FR3037239A1 - CAPILLARY COLORING PROCESS USING TITANIUM SALT, OXIDATION COLOR, AND INTERMEDIATE RINSE - Google Patents

Abstract

The present invention relates to a multi-step process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, in which said fibers are treated with i) a step containing at least one cosmetic composition Ci) comprising a) one or several salt (s) of titanium and b) optionally one or more particular carboxylic acids; and with ii) a dyeing step with a dye cosmetic composition Cii) comprising c) one or more oxidation dye (s) and optionally d) one or more chemical oxidizing agent (s) such as ) hydrogen peroxide or one or more system (s) generator (s) of hydrogen peroxide, iii) a step of intermediate rinsing said keratinous fibers preferably water, between step i) and ii ) or ii) and i)

Description

The present invention relates to a multi-step process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, in which the present invention relates to a process for staining keratinous fibers, in particular human keratinous fibers such as the hair, in which said fibers are treated with i) a cosmetic composition Ci) comprising a) one or more salt (s) of titanium and b) optionally one or more particular carboxylic acids; and with ii) a coloring cosmetic composition Cii) comprising c) one or more oxidation dye (s) and optionally d) one or more chemical oxidizing agent (s) such as peroxide d hydrogen or one or more system (s) generator (s) of hydrogen peroxide, it being understood that between step i) and ii) or ii) and i) the keratinous fibers are rinsed. 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. It is sought to increase the efficiency of the reaction of the oxidation dyes used during this process in particular in terms of power, color rise, color fastness on the keratinic fibers especially vis-à-vis light, successive washings, sweat and / or selectivity of the color between the root and the tip of said fibers. Indeed, such improvement (s) will (in) t in particular to reduce the levels of oxidation dyes present in the dye compositions, reduce the exposure time on keratinous fibers and / or use other families dyes with low dyeing power and which may have 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, or finally to lead to better qualities of use as a less staining of scalp, clothing, or even less coloration of the dye mixture (cleaner) during the application or the break time 3037239 2 This (these) purpose (s) is (are) achieved by the present invention which relates to a method for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, in which said fibers are treated, in several steps, with i) at least one stage of treatment of said fibers with a cosmetic composition Ci ) containing: (a) one or more titanium salts; in particular the titanium atom of said salt (s) is (are) of degree of oxidation 2, 3 or 4 denoted Ti (II), Ti (III) or Ti (IV), preferably Ti (IV) ); b) optionally one or more carboxylic acid (s) of the following formula (I) or a salt thereof; Wherein (A) is monovalent when n is 0 or polyvalent when n is 1 or more, hydrocarbon having 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 and / or amino groups; preferably A represents a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted with one or more hydroxyl and / or amino groups; n represents an integer inclusive between 0 and 10, preferably n is between 0 and 5, such as between 0 and 2; and ii) at least one dyeing step with a dye cosmetic composition Cii) containing: c) one or more oxidation dye (s); and d) optionally one or more chemical oxidizing agent (s), especially chosen from hydrogen peroxide or one or more hydrogen peroxide generator system (s); iii) at least one intermediate rinsing step of said fibers preferably with water, it being understood that: - firstly the composition Ci) is applied to said fibers, followed by one or more rinsing (s) of said fibers, preferably with water, then the composition Cii) is applied to said fibers; or else - firstly the composition Cii) is applied to said fibers, followed by one or more rinsing (s) of said fibers, preferably with water, then the composition Ci) is applied to said fibers. The process according to the invention has the advantage of coloring human keratin fibers, with stubborn coloring results. In particular, the dyeing method according to the invention makes it possible to lead to colorings which are resistant to washing, perspiration, sebum and light without altering the fibers. The homogeneity of the color between the root and the tip of the fibers is particularly good. In addition, the coloring process used makes it possible to induce a "rise" and / or a very satisfactory coloring power. Other objects, features, aspects and advantages of the present invention will become more apparent upon reading the following description and examples. a) the salt (s) of titanium: The cosmetic composition Ci) used according to step i) of the process according to the invention comprise one or more organic or inorganic salt (s) of titanium. The titanium salt (s) of the invention may be one or more organic (s) or inorganic (s) salt (s) of titanium. For the purposes of the present invention, the term "organic titanium salt" is intended to mean the salts themselves derived from the action of at least one organic acid on Ti, which may be of oxidation state 1, 2, 3 or 4, preferably of degree of oxidation 4 denoted Ti (IV). 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 selected from carboxy COOH, sulfuric SO3H, SO2H, and phosphoric PO31-12, PO4H2. In particular, the organic acid (s) is (are) to form the organic titanium salt (s) of the invention is (are) chosen from carboxylic acids (s) of formula (1) as defined above and preferably is or are an alpha-hydroxy acid such as lactic, glycolic, tartaric or citric acids. 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) carboxylic acid (s). Preferentially, the organic salt (s) of titanium a) of the invention is (are) chosen from those of formula (IA) below: ## STR1 ## Wherein (A) is the same as that of formula (I) - n, n 'and n "the same or different are 1, 2, 3 or 4 with n' + n "worth 6; 5 - M1 and M2, which are 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 of hydrogen; TiY designating Ti (01-1), r, or Ti (O) 12, or Ti (01-1) ,, i (0) ,, 2 with m1 + m2 = n ".

Preferentially, the radical A of the compound (IA) as defined above represents a monovalent (C 1 -C 6) alkyl or polyvalent (C 1 -C 6) alkylene group optionally substituted with one or more hydroxyl groups or one or more amino groups, preferably by one or more hydroxyl groups, and n representing an integer between 0 and 5 inclusive, such as between 0 and 2, particularly the carboxylic acid (s) used to form the organic titanium salt (s) of the invention are chosen from α-hydroxy acids and α-amino acids; preferably, the acid is chosen from citric acid, lactic acid, malic acid, tartaric acid, and glycolic acid, and serine, more preferentially chosen from lactic and glycolic acid.

