A CAPILLARY COLORING PROCESS USING A TITANIUM SALT, A COLOR, AND A PARTICULAR SOLVENT

专利摘要:
The present invention relates to a multi-step process for dyeing keratinous fibers, human keratinous fibers such as the hair, in which said fibers are treated by: i) at least one treatment step i) said fibers with a cosmetic composition Ci) comprising a) one or more titanium salt (s) and b) optionally one or more particular carboxylic acids; ii) at least one dyeing step with a dyeing cosmetic composition Cii) comprising c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably selected from orthodiphenols; d) at least one liquid organic compound having a solubility parameter value δH of Hansen greater than 0 and less than 16 MPa 1/2 and optionally e) one or more chemical oxidizing agent (s) such ( (s) hydrogen peroxide or one or more hydrogen peroxide generator systems; iii) optionally at least one step of intermediate rinsing said fibers, said step being implemented between step i) and ii) or between step ii) and i), depending on the order in which are put in said steps i) and ii).
公开号:FR3037241A1
申请号:FR1555395
申请日:2015-06-12
公开日:2016-12-16
发明作者:Boris Lalleman；Alain Lagrange
申请人:LOreal SA；
IPC主号:

专利说明:

[0001] 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 present in the form of a hair dye. treated by: i) at least one treatment step i) said fibers with a cosmetic composition Ci) comprising a) one or more salt (s) of titanium and b) optionally one or more particular carboxylic acids; ii) at least one dyeing step with a dyeing cosmetic composition Cii) comprising c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably selected from orthodiphenols; d) at least one liquid organic compound having a Hansen solubility parameter value 6H greater than 0 and less than 16 MPa 1/2 and optionally e) one or more chemical oxidizing agent (s) such ( s) that hydrogen peroxide or one or more system (s) generator (s) of hydrogen peroxide, iii) optionally at least one step of intermediate rinsing said fibers, said step being implemented between step i and ii) or between step ii) and i), depending on the order in which said steps i) and ii) are implemented. 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 sought to increase the efficiency of the reaction of the oxidation dyes used during this process, especially in terms of power, color rise, color fastness on keratinous fibers, in particular vis-à-vis light, successive washes, sweat and / or selectivity of the color between the root and the tip of said fibers. In fact, such improvement (s) will 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 capable of presenting 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 scalp, clothing, or less coloration of the dye mixture (cleaner) during application or break time. Furthermore, it is known to dye keratinous fibers and in particular human hair, with dyeing compositions 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 keratinous 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 from the surface and / or the core of the fiber are responsible their low dyeing power and their poor resistance to light, washing, or perspiration. There is therefore still progress to be made in this field to provide powerful, resistant and hair-respecting dyes from compositions containing especially natural dyes. In the field of coloration from natural extract such as orthodiphenols (ODPs), it is also known to dye keratin materials such as hair or skin from ODPs in the presence of a metal salt, in particular of manganese (Mn) and / or zinc (Zn). In particular, the patent applications FR 2814943, FR 2814945, FR 2814946 and FR 2814947 provide compositions for coloring the skin or keratinous fibers, comprising a dye precursor which contains at least one orthodiphenol, salts and oxides of Mn and / or Zn, 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. 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-pH metals for dyeing keratinous fibers in amounts similar to those used for dyes using an etching process, which consists in preparing the fibers before dyeing 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.
[0002] Other documents describe the use of ODPs associated with salts of Mn, Zn and other metal salts including titanium salts and a chemical oxidizing agent (FR297673, WO2011 / 086284, WO2011 / 086282, and FR2951374) . Nevertheless, improvements still need to be made, especially in terms of color tenacity with regard to shampoos and sweat.
[0003] 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 colorings which are satisfactorily resistant to external agents (light, weather, shampoos, sweat) which are stubborn and homogeneous, ie having low color selectivity between root and tip. , while remaining powerful and / or chromatic. In addition, it is necessary to obtain the satisfactory coloring performance, that the product is stable and has suitable use qualities. This purpose (s) is (are) achieved by the present invention which has A subject of the invention is a process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, in which said fibers are treated, in several steps, comprising: i) at least one treatment step i) said fibers using a cosmetic composition Ci) containing: a) one or more salt (s) 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; Formula (I) in which: -A represents a monovalent group when n is 0 or polyvalent when n is greater than or equal to 1, hydrocarbon comprising 1 to 50 carbon atoms, saturated or unsaturated, cyclic or non-cyclic, aromatic or nonaromatic, optionally interrupted by one or more heteroatoms and / or optionally substituted in particular with one or more hydroxyl 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 employing a dyed cosmetic composition Cii) containing: c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from orthodiphenols; d) at least one liquid organic compound having a Hansen solubility parameter value 6H greater than 0 and less than 16 MPa 1/2 and e) optionally one or more chemical oxidizing agent (s), in particular chosen (s) 20 among hydrogen peroxide or one or more hydrogen peroxide generator system (s); iii) optionally at least one step of intermediate rinsing said fibers, said step being implemented between step i) and ii) or between step ii) and i), depending on the order in which are put in said steps i) and ii).
[0004] The process according to the invention has the advantage of coloring human keratinous fibers with stubborn coloring results. 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, as is the homogeneity of the color between the root and the tip of the fibers. 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 titanium salt (s): The cosmetic composition Ci) used according to the treatment step i) of the process according to the invention comprises at least one or more titanium salt (s); in particular the titanium atom of said salt (s) is (are) of oxidation state 2, 3 or 3 denoted by Ti (II), Ti (III) or Ti (IV), preferably Ti (IV) 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" means 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 C-020 hydrocarbon chain, optionally unsaturated, linear or branched, a group 10 ( 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 carboxylic acid carboxylate group (s). Preferably, the organic salt (s) of titanium (a) of the invention is (are) chosen from those of formula (IA) below: ## STR1 ## IA) wherein: - A is the same as 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 of hydrogen; TiY denoting Ti (01-1), r, or Ti (O) 12, or Ti (01-1) ,, 1 (O) ,, 2 with m1 + m2 = n ", preferably the radical A of the compound (IA ) as defined above represents a monovalent (C1-C6) alkyl or polyvalent (C1-C6) alkylene group 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 between 0 and 5, such as between 0 and 2, particularly the one or more carboxylic acids 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 acid and glycolic.
[0005] Preferentially, the organic salt (s) of titanium a) of the invention is (are) chosen from those of formula (IB) below: 2- M + M + Formula (IB) in which: L 'and L ", which are identical or different, represent a divalent (hetero) arylene, (C6) alkylene, (C2-C6) alkenylene group, said alkylene and arylene groups being optionally substituted by one or more atoms or groups chosen 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, 25 - 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: ## STR2 ## By "inorganic titanium salt" is meant for the purposes of the present invention, the salts themselves derived from the action of an inorganic acid on Ti. The term "acidic" means an acid which does not contain any carbon atoms other than 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 Ti (III), Ti (III) or Ti (IV) salts.
