100,000 and 50,000,000. Even more preferably, the molecular weight is between 250,000 and 50,000. 800 000.
[0038] The non-cellulosic polysaccharide (s) of the invention generally represent from 0.01 to 30%, preferably from 0.1 to 20%, more preferably from 0.1 to 10% by weight of the total weight of the composition containing them used. according to the invention. D) the chemical oxidizing agent (s) According to one particular embodiment of the invention, the dyeing method also uses one or more chemical oxidizing agent (s) (s) ). By chemical oxidizing agent is meant an oxidizing agent different from the oxygen of the air. More particularly, the dyeing process employs 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 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. According to a preferred embodiment of the invention, the composition contains one or more chemical oxidizing agent (s) chosen from i) urea peroxide, ii) polymeric complexes which can release hydrogen peroxide selected from polyvinylpyrrolidone / H 2 O 2; iii) oxidases; iv) perborates and y) percarborates. 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. According to one particular embodiment of the invention, the chemical oxidizing agent or agents used preferably represent from 0.001% to 12% by weight of chemical oxidizing agents (of hydrogen peroxide) with respect to the total weight of the composition or the compositions containing them or, more preferably, from 0.2% to 2.7% by weight. e) the alkalinizing agent (s) According to one particular embodiment of the invention, the dyeing process uses one or more alkalinizing agent (s) e). It is base (s) allowing to increase the pH of the composition (s) in which it is located. The basifying agent is a Bronsted, Lowry or Lewis base. It can be mineral or organic. Particularly said agent is selected from i) (bi) carbonates, ii) ammonia, iii) alkanolamines such as mono-, di- and triethanolamines and their derivatives iv) oxyethylenated and / or oxypropylenated ethylene diamines, v) inorganic or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) basic amino acids such as arginine, lysine, ornithine, citruline and histidine, and viii) compounds of the following formula (XI): ## STR5 ## Formula (XI) in which W is a divalent (C1-C8) alkylene radical optionally substituted with at least one hydroxyl group or at least one (C1-C4) alkyl radical and / or optionally interrupted by at least one heterotatome such as oxygen, sulfur or with a group -N (Re) -; Ra, Rb, Rc, Rd and Re, identical or different, represent a hydrogen atom, a (C1-C4) alkyl or hydroxy (C1-C4) alkyl radical, preferably W represents a propylene radical. 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 metal such as the hydroxides of Group III, IV, V and VI metals, d) the hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide. The hydroxide may be formed in situ such as, for example, guanidine hydroxide by reaction of calcium hydroxide and guanidine carbonate. By (bi) carbonates i) is understood to mean: a) alkali metal carbonates (Met2 +, CO32-), alkaline earth metal (Met2 +, CO32-) ammonium ((R "4N +) 2, C032 -) or phosphonium ((R "4P +) 2, C032- with Met 'representing an alkaline earth metal and Met representing an alkali metal, and R", which are identical or different, represent a hydrogen atom, a group (CiC6 optionally substituted alkyl such as hydroxyethyl), and b) bicarbonates, also known as hydrogenocarbonates, of the following formulas: R '+, 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 (002, 35 H2O); and - Met2 + (1-1CO3) 2 with Met 'representing an alkaline earth metal.
[0039] More particularly, the basifying agent is chosen from alkali or alkaline earth metal (bi) carbonates and amino acids such as arginine; preferentially alkali metal (bi) carbonates and amino acids. There may be mentioned carbonates or hydrogenocarbonates of Na, K, Mg, Ca and their mixtures, and in particular Na hydrogen carbonate. These hydrogencarbonates can 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] = Na2CO3, sodium hydrogencarbonate or sodium bicarbonate [144-55-8] = NaHCO3, and sodium dihydrogen carbonate = Na (HCO3) 2. According to a particularly advantageous embodiment, the alkalinizing agent (s) (e) is (are) chosen from amino acids such as arginine and (bi) carbonates which are particularly alkaline or alkaline-earthy, alone or in mixtures. They are preferably together during the coloring process.
[0040] The alkalinizing agent (s) as defined above preferably represent from 0.001% to 10% by weight relative to the weight of the composition (s) containing them. More particularly from 0.005% to 8% by weight of the composition. 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 e) as defined above or from one or more other compositions.
[0041] Preferably, the water comes from at least one composition comprising at least one compound selected from a) to e) as defined above. 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. By organic solvent is meant an organic substance capable of dissolving or dispersing another substance without chemically modifying it.
[0042] Organic solvents: 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, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol. Preferably, the dye composition i.e 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 even more preferably between 5 and 30% by weight approximately.