Preferably, the organic titanium salt (s) a) of the invention is (are) chosen from those of the following formula (IB): embedded image in which: - L 'and L ", identical or different, represent a divalent group (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 with a (C1-C4) alkyl group; X 'and X', which are 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; 5 - Y and Y ', which are identical or different, are as defined for X' and X ", preferably Y and Y 'are identical and represent an oxygen atom; - Ra and Rb, identical or different, represent an atom hydrogen, or a (C1-C6) alkyl, (C2-C6) 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 counterion such as alkali metal (Na, K), alkaline earth (Ca) or organic cation such as ammonium, preferably ammonium. (s) organic (s) Titanium a) staining process is the dihydroxybis (lactato) titaniumIV salt such as those of the following formula: ## STR1 ## 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. inorganic acid "means an acid which does not contain carbon atoms 20 except carbonic acid. According to a particular embodiment of the invention, the titanium salt (s) a) is (are) inorganic (s). II (s) is (are) particularly selected from titanium halides, titanium sulphates and titanium phosphates. The inorganic titanium salts are preferably salts of Ti (II), Ti (III) or Ti (IV), more particularly Ti (III) or Ti (IV), more preferably Ti (IV). According to a preferred embodiment of the invention, the titanium salt (s) a) is (are) organic titanium salts, and more preferably organic Ti (IV) salts. According to an advantageous embodiment of the invention, the organic salt of Ti consists of a Ti (IV) atom and from 2 to 3 molar equivalents of at least one carboxylic acid of formula (I). The salt (s) of titanium a) is (are) present in the cosmetic composition i) of the dyeing process according to the invention in a content ranging from 0.001% to 20% by weight relative to the weight total of said composition i) as defined above. In particular, the titanium organic salt (s) and titanium inorganic 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. . B) one or more carboxylic acid (s) The cosmetic composition Ci) used according to step i) of the process according to the invention may also comprise one or more carboxylic acid (s) . 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 chosen from: i) (01-010) alkyl- [O (0) -OH] and ii) het- [C (O) -OH], with n an integer inclusive of between 1 and 4, preferably between 1 and 2, hetero-cyclic group such as pyrrolidone, the alkyl or hetero group may be optionally substituted with one or more groups, especially selected from OH, and (di) (01- 06) (alkyl) amino. According to an advantageous variant, the dyeing method also uses b) one or more carboxylic acid (s) of formula (I) as defined above. More preferentially, the carboxylic acid or acids b) are different from the carboxylic acids complexed with the Ti salts, preferably glycolic acid, citric acid, lactic acid or one of their salts. For example, if the carboxylic acid complexed with the titanium salt a) is lactic acid or its carboxylate salt (lactate), the second acid b) other than lactic acid or lactate, and may be for example the acid glycolic. The salts of the acids of formula (I) may be organic or inorganic base salts or alkalizing agents e) as defined below. Preferably the salts are salts of sodium hydroxide, ammonia, or potassium hydroxide or salts of organic amines such as alkanolamines. The acids of formula (I) or their salts are present in the composition i) in a content ranging from 0.1 to 20% by weight, relative to the total weight of said composition i). c) The oxidation dye (s) According to the present invention, the dye composition Cii) used according to step ii) of the process according to the invention comprises one or more oxidation dye (s) . 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 para-phenylenediamines, para-phenylenediamine, paratoluylenediamine and 2-chloro-para-phenylenediamine may be mentioned by way of example. 2,3-dimethyl paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 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 (p-hydroxyethyl) paraphenylenediamine, 4-N, N-bis (13-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (3-hydroxyethyl) amino-2-chloroaniline, 2-13-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N - (p-hydroxypropyl) paraphenylenediamine, 2 hydroxymethyl paraphenylenediamine, 2-methoxymethyl paraphenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, -p-hydroxyethyl) paraphenylenediamine, N- (13, γ-dihydroxypropyl) paraphenylenediamine, N- (4 'aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-13-hydroxyethyloxy para-phenylenediamine, 2-13-acetylaminoethyloxy para-phenylenediamine, N- (p-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, 2- thienyl paraphenylenediamine, 2-hydroxyethylamino-5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid.

Of the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-13-hydroxyethyl paraphenylenediamine, 2-13-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, la 2, 6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (p-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2-13-acetylaminoethyloxy-para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine and their salts acid addition are particularly preferred. Among the bis-phenylalkylenediamines, mention may be made, by way of example, of N, N'-bis- (13-hydroxyethyl) N, N'-bis- (4'-aminophenyl) -1,3-diamino propanol, N N, N'-bis- (13-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis - (13-hydroxyethyl) -N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N N, B- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis- (2,5-diaminophenoxy) -3,6-dioxaoctane, and their addition salts.

Among the para-aminophenols, para-amino phenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-chlorophenol may be mentioned by way of example; 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol 4-Amino-2-fluoro phenol, 4-amino-2-fluoro phenol, and their acid addition salts.