[0006] Preferably, the inorganic titanium salts are Ti (III) or Ti (IV) salts. Particularly preferably, the inorganic titanium salts are Ti (IV) salts. 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 of 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 total weight of said composition i) as defined above. In particular, the organic titanium salt (s) and the inorganic titanium salts according to the invention are soluble in water in a proportion of at least 0.0001 g / l, more preferably at least 1 g / l. B) one or more carboxylic acid (s) The cosmetic composition Ci) used according to the treatment step i) of the process according to the invention may also comprise one or more carboxylic acid (s) .
[0007] According to an advantageous variant, the cosmetic composition Ci) used according to the treatment step i) of the process according to the invention can also comprise b) one or more carboxylic acid (s) of formula (I) such (s) as previously defined. More preferentially, the carboxylic acid or acids b) are different from the carboxylic acids complexed with the Ti salts, preferably glycolic acid, lactic acid, citric acid or a salt thereof. 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 glycolic acid. 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 (1) or their salts may be present in the composition Ci) in a content ranging from 0.1 to 20% by weight, relative to the total weight of said composition Ci).
[0008] C) The dye (s) According to the present invention, the dyed cosmetic composition Cii) used according to the dyeing step ii) of the process according to the invention comprises c) one or more dyes selected from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably selected from orthodiphenols. Preferably, the total content of dyes in the dye composition Cii) is between 0.001 to 20% by weight; preferably between 0.001% and 10% by weight, preferably between 0.001% and 5% by weight, based on the weight of the composition Cii). According to a first embodiment of the invention, the dye coloring composition Cii) 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 preferably be chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts.
[0009] Preferably, the oxidation base (s) of the invention are chosen from para-phenylenediamines and heterocyclic bases. Among the paraphenylenediamines, there may be mentioned, for example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 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 (13-hydroxyethyl) paraphenylenediamine, 4-N, N-bis (13-hydroxyethyl) amino 2-methylaniline, 4-N, N-bis- (13-hydroxyethyl) amino-2-chloroaniline, 2-13-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl paraphenylenediamine, N- ( 13-hydroxypropyl) paraphenylenediamine, the hydroxymethyl alcohol para-phenylenediamine, 2-methoxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, -13-hydroxyethyl) paraphenylenediamine, N- (13, γ-dihydroxypropyl) para-phenylenediamine, N (4 'aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2-13-hydroxyethyloxy paraphenylenediamine, 2-13-acetylaminoethyloxy para-phenylenediamine, N- (13-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, thienyl paraphenylenediamine, 2-hydroxyethylamino-5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid.
[0010] Of the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-13-hydroxyethyl paraphenylenediamine, 2-13-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (13-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.
[0011] 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 4amino-2- (13-hydroxyethylaminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid. Among the ortho-aminophenols, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-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 [1,5-a] -pyridines oxidation bases or their addition salts described, for example, in the FR patent application. 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-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 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 with one or more (C1-C6) alkyl groups such as di (C1-C4) alkylpiperazinium; c) a (C1-C6) alkoxy group optionally substituted with one or more hydroxyl groups such as 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-diamino-3-methyl-1-isopropyl pyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 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 addition salts. 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.
[0012] 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-amin-5- (3- d 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 preferably chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. By way of example, mention may be made of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 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, 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-methyl pyrazol-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. According to a second embodiment of the invention, the dye coloring composition Cii) comprises one or more direct synthetic dye (s). The direct synthetic dye (s) that may be used in the context of the invention may be direct dyes anionic (also called acid dyes), cationic (also called basic dyes) or neutral dyes, fluorescent or not. These direct dyes are in particular chosen from those conventionally used in direct dyeing all current-use aromatic and / or non-aromatic dyes such as neutral, benzene, neutral, anionic (also called acid dyes) or cationic dyes (also known as dyes). basic), neutral azo dyes, anionic dyes (also called acid dyes) or cationic dyes (also called basic dyes), quinone direct dyes and in particular neutral, anionic (also called acid dyes) or cationic dyes (also called basic dyes) ), direct dyes azine, polyarylmethane such as triarylmethane, indoamine, polymethines such as styryl, porphyrins, metalloporphyrins, phthalocyanines, methine cyanines.
[0013] In the context of the present invention, the synthetic direct dye (s) are preferably present in a total amount ranging from 0.001 to 20% by weight, preferably 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 total weight of the dye composition. According to this second embodiment, the synthetic direct dye is preferably chosen from anionic direct dyes or dyes commonly known as "acid" direct dyes or "acid dyes" for their affinity with alkaline substances. Anionic direct dyes are understood to mean any direct dye comprising in its structure at least one SO3- sulphonate group and / or at least one O (O) O- carboxylate group and optionally one or more identical or different G- with G- anionic groups. , representing an anionic group selected from O-alkoxide, thiolate S-, carboxylate and thiocarboxylate: C (Q) Q'- with Q, Q 'identical or different representing an oxygen or sulfur atom; preferably G- represents a carboxylate i.e. Q and Q 'represents an oxygen atom. Preferably, the anionic direct dye (s) is (are) chosen from acidic nitro dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, and the like. acidic anthraquinone dyes and indigoids; each of these dyes having at least one cationic counterionic sulfonate or carboxylate group as defined above; preferentially alkali metal, alkaline earth metal or ammonium sulphonate or carboxylate; and their mixtures. By anionic direct dyes is meant any direct dye comprising in its structure at least one CO2R or 503R substituent with R denoting a hydrogen atom or a cation derived from a metal or an amine, or an ammonium ion.
[0014] 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 and indigoids; and their mixtures.
[0015] More particularly, the dye (s) of the invention are chosen from the direct dyes of formula (VI): ## STR2 ## Col represents the anionic portion of anionic direct dye or "acid" dye Comprising in its structure at least one sulphonate group and / or at least one carboxylate group and comprising m anionic charge (s): m and n, which may be identical or different, represent an integer between 1 and 10 inclusive; - Q +, identical or different, represents a cationic counterion, organic or mineral preferably selected from alkali or alkaline earth metal cations such as Na + or K. In the formula (VI) of the invention the radical Col (- m represents the anionic part of the "acid dyes" or "acid dyes" or anionic direct dyes and preferably Col (-) m has in its structure: o at least one sulphonate group and at least one (hetero) aryl group, it being understood that at least one sulphonate group is directly linked to a (hetero) aryl group, preferably an aryl group such as phenyl or benzo; and optionally, one or more anionic groups G- as defined above. According to another preferred embodiment of the invention, Col (-) m comprises in its structure: at least one carboxylate group and at least one (hetero) aryl group, it being understood that at least one carboxylate group is linked directly to a (hetero) aryl preferentially aryl group such as phenyl or benzo; and o optionally one or more anionic groups G- as defined above.