[0043] Adjuvants: The composition (s) of the dyeing process according to the invention may or 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 their mixtures other than non-cellulosic polysaccharides c) as defined above, inorganic or organic thickeners other than non-cellulosic polysaccharides c) such as defined above, 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 silicones or n volatile, modified or unmodified, film-forming agents, ceramides, preservatives, opacifying agents. The dyeing process of the invention may also use in addition to compounds a), b), c) and optionally d) at least one other particular carboxylic acid of formula (I) as defined above. More particularly, the carboxylic acid (s) of formula (I) are such that A represents a monovalent (C 1 -C 6) alkyl or polyvalent (C 1 -C 6) alkylene group optionally substituted with one or more hydroxy 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. weight at 25 ° 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 the ahydroxy acids. The preferred acids of the invention are selected from glycolic acid, lactic acid, tartaric acid, citric acid.
[0044] The salts of the acids of formula (I) may 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 chosen from surfactants such as anionic, nonionic surfactants or mixtures thereof and inorganic or organic thickeners. The above adjuvants are generally present in an amount for each of them ranging from 0.01% to 40% by weight relative to the weight of the composition, preferably from 0.1% to 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 coloring 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 carrying out 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 composition (s): In accordance with the present invention, the pH of at least one of the cosmetic compositions comprising at least one of ingredients a), b), c), d) is acidic, ie less than 7.0, preferably less than 5.0, especially at a pH between 0 and 4, more preferably between 0.5 and 3.5, preferably between 1 and 3. According to one embodiment , the pH of the cosmetic composition (s) containing one or more alkaline agents preferably chosen from (bi) carbonates is alkaline, ie greater than 7, preferably between 8 and 12 and, more particularly, between 8 and 10 inclusive. 5.
[0045] When the process according to the invention uses one or more ODPs, the composition containing the ODP (s) a) preferably has an acidic pH of less than 7, preferably less than 5, particularly at a pH between 0 and 0 inclusive. 4, more particularly between 0.5 and 3.5, preferably between 1 and 3. According to a particular embodiment of the invention, the composition containing the or titanium salts b) and not containing ( bi) carbonates have a pH of less than 7, and preferably less than 5, especially at a pH between 0 and 4 inclusive. The pH of these compositions can be adjusted to the desired value by means of alkalinizing agents such as defined above in e) or from acidifying agents usually used in dyeing keratin fibers or else using conventional buffer systems. 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 -O (O) -OH, preferably of formula (I) as defined above, preferably comprising between 1 and 4 carboxylic acid groups such as 1 or 2; or selected from: i) (C1-C10) alkyl- [C (O) -OH] n and ii) het- [C (O) -OH] n, where n is an integer from 1 to 4 inclusive of preferably between 1 and 2, hetero-cyclic group such as pyrrolidone, the alkyl or hetero group may be optionally substituted with one or more groups, especially selected from OH, and (di) (CiC6) (alkyl) amino.
[0046] Staining process in one or more steps The method for staining keratinous fibers consists of treating, in one or more steps, with one or more cosmetic compositions containing, taken together or separately in the one or more compositions, the following ingredients: a) one or more dye (s) such as previously defined, preferably ODP (s) as (s) previously defined; b) one or more titanium salt (s); optionally b1) one or more carboxylic acid (s) of formula (I) as defined above; c) one or more non-cellulosic polysaccharide (s) as defined previously; d) optionally one or more chemical oxidizing agent (s), especially chosen from hydrogen peroxide or one or more hydrogen peroxide generator system (s); preferably, the composition or at least one of the compositions used in the dyeing process is at acidic pH, ie less than 7, preferably less than 5, especially at a pH between 0 and 4 inclusive, more particularly between 0.5 and 3.5, preferably between 1 and 3. According to a particular embodiment of the invention, the dyeing process is carried out in at least two stages which comprises a first step in which the keratinous fibers are produced. are treated with a cosmetic composition comprising a) one or more dyes, preferably one or more ODP (s) as defined previously, b) one or more salt (s) of titanium and optionally b1) one or more carboxylic acid (s) as defined above and c) one or more non-cellulosic polysaccharide (s) as defined previously; followed by a second step in which is applied an alkaline cosmetic composition ie whose pH is greater than 7, and preferably between 8 and 12, especially between 8 and 10.5, which comprises e) one or more agents ( s) alkalinizing (s) and possibly d) one or more chemical oxidizing agent (s).