Ortho-aminophenols include, for example, 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2- amino phenol, and their addition salts. Among the heterocyclic bases, there 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 [1,5a] -pyridines oxidation bases or their addition salts described for example in the patent application FR 2801308. By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-amino-pyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-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] pyridine-7-yl) -ethanol; (3-amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-aminopyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-Amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-amino-pyrazolo [1,5-a] pyridin-7-ol; 2-13-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 position 2 by: a) a (di) (C1-C6) (alkyl) group amino, alkyl groups which may be substituted with one or more hydroxy, amino, or imidazolium groups; b) a heterocycloalkyl group comprising from 5 to 7 members, and from 1 to 3 heteroatoms, cationic or otherwise, optionally substituted with one or more (C1-C6) alkyl groups such as di (C1-C4) alkylpiperazinium; c) a (C1-C6) alkoxy group optionally substituted with one or more hydroxy groups such as 13-hydroxyalkoxy and their addition salts. Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88 169571; JP 05-63124; EP 0770375 or patent application VVO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2,4 dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and tautomeric forms, when tautomeric equilibrium exists. Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications VVO 94/08969, VVO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 diamino 1-methyl pyrazole, 4,5-diamino-1- (13-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4, 5-diamino-1,3-dimethyl pyrazole, 4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenyl pyrazole, 4-amino-1, 3-dimethyl-5-hydrazino pyrazole, 1-benzyl-4,5-diamino-3-methyl pyrazole, 4,5-diamino-3-tert-butyl-1-methyl pyrazole, 4,5 1-tert-butyl 3-methyl pyrazole, 4,5-diamino-1- (13-hydroxyethyl) -3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl pyrazole, 4, 5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-dia mino-3-methyl-1-isopropyl pyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl-3, 4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4- (13-hydroxyethyl) amino-1-methyl pyrazole, and their salts thereof; addition. Preferably, the heterocyclic oxidation bases of the invention are chosen from 4,5-diaminopyrazoles such as 4,5-diamino-1- (13-hydroxyethyl) pyrazole. 4-5-Diamino-1- (13-methoxyethyl) pyrazole can also be used.

Preferably, a 4,5-diaminopyrazole and even more preferably 4,5-diamino-1- (13-hydroxyethyl) pyrazole and / or a salt thereof will be used. As pyrazole derivatives, mention may also be made of diamino N, Ndihydropyrazolopyrazolones and especially those described in application FR-A-2 886 136 such as the following compounds and their addition salts: 2,3-diamino-6,7 Dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol 1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3- (pyrrolidin-1-yl) 6-a, 7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 4,5-diamino-1,2-dimethyl-1,2-dihydro-pyrazol-3-one, 4 5-Diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2-di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3 -one, 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-dimethylamino-6 7-Dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H, 6H-pyridazino [1,2-a] ] pyrazol-1-one, 4-aminodo-1,2-diethyl-5- (pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one, 4-amino-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, use will preferably be made of 4,5-diamino-1- (13-hydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2- a] pyrazol-1-one and / or a salt thereof.

The oxidation base (s) used in the context of the invention are generally present in an amount ranging from 0.001 to 10% by weight approximately of the total weight of the dyeing composition, preferably ranging from 0.005 to 5%. The additional couplers conventionally used for dyeing keratinous fibers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. By way of example, mention may be made of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 1-hydroxy-3-aminobenzene, 2-methyl-5-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-hydroxyethylaminophenol, 2,4-diamino-1- (11-hydroxyethyloxy) benzene, 2-amino-4- (11-hydroxyethylamino) -1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1 dimethylamino benzene, sesamol, thymol, 1-11-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 1-N- (11-hydroxyethyl) amino-3 , 4-methylene dioxybenzene, 2,6-bis (11-hydroxyethylamino) toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazole e-5-one, 1-phenyl-3-methyl pyrazole 5-one, 2,6-dimethyl pyrazolo [1,5-13] -1,2,4-triazole, 2,6-dimethyl-3-yl; , 2-c] -1,2,4-triazole, 6-methyl pyrazolo [1,5-4-benzimidazole, their acid addition salts, 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. d) the chemical oxidizing agent (s) According to one particular embodiment of the invention, the dyeing method also uses one or more chemical oxidizing agents (s) ). By chemical oxidizing agent is meant an oxidizing agent different from the oxygen of the air. More particularly, the dyeing process uses 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 polymeric complexes described in US 5,008,093; US 3,376,110; US 3037239115,183,901; iv) oxidases in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase); v) metal peroxides generating hydrogen peroxide in water such as calcium peroxide, magnesium peroxide; vi) perborates; and / or vii) percarborates.

According to an advantageous embodiment of the invention, the dye composition Cii) comprises one or more chemical oxidants d). The chemical oxidizing agent may be implemented by extemporaneously adding to the composition Cii), preferably just before the application of said composition to the keratinous fibers.

According to a preferred embodiment of the invention, the composition Cii) contains one or more chemical oxidizing agent (s) chosen from i) urea peroxide, ii) polymeric complexes capable of releasing hydrogen peroxide selected from polyvinylpyrrolidone / H 2 O 2; iii) oxidases; iv) perborates and v) 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 (s) used preferably represent from 0.01% to 12% by weight of chemical oxidizing agents (preferably hydrogen peroxide), preferably from 0, 2 to 6% relative to the total weight of the composition or compositions containing them or, more preferably, from 0.2% to 3% by weight. E) the alkalinizing agent (s) According to the total weight of the composition (s) a particular embodiment of the invention the coloring process uses one or more agent (s) alkalinizing (s) e). Preferably, the alkalinizing agent (s) e) are in the dyeing composition with the oxidation dye (s) c) as defined above. These alkalinizing agents are bases for increasing the pH of the composition or compositions in which it is located. The basifying agent is a Bronsted, Lowry or Lewis base. It can be mineral or organic. In particular, said agent is chosen 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 (II): 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 / 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 transition metal, such as Group III, IV, V and VI metal hydroxides, d) Lanthanide or actinide hydroxides, 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 (Met2 +, CO2), alkaline earth metal (Met2 +, CO2) ammonium carbonates ((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 (C-20 C6) optionally substituted alkyl such as hydroxyethyl), and b) bicarbonates, also called 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, H20); and Met2 + (1-1CO3-) 2 with Met 'representing an alkaline earth metal. More particularly, the basifying agent is chosen from alkali metal 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 mixtures thereof, and in particular Na hydrogen carbonate. These hydrogencarbonates may come from natural water, for example spring water from the Vichy basin, from La Roche Posay, Badoit water (see patent for example FR 2 814 943). Particularly mention may be made of sodium carbonate [497-19-8] = Na2003, sodium hydrogencarbonate or sodium bicarbonate [144-55-8] = NaHCO3, and sodium dihydrogen carbonate = Na (HCO3) 2 . According to a particularly advantageous embodiment, the alkalinizing agent (s) (e) is (are) chosen from ammonia and alkanolamines such as monoethanolamine, preferably ammonia. 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. T) the additional dye (s) According to one particular embodiment of the invention, the dyeing process uses one or more additional dye (s) different from c). In particular, the dyeing method uses in one of the compositions or in an additional composition f) one or more synthetic or natural direct dyes chosen from anionic, cationic and nonionic species, preferably cationic or nonionic species, or as single dyes in addition to the oxidation dye (s). Preferably the additional dye (s) are with (c).