[0016] According to yet another preferred embodiment of the invention Col% comprises in its structure: at least one carboxylate group, at least one carboxylate group and at least one (hetero) aryl group, it being understood that at least one group The sulfonate or carboxylate is directly attached to a (hetero) aryl preferentially aryl group such as phenyl or benzo; and o optionally one or more anionic groups G- as defined above. According to a particular embodiment of the invention, the dyes of formula (VI) are such that m is equal to n.
[0017] An advantageous variant of the invention relates to the dyes of formula (VI) for which m and n are 1, 2 or 3.
[0018] The preferred anionic dyes of formula (VI) of the invention are selected from acidic nitro dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, and the like; each of these dyes having at least one cationic counterionic sulfonate or carboxylate group as defined above; preferentially alkali metal, alkaline earth metal or ammonium sulphonate or carboxylate. As dyestuffs according to the invention, mention may be made of the dyes of formulas (VII), (VII '), (VIII), (VIII'), (IX), (IX '), (X), (X') , (XI), (XII), (XIII) and (XIV): c3a) the diaryl anionic azo dyes of formula (VII) or (VII '): R 1 R 7 R 10 (VII') formula (VII) and VII ') in which: R7, R8, R9, R10, R'7, R'8, R'9 and R'10, identical or different, represent a hydrogen atom or a group chosen from: i) alkyl ii) alkoxy, iii) alkylthio, iv) hydroxy, v) mercapto, vi) nitro, vii) R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X "- with R ° representing a hydrogen atom, an alkyl or aryl group, X, X 'and X", which may be identical or different, representing an oxygen, sulfur or NR with R representing a hydrogen atom or an alkyl group; viii) (0) 2S (0 -) -, W with W as previously defined for M or represents a cationic counter ion as defined above; ix) (0) C0--, W with W as previously defined; x) R "-S (O) 2-, with R" representing a hydrogen atom, an alkyl group, an aryl group, (di) (alkyl) amino, aryl (alkyl) amino group; preferentially a phenylamino or phenyl group; xi) R - S (O) 2 -X'- where R "is alkyl, optionally substituted aryl, X 'as previously defined; xii) (di) (alkyl) amino; xiii) aryl (alkyl) amino optionally substituted by one or more groups selected from nitro; nitroso; (O) 2S (O -) -, W and alkoxy with W as defined above; xiv) optionally substituted heteroaryl; preferably a benzothiazolyl group; xv) cycloalkyl in particular cyclohexyl, xvi) Ar-N = N- with Ar representing an optionally substituted aryl group, preferentially a phenyl optionally substituted with one or more alkyl groups, (0) 2S (O -) -, W or phenylamino; then two contiguous groups R7 with R8 OR R8 with R9 OR R9 with R10 together form a fused group benzo A 'and R'7 with R'8 OR R'8 with R'9 OR R'9 with R'10 together a fused benzo B 'group with A' and B 'optionally substituted with one or more groups selected from i) nitro; i) nitroso; iii) (0) 2S (0 -) -, W; iv) hydroxy; (v) mercapto; vi) (di) (alkyl) amino; vii) R ° - 10 C (X) -X'-; viii) R ° -X'-C (X) -; ix) R °-X'-C (X) -X "-; x) Ar-N = N- and xi) aryl (alkyl) amino optionally substituted, with W, R °, X, X ', X" and Ar as defined previously; W represents a sigma I bond, an oxygen or sulfur atom, or a divalent radical i) -N (R) - with R as defined above, or ii) methylene-C (Ra) (Rb) - with Ra and Rb identical or different, representing a hydrogen atom or an aryl group, or else Ra and Rb together with the carbon atom carrying them a cycloalkyl spiro; preferentially W represents a sulfur atom or Ra and Rb together form a cyclohexyl; it being understood that the formulas (VII) and (VII ') comprise at least one (O) 2S (O -) -, Q + or carboxylate (O) C (O -) -, Q + radical on one of the rings A, A ', B, B' or C with R1 R2R3R4 as defined previously; preferentially alkali metal, alkaline earth metal or ammonium sulphonate or carboxylate; As examples of dyes of formula (II), mention may be made of: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Red Acid Red 73, Red Acid Red 73, Red Acid Red 135, Red Acid Red 138, Food Red 1, Food Red 1 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, 30 Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2; and by way of example of dyes of formula (VII ') that may be mentioned: Acid Red 111, Acid Red 134, Acid yellow 38; c3b) azo anionic pyrrazolone dyes of formula (VIII) and (VIII '): formulas (VIII) and (VIII') in which: - R11, R12 and R13, which may be identical or different, represent a hydrogen atom, halogen, an alkyl group or - (O) 2S (O-), W with W as defined above; - R14 represents a hydrogen atom, an alkyl group or a group C (O) O-, W with W as defined above; - R15 represents a hydrogen atom; R16 represents an oxo group in which case R'16 is absent, or else R15 with R16 together form a double bond; - R17 and R18, identical or different, represent a hydrogen atom, or a group selected from: - (0) 2S (0 -) -, W with W as defined above; Ar - O - S (O) 2 - with Ar representing an optionally substituted aryl group; preferentially a phenyl optionally substituted with one or more alkyl groups; - R10 and R20 together form either a double bond or a benzo group D ', optionally substituted; R'16, R'16 and R'20, which may be identical or different, represent a hydrogen atom or an alkyl or hydroxy group; - R21 represents a hydrogen atom, an alkyl group, or alkoxy; Ra and Rb, identical or different, are as defined above, preferably Ra represents a hydrogen atom and Rb represents an aryl group; Y represents either a hydroxy group or an oxo group; R13 (VI I I) R13 R21 R21 R14 (V I I I) R16 R16 R14 R15 R18 N N R 19 R20 R17 17 R17 3037241 18 _ _ _ _ - represents a single bond when Y is oxo; and represents a double bond when Y represents a hydroxy group; it being understood that the formulas (VIII) and (VIII ') comprise at least one sulfonate group (O) 2S (O -) -, Q + on one of the rings D or E or the formulas (VIII) and (VIII') 5 comprise at least one carboxylate group (O) C (O -) -, Q + with Q + as defined above; preferably comprise at least one sulfonate group (O) 2S (O -) -, Q + on one of the rings D or E and more particularly sulphonate; By way of example of dyes of formula (VIII) mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and by way of example of dyes of formula (VIII '), mention may be made of Acid Yellow 17; c3c) anthraquinone