[0047] Preferentially, the cosmetic composition applied to the keratinous fibers during the second step further comprises d) one or more chemical oxidizing agent (s), chosen in particular from hydrogen peroxide or one or more system (s) generator (s) of hydrogen peroxide, preferably hydrogen peroxide.
[0048] The pause time after application of the composition 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. According to a particular embodiment of the invention, the process for staining keratinous fibers is carried out in two stages by the application to the keratin fibers of a dye composition comprising ingredients a), b), b1) and c ), as defined above, then, in a second step, a composition comprising the ingredient e) and optionally the ingredient d) as defined above is applied to said keratin fibers, it being understood that at least one of the two compositions is aqueous. Preferably, the composition comprising the dye (s) in particular ODP (s) a) is aqueous. Even more preferentially, the two compositions used in this embodiment are aqueous. For this staining process, the pause time after application 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 comprising the ingredient e) 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 method for dyeing keratin fibers is in two or three steps. According to this embodiment, the process for dyeing keratinous fibers is carried out in several steps by application to the keratinous fibers in a first step of a cosmetic composition comprising: a) one or more dyes, in particular one or more derivatives (s); ODP (s), in particular chosen from: - haematein, brazileine, gallic acid, tannic acid, when the dyeing process does not use a chemical oxidizing agent, ); or else - hematoxylin brasiline, when the dyeing process uses a chemical oxidizing agent d); b) one or more titanium salt (s) as defined previously and b1) optionally one or more carboxylic acid (s) of formula (I) as defined (s) previously with A representing a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted with one or more hydroxyl groups, and n representing an integer between 0 and 5 inclusive, 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: c) one or more non-cellulosic polysaccharide (s) as defined previously and particularly unmodified such as those selected from glucans, starches, amylose, amylopectin, glycogen, dextrans, mannans, xylans, arabans, galactans, galacturonans, chitin, chitosans, glucoronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acids and pectins, arabinogalactans, carrageenans, agars, gum arabic, tragacanth gums, ghatti gums, karaya gums, locust bean gums, galactomannans such as guar gums and their nonionic derivatives (hydroxypropyl guar), and mixtures thereof; preferentially xanthan and scleroglucan gums, more preferably scleroglucan gums; d) optionally one or more chemical oxidizing agent (s) selected from hydrogen peroxide or one or more hydrogen peroxide generator system (s); e) one or more basifying agent (s) chosen from amino acids such as arginine and (bi) carbonates particularly alkaline or alkaline earth, alone or in mixtures; it being understood that: the composition comprising the carboxylic acid (s) is at acidic pH, ie less than 7, preferably less than 5, particularly at a pH ranging between 1 and 3, and the composition comprising the agent (s) alkalizing agent is at alkaline pH, preferably between 8 and 12 and more particularly between 8 and 10. Particularly the dyeing process of the invention is carried out in at least two stages, in the first step the ingredients a), b ) and c) are applied together on the keratinous fibers, in particular the hair, then in the second step the ingredients d) and e) are applied together on said fibers. According to one 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 comprising: a) one or more ODP derivative (s) ), as defined above, especially chosen from among: - herneatin, brasiline, gallic acid, tannic acid, when the staining process does not involve chemical oxidizing agent d); or else - hematoxylin or 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; and c) one or more non-cellulosic polysaccharide (s) as defined previously; 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 as defined above; e) one or more basifying agent (s) chosen from amino acids and (bi) carbonates particularly alkaline or alkaline earth alone or in mixture; It being understood that: the composition comprising the carboxylic acid (s) is at acidic pH, ie less than 7, preferably less than 4b, particularly at a pH inclusive of between 1 and 3, and the composition comprising the basifying agent (s). is at alkaline pH, preferably between 8 and 12, and more particularly between 8 and 10. In some applications, the application temperature is generally between room temperature (15 to 25 ° C.) and 220 ° C. ° C and more particularly between 15 and 45 ° C. Thus, it is advantageous, after application of the composition 35 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 carried out by means of a hairdressing helmet, a hair dryer, an infrared dispenser and other conventional heating devices. Both heating and smoothing of the hair can be used to heat a heating iron at a temperature 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 drying of the keratinous fibers between each step, in particular before carrying out the last step comprising the application of a composition containing the ingredient ). The mechanical wiping and intermediate leveling steps are also referred to as "controlled rinsing" to differentiate themselves from "conventional rinsing" and "rinsing off". By "mechanical wiping" fibers is meant the rubbing of an absorbent object on the fibers and the physical removal by the absorbent object 10 of the surplus ingredient (s) not penetrated into 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. 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.