More particularly, the additional direct dyes are chosen from azo direct dyes; nitro dyes; (poly) methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro (hetero) aryl dyes; tri (hetero) arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures. The direct dyes are preferably cationic direct dyes. Mention may be made of the hydrazono cationic dyes of the formulas (IIIa) and (IIIa), the azo cationic dyes (IVa) and (IV'a) and the cationic diazo dyes (Va) below: in which formulas (IIIa) (IIIa), (IVa), (IV'a) and (Va): Hee represents a heteroaryl cationic radical, preferably carrying an optionally substituted endocyclic cationic charge, such as imidazolium, indolium or pyridinium, of preferably, one or more (Cl-08) alkyl groups, such as methyl; Het + -C (Ra) = NN (Rb) -Ar, An- (111a) Het + -N (Ra) -N = C (Rb) -Ar, An- (III'a) Het + -N = N-Ar, An (IVa) Ar + -N = N-Ar ", An- and Het + -N = N-Ar'-N = N-Ar, An (IV'a) (Va) ## EQU1 ## Ar + represents an aryl radical, such phenyl or naphthyl, carrying an exocyclic cationic charge, preferably ammonium, in particular tri (C1C8) alkylammonium such as trimethylammonium;> Ar represents an aryl group, in particular phenyl, which is optionally substituted, preferably by one or more groups electron donors, such as i) (C1-C8) optionally substituted alkyl, ii) (C1-C8) optionally substituted alkoxy, iii) (di) (C1-C8) (alkyl) amino optionally substituted on (s) alkyl group (s) with a hydroxyl group, iv) optionally substituted aryl (C1-C8) alkylamino, v) N- (C1-C8) alkyl-Naryl (C1-C8) alkylamino or, alternatively, Ar represents a group julolidine; Ar 'represents an optionally substituted divalent (hetero) arylene group, such as phenylene, in particular para-phenylene, or naphthalene, which are optionally substituted, preferably by one or more (C1-C8) alkyl, hydroxyl or (C1-C8) alkoxy groups; Ar "represents an optionally substituted (hetero) aryl group, such as phenyl or pyrazolyl, which are optionally substituted, preferably by one or more (C1-C8) alkyl, hydroxyl, (di) (C1-C8) (alkyl) groups; ) amino, (C1-C8) alkoxy or phenyl; Ra and Rb, which may be the same or different, represent a hydrogen atom or a (C1-C8) alkyl group, which is optionally substituted, preferably by a group hydroxyl, or alternatively, the substituent Ra with a substituent of Hee and / or Rb with a substituent of Ar and / or Ra with Rb together with the atoms which carry them a (hetero) cycloalkyl, in particular Ra and Rb represent a hydrogen atom or a (C 1 -C 4) alkyl group, which is optionally substituted by a hydroxyl group;> An - represents an anionic counterion, such as mesylate or halide. cationic dyes azo and hydrazono carrying a cationic charge endoc There are formulas (111a), (IIIa) and (IVa) as defined above. More particularly, those of the formulas (111a), (IIIa) and (IVa) derived from the dyes described in patent applications VVO 95/15144, VVO 95/01772 and EP-714954. Preferably, the cationic part is derived from the following derivatives: ## STR1 ## wherein R 1 is R 2 NN 111 H R2 (111a-1) (IVa-1) formulas (III-1) and (IV-1) with: - R1 representing a (C1-C4) alkyl group such as methyl; R2 and R3, which are identical or different, represent a hydrogen atom or a (C1-C4) alkyl group, such as methyl; and - R4 represent a hydrogen atom or an electron donor group, such as an optionally substituted (C1-C8) alkyl, (C1-C8) alkoxy or (di) (C1-C8) alkoxy group ( alkyl) amino optionally substituted on the alkyl group (s) by a hydroxyl group; in particular R4 represents a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferably OH; - An- represents an anionic counterion, such as mesylate or halide.

In particular, the dye of the formulas (IIIa-1) and (IVa-1) is chosen from the Basic Red 51, the Basic Yellow 87 and the Basic Orange 31 or corresponding derivatives: C1-13 \ [\ (CH3 H3C H3C H3C N-NN / NNC N-CH3 NI-12 An- / H3C An-H3C-An- Basic Red 51 Basic Orange 31 Basic Yellow 87 Of the natural direct dyes that can According to the invention, mention may be made of hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermetic acid, purpurogalline, protocatechaldehyde, indigo, isatin, Curcumin, spinulosin, apigenidine and orcein The extracts or decoctions containing these natural dyes and in particular poultices or henna extracts may also be used. Direct dye (s) are more particularly from 0.001% to 10% by weight and preferably from 0.005% to 5% by weight of the total weight of the product. Intermediate rinsing: The method according to the invention comprises at least one intermediate rinsing step iii) ie a rinsing step between the step of application to the keratinous fibers of the composition Ci) as defined above and Cii) as defined previously.