dyes of formula (IX) and (IX '): (IX) formulas (IX) and (IX') in which: R22, R23, R24, R25, R26 and R27, which are identical or different, represent a hydrogen, halogen, or a group selected from i) alkyl, ii) hydroxy, iii) mercapto, iv) alkoxy, y) alkylthio, vi) aryloxy or optionally substituted arylthio, preferably substituted by one or more groups selected from alkyl and W with W as defined above, vii) aryl (alkyl) amino optionally substituted by one or more groups selected from alkyl and (0) 2S (O -) -, W with W as defined above, viii ) (di) (alkyl) amino, ix) (di) (hydroxyalkyl) amino, x) (O) 2S (O -) -, W with W as previously defined; Z 'represents a hydrogen atom or a group NR28R29 with R28 and R29, which are identical or different, represent a hydrogen atom or a group chosen from among i) alkyl, ii) polyhydroxyalkyl such as hydroxyethyl, iii) aryl optionally substituted by one or more particularly alkyl groups such as methyl, n-dodecyl, n-butyl; (0) 2S (0 -) -, W with W as previously defined; R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X "- with R °, X, X 'and X" such As defined above, preferably R ° represents an alkyl group, iv) cycloalkyl; in particular cyclohexyl; - Z, represents a group selected from hydroxy and NR'28R'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined above; it being understood that the formulas (IX) and (IX ') comprise at least one sulfonate group (O) 2S (O -) -, Q +; By way of example of dyes of formula (IX), mention may be made of: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Blue Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3; and by way of example of dyes of formula (IX ') mention may be made of Acid Black 48; c3d) nitro dyes of formula (X), and (X '): (R 30) p NO 2 (X) (X') formulas (V) and (V ') in which: R30, R31 and R32, identical or different, represent a hydrogen atom, halogen, or a group selected from i) alkyl, ii) alkoxy optionally substituted by one or more hydroxyl groups, iii) alkylthio optionally substituted by one or more hydroxyl groups, iv) hydroxy , mercapto, y) nitro, nitroso, vi) (poly) haloalkyl, vii) R ° -C (X) -X'-, R °-X'-C (X) -, R °-X'-C (X) -X "- with R °; X, X 'and X" as defined above, viii) (0) 2S (0 -) -, W with W as defined previously, ix) (0) C0- -, W with W as defined above, x) (di) (alkyl) amino, xi) (di) (hydroxyalkyl) amino, xii) heterocycloalkyl such as piperidino, piperazino or morpholino especially R30, R31 and R32 represent an atom hydrogen; - R, and Rd, identical or different, represent a hydrogen atom or an alkyl group; - W is as defined previously; W is particularly - NH-; ALK represents a divalent alkylene group, linear or branched, at Cl-06; especially ALK is -CH2-CI-12-; n is 1 or 2; - p represents an integer inclusive between 1 and 5; Q represents an integer inclusive between 1 and 4; u is 0 or 1; when n is 1, J represents a nitro or nitroso group; especially nitro; when n is 2, J represents an oxygen or sulfur atom, or a divalent radical -S (O), with m representing an integer 1 or 2; preferentially, J represents a radical -SO2-; M 'is as defined previously for W; - I present or absent represents a benzo group optionally substituted with one or more R30 groups as defined above; It being understood that the formulas (X) and (X ') comprise at least one sulfonate group (O) 2S (O -) -, Q + or carboxylate (O) C (O -) -, Q +; By way of example of dyes of formula (X), mention may be made of: Acid Brown 13; Orange Acid 3; by way of example of dyes of formula (X '), mention may be made of: Acid Yellow 1, sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino 5-nitro acid benzenesulphonic acid, 2 (4'-N, N (2 "-hydroxyethyl) amino-2'-nitro) aniline ethanesulfonic acid, 4β-hydroxyethylamino-3-nitrobenzene sulfonic acid, and (c) the triarylmethane dyes of formula (XI): (XI) wherein R33, R34, R35 and R36, which may be identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; benzyl 3037241 21 optionally substituted with a group (O), S (O -) -, W with W and m as defined above; R37, R38, R36, R40, R41, R42, R43 and Raa, which may be identical or different, represent a hydrogen atom or a group selected from: i) alkyl, ii) alkoxy, alkylthio, iii) (di) (alkyl) amino, iv) hydroxy, mercapto, v) nitro, nitroso; vii) R ° -C (X) -X'-, R ° -X'-O (X) -, R ° -X'-C (X) -X "- with R ° representing an atom of hydrogen, an alkyl or aryl group; X, X 'and X ", which may be identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; viii) (0) 2S (0 -) -, W with W represents a hydrogen atom or a cationic counterion, ix) (O) 00--, W with W as defined above, or two contiguous groups R41 with R42 OR R42 with R43 OR R43 with R44 form together a benzo fused group with the optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (0) 2S (0 -) -, W; iv) hydroxy; mercapto; vi) ( di) (alkyl) amino; vii) R ° -C (X) -X'-; viii) R ° -X'-C (X) -; ix) R ° -X'-C (X) -X "-; with W, R 0, X, X ', X "as defined above, especially R 37 to R a represent a hydrogen atom, and R 41 to R a, identical or different, represent a hydroxyl group or (0) 2 S (O-) -, W, and when R43 together with R44 form a benzo group, it is preferably substituted with a group (O) 2S (0-) - with the proviso that at least one of the rings G, H, I or I ' comprise at least one sulphonate group (O) 2S (O -) -, Q + or carboxylate (O) C (O -) -, Q +, Examples of dyes of formula (XI) that may be mentioned: Acid Blue 1 Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid Green 50, c3f) xanthene dyes of formula (XII): ## STR2 ## wherein: R 45, R 46, R 47 and R 48, which may be identical or different, represent a hydrogen atom or a halogen atom; R 42, R 50, R 51 and R 52, which may be identical or different, represent a hydrogen atom, a hydrogen atom or a hydrogen atom; halogen, or a group chosen p armin i) alkyl; ii) alkoxy, alkylthio; iii) hydroxy, mercapto; iv) nitro, nitroso; v) (0) 2S (0 -) -, W with W representing a hydrogen atom or a cationic counterion; vi) (0) 00--, W with W as defined above; particularly R53 Rsa, Rss and R48represent a hydrogen or halogen atom; - G represents an oxygen atom, sulfur or a NR group, with Re as defined above; especially G represents an oxygen atom; L represents an alkoxide O-, W; a thioalkoxide S-, W or a group NRf, with Rf representing a hydrogen atom or an alkyl group, and W as defined above; W is particularly Na + or K +; L 'represents an