[0049] Drying means the action of evaporating organic solvents and / or water in one or more compositions used in the process of the invention, comprising or not one or more ingredients a) to e) such than previously defined. 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. A particular embodiment of the invention relates to a dyeing process which is carried out at room temperature (25 ° C).
[0050] 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 e) as defined previously can be aqueous or powder, with particularly at least one of said compositions being aqueous. According to a first variant, the kit comprises 5 compartments, the first 4 compartments respectively comprising the powder ingredients a), b), c) and e) as defined above and in the 5th compartment containing an aqueous oxidizing composition such as the water comprising d) as defined above.
[0051] In this other embodiment, at least one of the four compositions is aqueous and the derivative (s) orthodiphenol (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), 10) and c) the second compartment comprises d) in powder form or in an aqueous medium, preferably 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 the 2-compartment comprises d) in the form of a powder or in an aqueous medium, preferably second composition is aqueous and the 36 "compartment comprises c). According to a variant, the device according to the invention comprises; in addition, an additional composition comprising one or more treating 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, fathoms 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.
[0052] The invention also relates to the use of said dye cosmetic composition for dyeing keratinous fibers. The subject of the invention is also a cosmetic composition for dyeing keratinous fibers containing compounds a), b), b1), c), d) and e) 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 example serves to illustrate the invention without being limiting in nature. EXAMPLE 1 The following compositions are prepared from the following ingredients in the following proportions indicated in grams per 100 grams of composition: dyeing composition Composition I Quantity 76% hemp furlwood extract: a) 4 g Dihydroxybis (ammonium lactate) titanium (IV) at 50% by weight: b) 10.3 g Scleroglucan gum (sclerotium gum) marketed by Alban Muller under the trade name AMIGEL GRANULE: c) 1 g Ethanol 10 g 5 g Benzyl alcohol Glycolic acid 1 $ g Water qs 100 g Agent, pH (sulfuric acid) qsp pH = 2 ± 0.3 revealing composition: Composition B quantity Hydrogen peroxide (at 50%): d) 1.7 g sodium bicarbonate e) 5 g L-arginine: e) 7 g Hydroxypropyl starch phosphate marketed under the name STRUCTURE ZEA by AKZO NOBEL 5g Water gsp 100 g pH agent (soda) p H 10.2 ± 0.3 10 L The coloring composition 1 and then the composition B are applied with a brush to hair: - Caucasian with 90% natural and permanent white hair, - Chinese with 100% natural white hair. 45 minutes at 40 ° C. for composition 1 and 15 minutes at 40 ° C. for composition B. A rinsing is carried out before the application of composition B. At the end of these exposure times, the wicks are washed with Elsève multi-vitamin shampoo, rinsed and then dried with a helmet.
[0053] Results of colorations It is found that black locks are very intensely colored, which is corroborated with the colorimetric measurements below. In addition, it appears that the coloration is visually homogeneous and tenacious with respect to successive shampoos. The color of the locks was 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.
[0054] 10 Increase in color: The color variation between strands of causal hair at 90% natural white, or 100% Chinese hair before and after treatment or staining are defined by (AE *) according to the following equation AE * In this equation, L *, a * and b * represent the values measured on locks of hair after staining and Lo. *, ao * and bo * represent the values measured on strands of unstained virgin hair. The higher the value of AE *, the better the rise of the color. The color and color of the hair are shown in the table below. L * AE * Types of hair and treatment Reference no hair dyed Natural Caucasian 90% white 68.92 1.64 20,44 Natural Chinese 100% white 79,33 2,65 28,19 Composition 1 then B Natural Caucasian 90% white Black 20,47 0,63 1,04 52,20 Natural Chinese 100% white Black 22,74 0, 0.91 62.85 EXAMPLE 2 The following coloring compositions 3 and 4 are prepared according to the same protocol as in Example 1: Compositions Campex extract 76% hematoxylin a) 4 g 4 g Dihydroxybis (ammonium lactate ) titanium (IV) at 50% by weight b) 10.3 g 10.3 g PECTIN LOW METHOXYL CITRUS STANDARDIZED. sold under the name UNIPECTINE OF 600 1 g 20 3029409 48 C by CARGILL c) Xanthan gum (XANTHAN GUM) marketed under the name RHODICARE XC by Solvay c) - 1 g Ethanol 15 g 15 g Benzyl alcohol 5 g 5 g Glycolic acid 15 g 15 g Water qs 100 g qs 100 g pH agent Qsp pH = 2 After the keratinous fibers have been treated with compositions 3 and 4, the locks obtained are of a very powerful black, and intense. 5