According to one embodiment of the invention, water is preferably used during the intermediate rinsing step. In particular, the intermediate rinsing step is carried out with water without the addition of adjuvants as defined below. Preferably the intermediate rinse iii) is performed by treating the keratinous fibers with tap water. More preferably, the intermediate rinsing is carried out with tap water until the residual water is clear and visually transparent, in the case where said rinsing is carried out after the application of the coloring composition Cii in the case or the intermediate rinse is performed after the application of the composition Ci, said rinsing is carried out for 1s to 5 minutes, better from 5 seconds to 1 minute.

Preferably, the hair is dewatered after intermediate rinsing. 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. Organic solvents: As an additional 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. 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.

Adjuvants: The compositions of the dyeing method according to the invention may also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, nonionic, amphoteric, zwitterionic surfactants. or mixtures thereof, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof, mineral or organic thickeners and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, penetration, sequestering agents, perfumes, buffers, dispersants, conditioning agents such as, for example, volatile or nonvolatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, opacifying agents. Said adjuvants are preferably selected from surfactants such as anionic, nonionic surfactants or mixtures thereof and inorganic or organic thickeners. The adjuvants above are generally present in an amount for each of them between 0.01 and 40% by weight relative to the weight of the composition, preferably between 0.1 and 20% by weight relative to the weight of the composition.

Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition or to the composition (s) useful in the dyeing process according to the invention do not not, or not substantially, impaired by the 15 or additions contemplated. 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 keratinous fibers.

They can also be packaged in a pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam. pH of the compositions: Preferably, the pH of at least one of the cosmetic compositions comprising at least one of ingredients a) to e) is acidic, ie has a pH below 7.0, preferably below 5 , 0, especially at a pH between 0 and 4 inclusive, more preferably between 0.5 and 3.5, preferably between 1 and 3. Preferably the composition i) is acidic, preferably has a pH below 5 , 0, especially at a pH of 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 or compositions containing one or more a plurality of alkaline agents is alkaline, ie greater than 7, preferably of between 8 and 12 and more particularly of between 8 and 11 inclusive.

Preferably, the composition containing the alkaline agent (s) is the dye composition Cii) as defined above. According to one particular embodiment of the invention, the composition i) containing the titanium salt (s) a) and not containing alkalinizing agent e) has a pH of less than 7, and preferably less than 5, especially a pH between 0 and 4.

The pH of these compositions can be adjusted to the desired value by means of basifying agents as defined previously in e) or from acidifying agents usually used for dyeing keratinous fibers or else with the aid of conventional buffer systems. Among the acidifying agents of the compositions used in the invention, mention may be made, by way of example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid and carboxylic acids as defined. previously such as acetic acid, tartaric acid, citric acid, lactic acid, sulphonic acids. Multi-step dyeing process The dyeing process of the keratinous fibers of the invention implements: either the application on said fibers of the composition Ci), then at least one rinsing of said fibers preferably with water in particular with tap water, then the application on said fibers of the composition Cii); Or> the application on said fibers of the composition Cii), then at least one rinsing of said fibers preferably with water, in particular with tap water, then the application on said fibers of the composition Ci); wherein: - the cosmetic composition Ci) comprises a) one or more salt (s) of titanium; in particular the titanium atom of said salt (s) is (are) of degree of oxidation 2, 3 or 4 denoted Ti (II), Ti (III) or Ti (IV), preferably Ti (IV) ); and - the cosmetic composition Cii) comprises c) one or more oxidation dye (s). According to a particular embodiment, the composition Ci) of the dyeing process of the invention further comprises b) one or more carboxylic acid (s) of the following formula (I) or a salt thereof; ## STR2 ## 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 is a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted with one or more hydroxy groups; n represents an integer between 0 and 10 inclusively, preferably n is between 0 and 5, such as between 0 and 2. Preferably, the titanium organic salt (s) of the composition i) the process of the invention is (are) chosen from those of formula (IA), (IB), or the dihydroxybis (lactato) titaniumIV salt as defined above. According to one particular embodiment of the invention, the dyeing method implements the application on said fibers of the composition Ci) as defined above, then a rinsing preferably with water of said fibers, then the application 10 on said fibers of the composition Cii) as defined above. Particularly in the dyeing process of the invention the pause time on the keratinous fibers of the composition i) as defined above is between 5 minutes and 2 hours, more particularly between 5 minutes and 1 hour, preferably between 5 and 30 minutes. Preferably, the pause of the composition i) on the keratinous fibers is carried out at a temperature of between 20 ° C. and 50 ° C., more preferably between room temperature (27 ° C.) and 40 ° C. Between the application of the compositions Ci) and Cii) or Cii) and Ci), at least one rinsing is carried out in the process of the invention. Preferably a rinse is carried out with tap water, preferably until the residual rinse water of the keratin fibers 20 is clear and visually transparent, identical to the water before treatment of the keratinous fibers. According to one particular embodiment, the composition Cii) of the dyeing method of the invention further comprises one or more chemical oxidizing agent (s), in particular chosen from hydrogen peroxide or one or more several system (s) 25 hydrogen peroxide generator (s) as defined previously. The composition Cii) which comprises at least one oxidation dye and at least one chemical oxidizing agent is also called "ready-to-use" oxidation dye composition. This ready-to-use coloring composition is preferably carried out a few minutes before application, in particular between 1 minute and 20 minutes, more particularly between 5 minutes and 10 minutes before application. The ready-to-use composition is prepared by uniformly mixing the dye composition comprising c) at least one oxidation base as defined above and optionally at least one coupler as defined above, with an oxidizing composition comprising d) at minus a chemical oxidizing agent as defined above. Once the ready-to-use coloring composition is prepared, it is preferably applied immediately to the keratinous fibers. The pause time of the composition ii) and in particular of the ready-to-use coloring composition, on the keratin fibers is between 1 minute and 2 hours, preferably between 5 minutes and 1 40 hours, more preferably the time of break is 15 to 30 minutes.