oxygen atom, sulfur atom or an ammonium group: N + RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an optionally substituted alkyl or aryl group; L 'is particularly an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (0), S (0 -) -, W with m and W as defined above; Q and Q ', which may be identical or different, represent an oxygen or sulfur atom; Especially Q and Q 'represent an oxygen atom; - W is as defined previously; it being understood that the formula (XII) comprises at least one sulfonate group (O) 2S (O -) -, Q + or carboxylate (O) C (O -) -, Q + with Q + as defined previously; By way of example of dyes of formula (VII), mention may be made of ammonium salts derived from: Acid Yellow 73; Acid Red 51; Acid Red 87; Acid Red 92; Acid Red 95; Purple Acid 9; c3g) indigo dyes of formula (XIII): (XIII) formula (XIII) in which: R53, R54, R55, R56, R57, R58, R59 and R60, identical or different, represent a hydrogen atom or a group selected from i) alkyl; ii) alkoxy, alkylthio; iii) hydroxy, mercapto; iv) nitro, nitroso; v) R ° -C (X) -X'-, R °-X'-C (X) -, R °-X'-C (X) -X "- 3037241 23 with R ° representing an atom of hydrogen, an alkyl or aryl group; X, X 'and X ", which may be identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; vi) (0) 2S (0 -) -, W with W as previously defined; vii) (0) C0--, W with W as defined above; - G represents an oxygen atom, sulfur or a NR group, with Re as defined above; especially G represents an oxygen atom; - R, and Rh, identical or different, represent a hydrogen atom or an alkyl group; It being understood that the formula (XIII) comprises at least one sulfonate group (O) 2S (O -) -, Q + or carboxylate (O) C (O -) -, Q + with Q + as defined previously; By way of example of dyes of formula (XIII) mention may be made of Acid Blue 74 and indigo carmine (or indigotin 1, blue C1 # 1) is a blue dye (E132 number) extracted from natural indigo. C3h) quinoline-derived dyes of formula (XIV): R64 R61 R6 R63 (XIV) HO-R61 represents a hydrogen atom, halogen atom or an alkyl group; - R62, R63, and R64, identical or different, represent a hydrogen atom or a group (0) 2S (0 -) -, W with W as defined above; or else R61 with R62, or R61 with R64, together form a benzo group optionally substituted with one or more (0) 2S (0 -) - groups, W with W representing a hydrogen atom or a cationic counterion; it being understood that formula (IX) comprises at least one sulfonate group (O) 2 S (O -) -, Q + with Q + as defined above. By way of example of dyes of formula (IX), mention may be made of ammonium salts derived from: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5. More particularly, the dyes of formula (VII) to (XIV) useful for the invention are chosen from the following salts: (Acid Red 87 (XIV) CI 45380) (ammonium salts of 2,4-dinitro-1-naphtho-7- (AC) 10316) sulfonic acid (X ') (Acid Orange 3 (XII) CI 10383) (Acid Yellow 9 / Food Yellow 2 (VII) CI 13015) (Direct Red 45 / Food Red 13 (VII) CI 14780) (Acid Black 52 (VII) CI 13711) ( Acid Yellow 36 (VII) CI 13065) (ammonium salt of 1-hydroxy-2- (2 ', 4'-xylyl-5-CI 14700) sufonatoazo) -naphthalene-4-sulfonic acid / Food Red 1 (VII) (Acid Red 14 / Food Red 3 / Mordant Blue 79 (VII) CI 14720) (ammonium salt of 4-hydroxy-3 - [(2-methoxy-5- C. 14805) nitrophenyl) diaza] -6- (phenylamino) naphthalene-2-sulfonic acid / Acid Brown 4 (VII) ((VII) Acid Orange 7 / Pigment Orange 17 / Solvent Orange 49 CI 15510) ( Food Yellow 3 / Pigment Yellow 104 (VII) CI 15985) (Acid Red 27 / Food Red 9 (VII) CI 16185) (Acid Orange 10 / Food Orange 4 (VII) CI 16230) (Acid Red 44 (VII) CI 16250 ) (Acid Red 33 / Food Red 12 (VII) Cl 17200) (Acid Red 184 (VII) Cl 15685) (Acid Violet 3 (VII) Cl 19125) (ammonium salt of 1-hydroxy-2-acid) (4'-acetamido 3037241 Cl 18055) phenylazo) -8-acetamido-naphthalene-3,6-disulfonic acid / Acid Violet 7 / Food Red 11 (VII) Cl 18130) (Acid Red 135 (VII) Cl 19130) (Acid Yellow 27 (VIII) Cl 19140) (Acid Yellow 23 / Food Yellow 4 (VIII) Cl 20170) (4 '- (sulphonato-2 ", 4" -dimethyl) -bis- (2,6-phenylazo) -1, 3-Dihydroxybenzene / Acid Orange 24 (VII) CI 20470) (ammonium salt of 1-amino-2- (4'-nitrophenylazo) -7-phenylazo-8-hydroxy-naphthalene-3,6- disulfonic acid / Acid Black 1 (VII) 0.I. 23266) (4 - ((4-methylphenyl) sulfonyloxy) -phenylazo) 2,2'-dimethyl-4 - ((2-hydroxy-5,8-disulfonato) naphthylazo) biphenyl / Acid Red 111 (VII ') CI 27755 ) Food Black 2 (VII) C 25440) 1- (4'-sulfonatophenylazo) -4 - ((2 "-hydroxy-3" -acetylamino) -, 8 "-disulfonato) naphthylazo) -6-sulfonatonaphthalene (tetrasodium salt) / Food Black 1 (VII) Cl 42090) Acid Blue 9 (XI) Cl 60730) Acid Violet 43 (IX) Cl 61570) Acid Green 25 (IX) 0.I. 62045) Ammonium salt of 1-amino-4-cyclohexylamino-9,10-anthraquinone 2-sulfonic acid / Acid Blue 62 (IX) 0.1. 62105) Acid Blue 78 (IX) CI 14710) 4-Hydroxy-3 ((2-methoxyphenyl) -azo) -1-naphthalenesulfonic acid ammonium salt / Acid Red 4 (VII) 2-piperidino acid 5-nitro benzene sulfonic acid (X ') 2 (4'-N, N (2 "-hydroxyethyl) amino-2'-nitro) aniline ethane sulfonic acid (X') 4f3-hydroxyethylamino-3-nitrobenzene sulfonic acid ( X ') CI 42640) (Acid Violet 49 (XII) CI 42080) (Acid Blue 7 (XI) CI 58005) (1,2-Dihydroxy-3-sulfo-anthraquinone / Mordant Red 3 (IX) 0.1, 62055) ( 1-Amino-9,10-dihydro-9,10-dioxo-4- (phenylamino) -2-anthracenesulfonic acid / Acid Blue 25 (IX) CI 14710) (4-hydroxy-3 - ((2-methoxyphenyl) azoic acid) 1-naphthalenesulfonic acid / Acid Red 4 (VII) Most of these dyes are described in particular in the Color Index published by The Society of Dyers and Colorists, PO Box 244, Perkin House, 82 Grattan Road, Bradford, Yorkshire, BD1 2JBN England The most preferred anionic dyes designated in Color Ind eg under code CI 58005 (monosodium salt of 1,2-dihydroxy-9,10-anthraquinone-3-sulfonic acid), CI 60730 (monosodium salt of 2 - [(9,10-dihydro-4) 910-dihydroxy-9,10-dioxo-1-anthracenyl) -amino] -5-methyl-benzenesulfonic acid), CI 15510 (monosodium salt of 4 - [(2-hydroxy-1-naphthalenyl) -azo] - benzenesulphonic), CI 15985 (disodium salt of 6-hydroxy-5 - [(4-sulfophenyl) azo] -2-naphthalenesulfonic acid), CI 17200 (disodium salt of 5-amino-4-acid) 3-hydroxy-3- (phenylazo) -2,7-naphthalene disulfonic acid), CI 20470 (disodium salt of 1-amino-2- (4'-nitrophenylazo) -7-phenylazo-8-hydroxy-3-acid, 6-naphthalenesulphonic acid), CI 42090 (disodium salt of N-ethyl-N- [44 [4- [ethyl [3-sulphophenyl) methyl] amino] phenyl] (2-sulphophenyl) methylene] -2 5-cyclohexadien-1-ylidene] -3-sulfobenzenemethanaminium hydroxide, internal salt), CI 61570 (Disodium salt of 2, 2 '- [(9,10-dihydro-9,10-dioxo-1) acid, 4-anthracenediyl) -diimino] -bis- [5-methyl] -benzene sulfonic acid. The composition used according to the invention may of course comprise a mixture of dyes of formulas (VII), (VII '), (VIII), (VIII'), (IX), (IX '), (X), (X '), (XI), (XII), (XIII) and (XIV). It is also possible to use compounds corresponding to the mesomeric, tautomeric forms of structures (VII) to (XIV).