权利要求:
Claims (20)
[0001]
REVENDICATIONS1. A process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, in which said fibers are treated, in one or more steps, with one or more cosmetic compositions containing, taken together or separately in the one or more compositions, the the following ingredients: (a) one or more dyes chosen from oxidation dyes and synthetic direct dyes and dyes of natural origin; b) one or more salt (s) of Ti; optionally b1) one or more carboxylic acid (s) of formula (I) below,; ## STR3 ## and its salts, in which: A represents a monovalent group when n is 0 or polyvalent when n is greater than or equal to 1, a hydrocarbon comprising from 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 not one or more hydroxyl groups; preferably A represents a monovalent (C1-C6) alkyl or polyvalent (CiC6) alkylene group optionally substituted by 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; c) one or more non-cellulosic polysaccharide (s); preferably at least one of the compositions used in the dyeing process is at acidic pH, ie less than 7.0, preferably less than 5, especially at a pH of between 0 and 4, more particularly between 0, 5 and 3.5, preferably between 1 and 3.
[0002]
2. The method of dyeing according to claim 1, characterized in that the dye (s) a) are chosen from direct dyes, preferably from direct dyes of natural origin, better from orthodiphenols (ODPs).
[0003]
3. Staining process according to any one of the preceding claims, characterized in that the ingredient a) is an aromatic ring ODP, this aromatic ring O HO 3029409 being chosen from benzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene, phenanthrene, isoindole, indoline, isoindoline, benzofuran, dihydro-benzofuran, chroman, isochromane, chromene, isochromene, quinoline, tetrahydroquinoline and isoquinoline, said aromatic ring having at least two hydroxy groups carried by two contiguous adjacent atoms of the aromatic ring.
[0004]
4. Staining process according to any one of the preceding claims, characterized in that ingredient a) is a ODP of formula (II) below or one of its 10 oligomers, tautomers, optical isomers, geometric isomers, and that its salts or its solvates such as hydrates: OH formula (II) in which: 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 (Ci- C20) alkyl or (C1-C20) alkoxycarbonyl, vi) optionally substituted amino, vii) C20) linear or branched alkyl optionally substituted, viii) (C2-C20) optionally substituted linear or branched alkenyl, ix) optionally substituted cycloalkyl, x) C20) alkoxy, xi) (C1-C20) alkoxy (C1-C20) alkyl, xii) (C1-C20) alkoxyaryl, xiii) aryl which may be optionally substituted, xiv) aryl, xv) substituted aryl, xvi) heterocyclic, saturated or unsaturated, bearing or not a cationic or anionic charge, optionally substituted and / or optionally fused with an aromatic ring, preferably benzene, said aromatic ring being optionally substituted, in particular by one or more hydroxyl or glycosyloxy groups, xvii) a radical containing one or more atoms of silicon; 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, R1 to R4 together form from one to four rings; more particularly, R2 and R3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring carrying both hydroxy.
[0005]
5. Staining process according to any one of the preceding claims, characterized in that the derivative (s) ODP (s) a) are chosen from: 5 - flavanols such as catechin and epichatechin gallate, - 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 tetrahydroxy-3,3 ', 4,5'-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, - orthopolyhydroxyisocoumarins, - orthopolyhydroxycoumarones, 20 - orthopolyhyds oxyocoumarones, - orthopolyhydroxychalcones, - orthopolyhydroxychromones, - 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, - proanthocyanidins and in particular proanthocyanidins Al, A2, Bl, B2, B3 and C1 C1, - chromanics, and chromenics, - proathocyanines, - the tannic acid, ellagic acid, and mixtures of the foregoing compounds; preferably the derivative (s) orthodiphenol (s) are chosen from haematein, brasiline, gallic acid, tannic acid, hematoxylin and brasiline and mixtures thereof.
[0006]
6. Staining process according to any one of claims 3 to 5, characterized in that the derivative (s) ODP (s) natural (s) a) is (are) chosen (s) from the extracts animals, bacteria, fungi, algae, plants and fruits.
[0007]
7. A method of dyeing according to any one of the preceding revendtCations, characterized in that the acid (s) b1) is (are) of formula (I) with A representing a monovalent group (C1-C6) alkyl or polyvalent (C1-C6) alkylene optionally substituted with one or more hydroxyl groups, and n representing an integer between 0 and 5 inclusive, such as between 0 and 2, especially the carboxylic acid or acids of the invention are chosen from the EO hydroxy acids; preferably the acid is selected from citric acid, lactic acid, tartaric acid, and glycolic acid.
[0008]
8. Staining process according to any one of the preceding claims, wherein the acid (s) b1) of formula (I) or their salts, is (are) present in the composition or compositions containing them in a content ranging from 0.1 to 20% by weight.
[0009]
9. Staining process according to any one of the preceding claims, characterized in that the salt (s) of titanium are chosen from organic or inorganic titanium salts, preferably from organic titanium salts and from (s) which (s) titanium is in particular of oxidation state 2, 3 or 4 preferably of oxidation degree 4.
[0010]
10. Coloring process according to the preceding claim, characterized in that the organic salt (s) of titanium b) is (are) from (s) the reaction of organic acid (s) (s) ) on titanium, wherein the organic acid (s) is (are) chosen from organic acids which comprise a) at least one C 1 -C 20 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, phosphoric acid P031-12, 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 acid, lactic acid; , tartaric, and glycolic and better still lactic and glycolic acids. 35
[0011]
11. Staining process according to any one of the preceding claims, characterized in that the acid (s) b1) is (are) of formula (I) as defined in claim 1 or 7 and the last one (s) is (are) different from the organic acid (s) of the titanium salt as defined in claim 9. 3029409 53
[0012]