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 preferably especially between 0.5 and 3.5 and more preferably between 1 and 3. In particular the composition Ci) according to the invention is at pH 5 acid preferably less than 5, particularly at a pH inclusive between 0 and 4, plus particularly between 0.5 and 3.5 and more preferably between 1 and 3. Preferably, the compositions used in the process of the invention are aqueous.

According to one particular embodiment of the invention, the coloring composition Cii) comprising the oxidation dye (s) as defined above furthermore comprises one or more alkalinizing agents (e) as defined above, preferably ammonia or monoethanolamine. In particular, the pH of the composition comprising one or more alkalinizing agents, preferably the composition Cii) is between 8 and 12, particularly between 8 and 11 After the application of the compositions Ci), the rinsing of the keratin fibers and the application of the composition ii), and vice versa, the dyeing process of the invention may use one or more shampoos, followed by one or more rinsing with water of the keratinous fibers and optionally followed by drying by heat treatment by heating at a temperature 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. It is also possible to use, as a means for heating and smoothing the hair, a heating iron at a temperature between 60 and 220 ° C and preferably between 120 and 200 ° C. 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 that 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 (s). As a thermal source there may be mentioned a hair dryer, hair helmets, a hair straightener, an infrared dispenser and other conventional heating devices. One particular embodiment of the invention relates to a coloring process which is carried out at room temperature (25 ° C). In all the particular modes and variants of the processes described above, the compositions mentioned are ready-to-use compositions which may result from the extemporaneous mixing of two or more compositions, and in particular of compositions present in dyeing kits.

The following examples serve to illustrate the invention without however being limiting in nature.

EXAMPLES OF COLORING Example 1: Pretreatment with Ti at an Oxidation Staining The following compositions are prepared from the following ingredients in the following proportions per 100 grams of composition: Pre-treatment composition Ci): Ingredients Amount Dihydroxybis (ammonium lactate) titanium (IV) at 50% by weight 10.3g Glycolic acid 15 g pH agent Qsp pH = 2 ± 0.3 Water qs 100 g 10 Coloring composition Cii) ': Ingredients quantity N, N-bis sulphate (2-hydroxyethyl) -p-phenylenediamine sold under the reference JAROCOL BHP by VIVIMED 5.10-3 mol 2,4-diaminophenoxyethanol hydrochloride (sold under the reference 24 DAPE LO-BLUE by DRAGON CHEMICAL) 5.10-3 mol 20% ammonia in water 10 g Water qs 100 g The composition Ci) of pre-treatment is applied to a pair of locks of 15 Caucasian hair 90% natural white (90 BN) and permed (90 BP) respecting a bath ratio of 10 grams composi i) for 1 gram of wick treated. The composition Ci) is left for 45 minutes at 40 ° C on each wick, then each wick is rinsed for 5 seconds and then wrung. The coloring composition C11) is mixed with an oxidizing composition 20 volumes (6% H 2 O 2), at the rate of 5 grams of coloring composition per 5 grams of oxidizing composition. The coloring composition mixture Ci1) + oxidizing composition leads to the composition Cii which is then applied to each wick and left paused 30 minutes at 27 ° C. For comparison, the above process is repeated with the coloring composition and the oxidizing composition Ci 1) except that the wicks previously wetted and dewatered have not been pre-treated with the composition Ci). At the end of these exposure times, the locks are rinsed and washed with the lnoa post Color shampoo, rinsed and then dried with a helmet. Results of colorations It is found that black locks are very intensely colored. In addition, it appears that the coloration is visually more homogeneous (less selective) with the method of the invention than when the coloring process does not implement pretreatment with titanium salt.

These results are corroborated with the measurements of L. a. and b spectrophotometer 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 designate respectively the intensity of the color (L *), a * indicates the green / red color axis and b * the blue / yellow color axis. Color selectivity (4E * selec): The selectivity of the coloring between the root and the keratin fiber tip is represented by the color variation between the hair strands at 90% natural white (90 BN), and hair permuted blanks (90 BP) defined by (4E * selec) according to the following equation: E * selec = V (L * -L0 *) 2 ± (a * _ ao *) 2 ± (3 * _ bo *) 2 In this equation, L *, a * and b * represent the values measured on hair strands 90 BP after staining and Lo *, ao * and bo * represent the values measured on locks of hair 90 BN after staining. The lower the value of 4E *, the lower the selectivity, and the better the homogeneity of the color from root to tip. The results L, a, b of selectivity of the color are listed in the table below: Method Type of AE * Selec Color on hair hair Invention: Pre-treatment composition 90 BN 1.25 Black blue Ci) then rinse and Cii) coloring composition Cii '+ oxidant) 90 BP Comparative: Coloring composition Cii' 90 BN 4.48 Dark blue + oxidizing ii) 90 BP. It appears that pretreatment in the staining process significantly improves the homogeneity of the color, since the selectivity 4E * is much lower with the method of the invention than that of the comparative. EXAMPLE 2 Posttreatment with Ti to an Oxidation Stain Strands of 90% white permed hair (BP) are stained by the commercial colorations 7.4 and 6.64 (mixture 1 + 1 by weight with the oxidant lnoa 20 Volumes ) at the rate of 5 g of dye mixture for 1 g of hair. Each dye + oxidant mixture constitutes respectively Cii) 7.4 and Cii) 6.64.