[0019] More particularly the dye (s) according to the invention are chosen from those of formula (VII), (VIII), (IX) and (XIII), and mixtures thereof, preferably chosen from those of formula (XIII). Preferably, the direct anionic dye (s) is (are) chosen from among the dyes of formulas (XIII), and in particular indigo carmine. Preferably, the direct anionic dye (s) are chosen from the direct dyes of formula (VI): ColOrn (C) +) (VI) 10 - Col ", represents the anionic portion of anionic direct dye or "acid" dye comprising in its structure at least one sulphonate group and / or at least one carboxylate group and comprising m anionic charge (s): m and n, identical or different, represent an integer between 1 and 10, inclusive, which may be identical or different, represents a cationic, organic or inorganic counterion, preferably chosen from alkali or alkaline earth metal cations, such as Na + or K +, provided that when a), b) and c) are present in the same composition then c) is different from an azo anionic direct dye comprising a 1,8-dihydroxynaphthalene-3,5-disulfonate group, in particular c) is (are) selected from the following anionic direct dyes: anio azo dyes diaryl compounds of formula (VII): R'7 formula (VII) in which: R7, R8, R9, R10, R'7, R'8, R'9 and R'10, which are identical or different, represent a a hydrogen atom or a group chosen from: i) alkyl, ii) alkoxy, iii) alkylthio, iv) hydroxy, v) mercapto, vi) nitro, vii) R ° -C (X) -X'-, R ° -X'-C (X) -, R °-X'-C (X) -X "- with R ° representing a hydrogen atom, an alkyl or aryl group; X, X 'and X ", which may be identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; viii) (0) 2S (0 -) -, W with W as defined previously for M or represents a cationic counterion as defined above; ix) (0) C0--, W with W as defined above; x) R "-S (O) 2-, with R "representing a hydrogen atom, an alkyl group, an aryl, (di) (alkyl) amino, aryl (alkyl) amino group, preferentially a phenylamino or phenyl group; xi) R - S (O) 2-X with R 3037241 representing an optionally substituted alkyl, aryl group, X 'as defined above; xii) (di) (alkyl) amino; xiii) aryl (alkyl) amino optionally substituted with one or more groups selected from nitro; nitroso; (0) 2S (0 -) -, W and alkoxy with W as previously defined; xiy) optionally substituted heteroaryl; preferentially a benzothiazolyl group; xy) cycloalkyl; especially cyclohexyl, xyi) Ar-N = N- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups, (0) 2S (O -) -, W or phenylamino; Or two contiguous groups R7 with R8 OR R8 with R9 OR R9 with R10 together form a fused group benzo A '; and R'7 with R'8 OR R'8 with R'9 OR R'9 with R'10 together form a fused group benzo B '; with A 'and B' optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (0) 2S (0 -) -, W; iv) hydroxy; y) mercapto; yi) (di) (alkyl) amino; vii) R ° - 15 C (X) -X'-; viii) R ° -X'-C (X) -; ix) R °-X'-C (X) -X "-; x) Ar-N = N- and xi) aryl (alkyl) amino optionally substituted, with W, R °, X, X ', X" and Ar as defined previously; with the proviso that: - formula (VII) comprises at least one (O) 2S (O -) -, Q + or carboxylate (0) C (O -) -, or Q + sulfonate radical on one of the A or B rings; preferentially alkali metal, alkaline earth metal or ammonium sulphonate or carboxylate; when (a), (b) and (c) are present in the same composition, then (c) is different from an azo anionic direct dye comprising a 1,8-dihydroxynaphthalene-3,5-disulphonate group; The anthraquinone dyes of formula (IX): R 22 ID Z (IX) formulas (IX) in which: R 22, R 23, R 24, R 28, R 28 and R 27, which are identical or different, represent a hydrogen or halogen atom; or a group selected from i) alkyl, ii) hydroxy, iii) optionally substituted mercapto, iv) alkoxy, y) alkylthio, yi) aryloxy or arylthio, preferably substituted by one or more groups selected from alkyl and (0) 2S (0 -) -, W with W as defined above, vii) aryl (alkyl) amino optionally substituted by one or more groups selected from alkyl and (0) 2S (O -) -, W with W as defined previously, viii) (di) (alkyl) amino, ix) (di) (hydroxyalkyl) amino, x) (O) 2S (O -) -, W with W as previously defined; Z 'represents a hydrogen atom or a group NR28R20 with R28 and R29, identical or different, represent a hydrogen atom or a group chosen from i) alkyl, ii) polyhydroxyalkyl such as hydroxyethyl, iii) aryl optionally substituted by one or more particularly alkyl groups such as methyl, n-dodecyl, n-butyl; (0) 2S (0 -) -, W with W as previously defined; R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X "- with R °, X, X 'and X" such as defined above, preferably R ° represents an alkyl group, iv) cycloalkyl; in particular cyclohexyl; - Z, represents a group selected from hydroxy and NR'28R'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined above; it being understood that formula (IX) comprises at least one sulfonate group (O) 2S (O -) -, Q +; indigo dyes of formula (XIII): embedded image in which: R53, R54, R55, R58, R57, R58, R59 and R80, which may be identical or different, represent a hydrogen atom or a group selected from i) alkyl; ii) alkoxy, alkylthio; iii) hydroxy, mercapto; iv) nitro, nitroso; v) R ° -C (X) -X'-, R °-X'-C (X) -, R °-X'-C (X) -X "- with R ° representing a hydrogen atom, an alkyl or aryl group X, X 'and X ", which may be identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; vi) (0) 2S (0 -) -, W with W representing a cationic counter ion; vii) (0) C0--, W with W as previously defined; G represents an oxygen atom, sulfur atom or a NR group, with Re as defined above; especially G represents an oxygen atom; - R, and Rh, identical or different, represent a hydrogen atom or an alkyl group; it being understood that at least one of the groups R53, R54, R55, R56, R57, R58, R59 or R60 represents a sulfonate group (O) 2S (O -) -, W or carboxylate (O) C (O-) -, W.