12. Coloring method according to any one of the preceding claims, characterized in that the organic salt (s) titanium (s) b) is (are) chosen from those of formula (IA) following: 5 0M2 A ## STR2 ## wherein: A is as defined in claim 1 or 7; n, n ', n ", identical or different, are 1, 2, 3, 4 with n' + n" = 6; M1 and M2, which may be identical or different, represent a cationic counterion such as an alkali metal (Na, K), alkaline-earth (Ca) or organic metal cation such as ammonium, preferably ammonium or a hydrogen atom; - designating Ti (01-1), r, or Ti (0), r / 2, or Ti (OH), i (0) ,, 2 with m1 + m2 = n ", preferably, the salt (s) The titanium organic (s) of the dyeing process is the dihydroxybis (lactate) titaniumlV salt such as those of the following formula: ## STR2 ##
[0013]
13. Staining process according to any one of the preceding claims, characterized in that said process uses c) one or more non-cellulosic polysaccharide (s) of natural origin, preferably unmodified (s). chemically, and not associative (s); particularly the non-cellulosic polysaccharide (s) is (are) chosen from glucans, starches (such as those derived, for example, from cereals such as wheat, corn or rice, from vegetables such as sweet pea, tubers such as potatoes or cassava), amylose, amylopectin, glycogen dextrans, mannans, xylans, arabans, galactans, galacturonans, chitin, chitosans, glucoronoxylans, arabinoxylans, xyloglucans, glucomannans, pectic acids and pectins, arabinogalactans, carrageenans, agars, gum arabic, tragacanth gums, ghatti gums, karaya gums, carob, galactomannans such as guar gums and their nonionic derivatives (hydroxypropyl guar), and mixtures thereof, preferentially xanthan and scleroglucan gums, more preferably scleroglucan gums.
[0014]
14. The method of dyeing according to any one of the preceding claims, characterized in that said process uses d) one or more chemical oxidizing agent (s) chosen (s) from peroxide of hydrogen or one or more system (s) generator (s) of hydrogen peroxide in particular selected from hydrogen peroxide or urea peroxide, preferably hydrogen peroxide. 10
[0015]
15. The method of dyeing according to any one of the preceding claims, characterized in that the dyeing process uses e) one or more alkalinizing agent (s) particularly selected from: i) the (bi ) carbonates, ii) ammonia, iii) alkanolamines such as mono-, di- and triethanolamines and their derivatives iv) oxyethylenated and / or oxypropylenated ethylenediamines, v) inorganic or organic hydroxides, vi) silicates alkali metals such as sodium metasilicates, vii) basic amino acids such as arginine, lysine, ornithine, citruline and histidine, and viii) compounds of the following formula (XI): Ra Embedded image in which W is a divalent (C1-C8) alkylene radical optionally substituted with at least one hydroxyl group or at least one (C1-C4) alkyl radical and ## STR2 ## / or optionally interrupted by at least one heterotatome such that oxygen, sulfur or by a group -N (Re) -; Ra, Rb, Rc, Rd and Re, identical or different, represent a hydrogen atom, a (C1-C4) alkyl or hydroxy (C1-C4) alkyl radical, preferably W represents a propylene radical, preferably the agent or agents The alkalizing agents are chosen from (bi) carbonates and amino acids, alone or in mixtures.
[0016]
16. Coloring process according to any one of the preceding claims, characterized in that the cosmetic composition (s) used comprises one or more organic solvent (s), especially chosen from lower C 1 -C 4 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. 3029409 55
[0017]
17. The method of dyeing according to any one of the preceding claims, characterized in that said process is carried out in at least two stages which comprises a first step in which the keratinous fibers are treated with a cosmetic composition comprising a) one or more dye (s) in particular orthodiphenol (s) as defined in any of claims 1 to 5, b) one or more titanium salt (s) chosen especially from organic titanium salts as defined (s) ) in any one of claims 1, 10 to 12 and b1) one or more carboxylic acid (s) of formula (I) as defined in any one of claims 1, 7, 10 or 11 and c) one or more non-cellulosic polysaccharide (s) as defined in claim 1 or 13; followed by a second step in which is applied an alkaline cosmetic composition ie whose pH is greater than 7, and preferably between 8 and 12 inclusive, particularly between 8 and 10.5, which comprises e) one or more agent (Alkalizer (s) as defined in claim 15, preferentially the cosmetic composition applied to the keratinous fibers in the second step further comprises d) one or more oxidizing agent (s) chemical (s) as defined in claim 14, in particular chosen from hydrogen peroxide or one or more system (s) generator (s) of hydrogen peroxide, preferably hydrogen peroxide. 20
[0018]
18. A method of dyeing according to the preceding claim made in several steps by application to the keratin fibers in a first step of a cosmetic composition comprising: a) one or more derivative (s) of ODP (s), such (s) as defined in any one of claims 1 to 6, especially chosen from: - haematin, brazile, gallic acid, tannic acid, when the dyeing process does not implement chemical oxidizing agent d) or - hematoxylin brasiline, when the dyeing process uses a chemical oxidizing agent d); B) one or more organic titanium salt (s) as defined in any one of claims 1, 10 to 12; 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 in any one of claims 1, 7, 10 or 11; and c) one or more non-cellulosic polysaccharide (s) as defined in any of claims 1 or 13; 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 (s) from among 3029409 56 hydrogen peroxide or one or more hydrogen peroxide generating system (s) as defined in claim 14; e) one or more basifying agent (s) chosen from amino acids and (bi) carbonates particularly alkaline or alkaline earth alone or in mixture; It being understood that: the composition comprising the carboxylic acid (s) is at acidic pH, ie less than 7, preferably less than 5, particularly at a pH ranging between 1 and 3, and the composition comprising the agent (s) The alkalizing agent is at alkaline pH, preferably between 8 and 12 and more particularly between 8 and 10.
[0019]
19. Cosmetic composition for dyeing keratinous fibers containing compounds a), b), b1), c), d) and e) as defined according to any one of claims 1 to 18.
[0020]
20. Multi-compartment device comprising 2 to 5 compartments containing 2 to 5 compositions, in which are distributed ingredients a), b), b1), c), d) and e), as defined according to one of the following: any of claims 1 to 18, said compositions being aqueous or powdery, with at least one of these compositions being aqueous.