Each composition Cii) 7.4 and Cii) 6.64 is left paused for 30 minutes at 27 ° C. on a wick, then each of the wicks is rinsed until the residual color of the rinsing water disappears., then wrung out. Post-treatment composition Ci): Ingredients amount Dihydroxybis (ammonium lactate) titanium (IV) at 50% by weight 10.3g Glycolic acid 15 g pH agent (HCI) Qsp pH = 2 ± 0.3 Water qs 100 g Partly wicks is then treated with the titanium composition Ci at a rate of 2.5 g per 1 g of hair and then left for 15 minutes at 40 ° C., drained and dried in the helmet.

Evaluation on the tenacity: Each lock treated with the composition Ci) is then immersed in a flask containing 100 ml of water for 72 hours compared to each of the locks not treated with the composition Ci) (simply stained).

The flasks are then visually observed after 1 hour of immersion and after 72 hours of immersion. After 1 hour or 72 hours of immersion, the water containing the locks treated with the composition Ci) is hardly colored, unlike the water containing the locks not treated with the composition Ci). These results are corroborated with the measurements of L. a. and b the Minolta CM-3600D spectrophotometer.

## EQU1 ## In this equation, L *, a * and b * represent the following equations: ## EQU1 ## values measured on hair strands 90 BP after staining before immersion and L1 *, ai * and bi * represent the values measured on strands of hair 90 BP after staining and after immersion 72 hours in water. The lower the value of DE *, the less the color loss of the colored wick occurs. The loss of color results are listed in the table below: Type of locks and treatment DE * loss Wick stained by shade 7.4 (Composition Cii) 74) not treated with composition Ci) - Immersed (comparative) 9.03 Wick colored by the shade 7.4 and then treated with the composition Ci) - Immersed (invention) 3.67 Wick colored by the shade 6.64 (composition Cii) 664) not treated with the composition Ci) - Immersed (comparative) 15.47 Colored wick by the grade 6.64 and then treated with the composition Ci) - Immersed (invention) 13,13 It appears clearly that on the dried locks before and after immersion in the water 10 the color losses of the locks treated with the composition Ci) are significantly less than that of non-IC treated locks, this results in much smaller DE * values in the case of treated locks. 15

Claims (18)