[0020] Preferably, the synthetic direct dye (s) according to the invention are chosen from anionic direct dyes. Preferably, the direct anionic dye (s) is (are) chosen from dyes of formulas (VII), (IX), (XIII), and mixtures thereof. They are preferably selected from indigo carmine, Acid Blue 62, Acid Red 18, Acid Black 1, and mixtures thereof. According to this embodiment, the total content of anionic direct dyes in the dye composition Cii) is preferably between 0.001 and 20% by weight; preferably between 0.001% and 10% by weight, preferably between 0.001% and 5% by weight, relative to the weight of the composition Cii). According to another particular embodiment of the invention, the direct dye (s) are chosen from cationic direct dyes or 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:> He + representing a cationic heteroaryl radical, preferably with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally substituted preferentially by one or more groups (C1- C8) alkyl such as methyl, where Ar + represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge preferably ammonium, especially tri (C1-C8) alkylammonium, such as trimethylammonium,> Ar represents an aryl group, in particular phenyl, optionally substituted, preferentially by a or more electron donor groups such as i) optionally substituted (C1-C8) alkyl, optionally substituted (C1-C8) alkoxy, optionally substituted (iii) (C1-C8) alkyl (alkyl) amino on the group or groups alkyl 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 1 is an optionally substituted divalent (hetero) arylene group, such as phenylene, especially para-phenylene, or naphthalene, optionally substituted, preferably with one or more (C 1 -C 8) alkyl, hydroxyl or (C 1 -C 8) alkoxy groups; ; > Ar "is an optionally substituted (hetero) aryl group such as optionally substituted phenyl or pyrazolyl, preferentially by one or more (C1-C8) alkyl, hydroxyl, (di) (C1-C8) (alkyl) amino groups; (C1-C8) alkoxy or phenyl, Ra and Rb, identical or different, representing a hydrogen atom or a group (C1-C8) alkyl optionally substituted, 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 with a hydroxyl group> C2- represents anionic counterion as defined above According to a preferred variant of the invention, the cationic dyes are chosen from polymethine dyes of formula ( Villa) and (VIll'a) VV + - [C (Rc) = C (Rd)], ', - Ar', Q Ar- [C (Rd) = C (Rc)] ,,, - VV ' +, (Villa) (VIll'a) formulas (Villa) or (VIll'a) with: - W + representing a heterocyclic or cationic heteroaryl group, particularly comprising a quaternary ammonium optionally substituted with one or more groups (C1-C8) alkyl optionally substituted in particular with one or more hydroxyl groups; - representing a heterocyclic or heteroaryl as defined for VV +; Ar represents a (hetero) aryl group such as phenyl or naphthyl, optionally substituted preferentially by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (C1-C8) alkyl groups, preferably C1-C4 groups such as methyl; iii) one or more hydroxyl groups; iv) one or more (C1-C8) alkoxy groups such as methoxy; v) one or more hydroxy (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, piperidinyl or heteroaryl such as pyrrolidinyl, pyridinyl and imidazolinyl; Ar 'is a (hetero) aryl radical as defined for Ar; - m 'represents an integer inclusive between 1 and 4, particularly m is 1 or 2; more preferably 1; Rc, Rd, identical or different, represent a hydrogen atom or a (C1-C8) alkyl group optionally substituted, preferentially C1-C4, or else Rc contiguous with VV + or V r + and / or Rd contiguous with 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.
[0021] More particularly mention may 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 VVO 95/15144, VVO 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: (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 R4 represents a hydrogen atom or an electron-donor group such as (CiC8) optionally substituted alkyl, (C1-C8) optionally substituted alkoxy, (di) (C1C8) (alkyl) amino optionally substituted on the alkyl group or groups; by a hydroxyl group; particularly R 4 is a hydrogen atom, - Z represents a CH group or a nitrogen atom, preferably CH 2 -C 2 - as defined above, preferably represents a halide or a mesylate. In particular, 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: C1-13, CH3 H3C H3CN ## STR2 ## With Q-as previously defined, preferably represents a halide or a mesylate.
[0022] Preferably, the cationic synthetic direct dye (s) is / are present in the dye composition Cii) in a total content of from 0.001% to 10% by weight, preferably from 0.001 to 5% of the total weight of the composition Cii).
[0023] Preferably, the synthetic direct dye (s) is / are present in the dye composition Cii) in a total content of from 0.001% to 10% by weight, preferably from 0.001 to 10% by weight. 5% of the total weight of the composition Cii). According to a third embodiment of the invention, the coloring dye composition Cii) comprises one or more dyes of natural origin. The dyes of natural origin, may be chosen among lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidine, orceins, polyphenols or orthodiphenols (also called ODPs in the following of the description) 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) (also called ODP (s)).
[0024] 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).