类似技术:

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FR2976793A1|2012-12-28|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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FR3014682A1|2015-06-19|CAPILLARY COLORING PROCESS IMPLEMENTING AT LEAST ONE ORTHODIPHENOL, A TITANIUM DERIVATIVE, AND A CARBOXYLIC ACID

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FR2981569A1|2013-04-26|Coloring keratin fibers, preferably hair, comprises treating fibers with orthodiphenol derivatives, cyclodextrins, metal salts, hydrogen peroxide or its generating system, |carbonates, and alkalizing agents different from |carbonates

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---

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---

FR2996124A1|2014-04-04|A CAPILLARY COLORING PROCESS USING AT LEAST ONE ORTHOMETHOXYPHENOL DERIVATIVE, A MANGANESE OR ZINC SALT, HYDROGEN PEROXIDE AND | CARBONATE

同族专利:

---

公开号 | 公开日

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BR112017011007A2|2018-02-14|

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FR3029409B1|2016-12-09|

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US10524998B2|2020-01-07|

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EP3229757A1|2017-10-18|

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US20170354584A1|2017-12-14|

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ES2724362T3|2019-09-10|

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JP2017537162A|2017-12-14|

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CN107205896A|2017-09-26|

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EP3229757B1|2019-02-27|

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WO2016091817A1|2016-06-16|

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FR3029405B1|2014-12-08|2019-08-02|L'oreal|CAPILLARY COLORING PROCESS USING AT LEAST ONE COLOR, TITANIUM SALT, AND INSOLUBLE SILICATE|