REVENDICATIONS1. A process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, in which said fibers are treated, in several steps, with: i) at least one treatment stage i) said fibers with a cosmetic composition Ci) containing a) one or more salts of titanium; in particular the titanium atom of said salt (s) is (are) oxidation state 2, 3 or 4 noted Ti (II), Ti (III) or Ti (IV), preferably Ti (IV) ; b) optionally one or more carboxylic acid (s) of the following 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 and / or amino groups; preferably A represents a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group optionally substituted with one or more hydroxyl and / or amino groups; n represents an integer inclusive between 0 and 10, preferably n is between 0 and 5, such as between 0 and 2; and ii) at least one step of coloring said fibers with a cosmetic composition Cii) containing: c) one or more oxidation dye (s); and d) optionally one or more chemical oxidizing agent (s), in particular chosen from hydrogen peroxide or one or more hydrogen peroxide generator system (s); iii) at least one step of intermediate rinsing of said fibers, preferably with water, it being understood that: firstly the composition i) is applied to said fibers, followed by one or more rinsing (s); said fibers, preferably water, and then the composition Cii) is applied to said fibers; or else - firstly the composition C ii) is applied to said fibers, followed by one or more rinsing (s) of said fibers, preferably with water, then the composition Ci) is applied to said fibers. 2. dyeing process according to the preceding claim, characterized in that a) the salt (s) titanium of the invention is (are) chosen from (s) salt (s) organic (s) in particularly from the organic salt (s) of Ti (IV); preferably chosen from among those of the following formula (IA): embedded image Formula (IA) in which: A is identical to that of formula (I) as defined in the preceding claim; 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, chosen in particular from alkali metal cations such as Na, or K, alkaline earth metal such as Ca or organic such as ammonium, preferably ammonium or a hydrogen atom. ; TiY denoting Ti (01-1), r, or Ti (O) 12, or Ti (01-1) ,, i (O) ,, 2 with m1 + m2 = n ". 3. dyeing process according to the preceding claim, characterized in that a) the salt (s) of titanium is (are) chosen from those of formula (IA) whose radical A represents a monovalent group (C1). -C6) alkyl or polyvalent (C1-C6) alkylene optionally substituted with one or more hydroxyl groups or one or more amino groups, preferably with one or more hydroxyl groups, and n representing an integer inclusive of between 0 and 5, such that between 0 and 2, particularly the carboxylic acid (s) used to form the organic titanium salt (s) of the invention are chosen from α-hydroxy acids and α-amino acids; preferentially, the acid is chosen from citric acid, lactic acid, malic acid, tartaric acid, and glycolic acid, and serine, more preferentially chosen from lactic and glycolic acid. 4. dyeing process according to any one of the preceding claims, characterized in that a) the salt (s) of titanium is (are) chosen from those of 3037239 formula (IB): 28 2- M + M + Formula (IB) wherein: - L 'and L ", identical or different, represent a divalent group (hetero) arylene, C6) alkylene, (C2-C6) alkenylene, said alkylene and arylene groups being optionally substituted with one or a plurality of atoms or groups selected from halo, (C1-C4) alkyl, hydroxy, thiol, and (di) (C1-C4) (alkyl) amino, carboxy, and / or optionally interrupted by one or more heteroatoms such as oxygen; Preferably L 'and L "are identical and represent a methylene or ethylene group optionally substituted with a (C1-C4) alkyl group; X 'and X', which are 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 may be identical or different, are as defined for X' and X ", preferably Y and Y 'are identical and represent an oxygen atom, and Ra and Rb, which may be identical or different, represent an atom hydrogen, or a (C1-C6) alkyl, (C2-C6) alkenyl, or (hetero) aryl group, particularly Ra and Rb, identical represent a hydrogen atom or a (C1-C4) alkyl group, Preferably hydrogen, 20 - 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. 5. A dyeing process according to any one of the preceding claims, characterized in that a) the salt (s) of titanium is (are) chosen from dihydroxybis (lactato) titaniumIV salts, in particular those of formula following: 2-OH 0 0, 1 r0 0 2NH4 + / TiN H3C 0 0 C OH 3037239 6. The method of dyeing according to claim 1, characterized in that a) the salt (s) titanium of the invention is (are) chosen (s) from (s) inorganic salt (s) in especially inorganic salt (s) of Ti (II), Ti (III) and Ti (IV), more particularly of Ti (III) and Ti (IV) even more particularly of Ti (IV); preferentially, the titanium salt (s) a) is (are) chosen from titanium halides, titanium sulphates and titanium phosphates. 7. A dyeing process according to any one of the preceding claims, characterized in that a) the titanium salt (s) is (are) present in the composition i) in a content ranging from 0.001% to 20%. % by weight relative to the total weight of the compositions i). 8. dyeing process according to any one of the preceding claims, characterized in that the composition Ci) comprises b) one or more carboxylic acid (s) of formula (I) or one of their salt (s) ) as defined in claim 1; the carboxylic acid (s) b) is (are) different from the carboxylic acids complexed with the Ti salts as defined in any one of claims 1 to 5, preferably glycolic acid, lactic acid, citric acid or a salt thereof. 20 9. The method of dyeing according to any one of the preceding claims, characterized in that the composition Ci) comprises b) one or more carboxylic acid (s) of formula (I) or one of their salt (s) as defined in claim 1 in a content of from 0.1 to 20% by weight, based on the total weight of the composition i). 10. Coloring method according to any one of the preceding claims, characterized in that the composition Ci) is acidic, in particular has a pH of less than 5.0, more particularly at a pH of between 0 and 4, preferably between 0 and 0. , 5 and 3.5, more preferably between 1 and 3. 11. The method of dyeing according to any one of the preceding claims, characterized in that the composition Cii) comprises c) one or more oxidation dye (s) chosen from oxidation bases, and optionally one or more couplers; the oxidation base (s) is (are) particularly chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts, and the the coupler (s) is (are) particularly selected from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. 12. A dyeing process according to any one of the preceding claims, characterized in that the composition Cii) comprises c) one or more oxidation base (s) present (s) in an amount ranging from 0.001 to 10% by weight of the weight total of the composition ii), preferably ranging from 0.005 to 5% by weight of the composition ii); and optionally one or more coupler (s) present (s) in total amount ranging from 0.001 to 10% by weight of the total weight of the composition ii), preferably from 0.005 to 5% by weight relative to the total weight of the composition ii). 10 13. The method of dyeing according to any one of the preceding claims, characterized in that the composition Cii) comprises d) one or more chemical oxidizing agent (s); particularly the chemical oxidizing agent (s) is (are) chosen from hydrogen peroxide, urea peroxide; polymeric complexes which can release hydrogen peroxide such as polyvinylpyrrolidone / H 2 O 2, oxidases in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase), metal peroxides generating hydrogen peroxide in water such as calcium peroxide, magnesium peroxide, perborates and percarborates; Particularly the chemical oxidizing agent (s) is (are) selected from hydrogen peroxide. 14. Coloring process according to any one of the preceding claims, characterized in that the method uses e) one or more basifying agent (s); particularly the alkalinizing agent (s) e) is (are) in the dye composition Cii) as defined in any one of claims 1, 11 to 13; preferably the alkalinizing agent (s) e) is (are) chosen 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) 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 (II): ## STR2 ## Formula (II) wherein W is a divalent radical (C1-C8) alkylene optionally substituted with at least one hydroxyl group or at least one (C1-C4) alkyl radical and / or 3037239 optionally interrupted by at least one heterotatome such as 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 VV 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 sodium or potassium hydroxides, c) the hydroxides of an alkali metal, transition metal, such as Group III, IV, V and VI metal hydroxides; d) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide; more preferably, the alkalinizing agent (s) e) is (are) chosen from ammonia and alkanolamines such as monoethanolamine, even more preferentially ammonia. 15. A dyeing method according to any one of the preceding claims, characterized in that the composition Ci) as defined in any one of claims 1 to 10, is applied first to the keratinous fibers, preferably rinsing with water is then performed on said fibers, and then the composition Cii) as defined in any one of claims 1, 11 to 14 is applied to said fibers. 20 16. A dyeing method according to any one of claims 1 to 14, characterized in that the dye composition Cii) as defined in any one of claims 1, 11 to 14, is applied first to the keratinous fibers, a rinse preferably water is then made on said fibers, and then the composition Ci) as defined in any one of claims 1 to 10 is applied to said fibers. 17. The method of dyeing according to any one of the preceding claims, characterized in that the pause time on the keratinous fibers of the composition Ci) as defined in any one of claims 1 to 10 is between 30 minutes and 2 hours, particularly between 5 minutes and 1 hour, preferably between 5 minutes and 30 minutes and / or the pause of the composition Ci) on the keratin fibers is maintained at a temperature between 20 ° C and 50 ° C, preferably between room temperature (27 ° C) and 40 ° C. 35 18. The method of dyeing according to any one of the preceding claims, characterized in that the pause time on the keratin fibers of the composition Cii) as defined in any one of claims 1, 11 to 14 is between 1 minutes and 2 hours. preferably between 5 minutes and 1 hour, more preferably the pause time is 15 to 30 minutes and / or the pause of the composition Cii) on the keratinous fibers is maintained at a temperature of between 20 ° C. and 50 ° C. ° C, preferably between room temperature (27 ° C) and 40 ° C.