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FR3029406B1|2014-12-08|2016-12-09|Oreal|CAPILLARY COLORING PROCESS USING AT LEAST ONE DYE, ONE TITANIUM SALT, AND ANIONIC THICKENING POLYMER|

---

FR3029407B1|2014-12-08|2016-12-09|Oreal|A CAPILLARY COLORING PROCESS USING AT LEAST ONE DIRECT AND / OR NATURAL COLOR, TITANIUM SALT, CELLULOSIC POLYSACCHARIDE AND, WHERE POSSIBLE, A PARTICULAR ORGANIC SOLVENT|FR3029407B1|2014-12-08|2016-12-09|Oreal|A CAPILLARY COLORING PROCESS USING AT LEAST ONE DIRECT AND / OR NATURAL COLOR, TITANIUM SALT, CELLULOSIC POLYSACCHARIDE AND, WHERE POSSIBLE, A PARTICULAR ORGANIC SOLVENT|

---

FR3029406B1|2014-12-08|2016-12-09|Oreal|CAPILLARY COLORING PROCESS USING AT LEAST ONE DYE, ONE TITANIUM SALT, AND ANIONIC THICKENING POLYMER|

---

FR3029405B1|2014-12-08|2019-08-02|L'oreal|CAPILLARY COLORING PROCESS USING AT LEAST ONE COLOR, TITANIUM SALT, AND INSOLUBLE SILICATE|

---

FR3082710B1|2018-06-20|2021-11-26|Oreal|DEVICE FOR DISTRIBUTION OF A HAIR COLORING PRODUCT IMPLEMENTING A COLORING COMPOSITION AND AN OXIDIZING COMPOSITION INCLUDING A SCLEROGLUCAN GUM.|

---

FR3082742B1|2018-06-20|2020-05-29|L'oreal|HAIR COLORING COMPOSITION COMPRISING AN OXIDATION DYE, A SCLEROGLUCAN GUM, AND AN ALKYLPOLYGLYCOSIDE.|

---

FR3082741B1|2018-06-20|2020-11-27|Oreal|HAIR COLOR COMPOSITION CONSISTING OF AN OXIDIZING COLOR, A SCLEROGLUCAN GUM AND A SPECIAL CARBOXYLIC ACID.|

法律状态:
2015-11-10| PLFP| Fee payment|Year of fee payment: 2 |

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2016-06-10| PLSC| Search report ready|Effective date: 20160610 |

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2016-11-11| PLFP| Fee payment|Year of fee payment: 3 |

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2017-11-13| PLFP| Fee payment|Year of fee payment: 4 |

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2019-11-15| PLFP| Fee payment|Year of fee payment: 6 |

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2021-09-10| ST| Notification of lapse|Effective date: 20210806 |

优先权:

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申请号 | 申请日 | 专利标题

---

FR1462064A|FR3029409B1|2014-12-08|2014-12-08|A CAPILLARY COLORING PROCESS USING AT LEAST ONE COLOR, AN ORGANIC TITANIUM SALT, AND A NON-CELLULOSIC POLYSACCHARIDE|FR1462064A| FR3029409B1|2014-12-08|2014-12-08|A CAPILLARY COLORING PROCESS USING AT LEAST ONE COLOR, AN ORGANIC TITANIUM SALT, AND A NON-CELLULOSIC POLYSACCHARIDE|

---

EP15808561.3A| EP3229757B1|2014-12-08|2015-12-07|Hair dyeing process using at least one dye, an organic titanium salt, and a non-cellulosic-based polysaccharide|

---

BR112017011007A| BR112017011007A2|2014-12-08|2015-12-07|keratin fiber dyeing process, cosmetic dyeing composition and multi-compartment device|

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JP2017548333A| JP2017537162A|2014-12-08|2015-12-07|Hair dyeing method using at least one dye, organic titanium salt, and non-cellulosic polysaccharide|

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US15/534,296| US10524998B2|2014-12-08|2015-12-07|Hair dyeing process using at least one dye, an organic titanium salt, and a non-cellulosic-based polysaccharide|

---

ES15808561T| ES2724362T3|2014-12-08|2015-12-07|Hair dyeing process using at least one dye, an organic titanium salt and a non-cellulosic base polysaccharide|

---

CN201580075673.6A| CN107205896A|2014-12-08|2015-12-07|Use the hair colouring methods of at least one dyestuff, organic titanium salt and non-cellulose Quito sugar|

---

PCT/EP2015/078847| WO2016091817A1|2014-12-08|2015-12-07|Hair dyeing process using at least one dye, an organic titanium salt, and a non-cellulosic-based polysaccharide|