[0025] 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. More particularly, the ODP (s) a) represents a compound of formula (II), or one of its oligomers, tautomers, optical isomers, geometric isomers, and its salts or solvates such as hydrates: OH (II) in which: R1 to R4, which may be identical or different, represent: i) a hydrogen atom, ii) halogen, or a group chosen from iii) hydroxy, iv) carboxy, y) carboxylate, (CiC20) 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 unsaturated, bearing or not a cationic or anionic charge, optionally substituted and / or optionally preferably fused with a benzene aromatic ring, 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 together with the carbon atoms carrying them a saturated or unsaturated aromatic or non aromatic ring 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 bearing them a pyrrolyl radical. According to a variant, R2 and R3 form a pyrrolyl or pyrrolidinyl radical fused to the benzene ring bearing the two hydroxyls. Within the meaning of the present invention, and unless a different indication is given: saturated or unsaturated cycles, optionally condensed, may also be optionally substituted; the "alkyl" radicals are saturated, linear or branched hydrocarbon radicals, generally C 1 -C 20 radicals, especially C 1 -C 10 radicals, preferably C 1 -C 6 alkyl radicals, such as methyl, ethyl, propyl or butyl, pentyl and hexyl; the radicals "alkenyl" are hydrocarbon radicals, linear or branched, unsaturated at 02-020; preferably comprising at least one double bond such as ethylene, propylene, butylene, pentylene, methyl-2-propylene and decylene; The "aryl" radicals are mono- or polycyclic carbon radicals, condensed or not, preferably comprising from 6 to 30 carbon atoms and of which at least one ring is aromatic; preferentially chosen from the aryl radical is phenyl, biphenyl, naphthyl, indenyl, anthracenyl, and tetrahydronaphthyl; the "alkoxy" radicals are alkyl-oxy radicals with alkyl as defined above, preferably at 01-010, such as methoxy, ethoxy, propoxy and butoxy; the radicals "alkoxyalkyl" are radicals (01-020) alkoxy (01-O20) alkyl, such as methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, etc .; the "cycloalkyl" radicals are C 4 -C 8 cycloalkyl radicals, preferably cyclopentyl and cyclohexyl radicals; the cycloalkyl radicals may be substituted cycloalkyl radicals, in particular with alkyl, alkoxy, carboxylic acid, hydroxy, amine and ketone groups; the "alkyl" or "alkenyl" radicals, when they are "optionally substituted", may be substituted with at least one atom or group borne by at least one carbon atom chosen from: i) halogen; ii) hydroxy; iii) (01-02) alkoxy; iv) (C1-C10) alkoxycarbonyl; v) (poly) hydroxy (02-04) alkoxy; vi) amino; vii) 5- or 6-membered heterocycloalkyl; viii) optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, and optionally substituted by a (C0 4) alkyl radical, preferably methyl; ix) amino substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally carrying at least: a) a hydroxyl group, b) an amino group optionally substituted with one or two radicals (I-03) 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 which may or may not be different from nitrogen; c) a quaternary ammonium group -N + R'R "R", M- for which R ', R ", which may be identical or different, represent a hydrogen atom, or a C1-C4 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, preferably imidazolium, and optionally substituted by a radical (01-04) alkyl, 3037241 36 preferentially methyl (x) acylamino (-N (R) -C (O) -R ') in which the radical R is a hydrogen atom, a (C1-C4) alkyl radical optionally carrying at least one hydroxyl group; and the radical R 'is a C 1 -C 2 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 or 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 radical (01-04) alkyl optionally bearing at least one hydroxyl group and radical R 'represents a radical (01-04) alkyl, a phenyl radical; xii) aminosulphonyl ((R) 2N-S (O) 2-) in which the R radicals, which may be identical or different, represent a hydrogen atom, a (C 1 -C 4) alkyl radical which may optionally carry 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: -010) alkyl, preferably of 01-08, optionally substituted by one or more radicals selected from hydroxyl, (01-02) alkoxy, (poly) hydroxyalkoxy to 02-04, acylamino, amino substituted by two radicals; alkyl, identical or different, at Cl-04, 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 ring members, preferably 5 or 6-membered, optionally substituted saturated or unsaturated compound optionally comprising another heteroatom identical to or different from nitrogen; ii) halogen; iii) hydroxy; iv) alkoxy in 01-02; v) C1-C10 alkoxycarbonyl; vi) (poly) hydroxyalkoxy at 02-04; vii) amino; viii) 5- or 6-membered heterocycloalkyl; ix) optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, and optionally substituted by a (1-4C) alkyl radical, preferably methyl; x) amino substituted with one or two identical or different C 1 -C 6 alkyl radicals optionally bearing at least: a) a hydroxy, b) amino group optionally substituted 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-ion; of the organic acid, mineral or of the corresponding halide, d) a 5- or 40-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted by a (C1-C4) alkyl radical, preferentially hyl; xi) acylamino (-N (R) -C (O) -R ') in which the radical R is a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and radical R 'is a C 1 -C 2 alkyl radical; xii) carbamoyl ((R) 2 N-C (O) -) in which the radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; xiii) alkylsulfonylamino (R'S (O) 2 -N (R) -) in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a C 1 -C 4 alkyl radical, a phenyl radical; xiv) aminosulphonyl ((R) 2N-S (O) 2-) in which the R radicals, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; (xv) carboxy in 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 0, N and S, preferably 0 or N, optionally substituted by 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.
[0026] 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.
[0027] According to a particular embodiment of the invention, the composition comprises as ingredient c) one or more synthetic orthodipenol (s) According to another preferred embodiment of the invention, the dyeing composition 5 used in the process for dyeing keratinous fibers comprises as dye one or more of ODP (s) natural (s). 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 cyanidin, delphinidin, petunidine, anthocyanins or anthocyanins such as myrtillin, orthohydroxybenzoates, for example salts of gallic acid, flavones such as luteolin, hydroxystilbenes, for example tetrahydroxy-3,3 ', 4,5'-stilbene, optionally oxylated (for example glucosylated), 3,4-dihydroxyphenylalanine and its derivatives, 2,3-dihydroxyphenylalanine and its derivatives, , 5-dihydroxyphenylalanine and its derivatives, 20 - dihydroxycinnamates such as caffeic acid and chlorogenic acid, - orthopolyhydroxycoumarines, - orthopolyhydroxyisocoumarines, - orthopolyhydroxycoumarones, - orthopolyhydroxyisocoumarones, 25 - orthopolyhy droxychalcones, 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 proanthocyanidines Ai, A2, Bi, B2, B3 and ci, chromium and chromene compounds, proathocyanines, tannic acid, ellagic acid; and mixtures of the foregoing compounds.
[0028] 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; carbon or carbon-carbon double bond, as illustrated by the formula (A1) denoting the family of chromenes and the formula (A2) denoting the family of chromanes below: (A1) (A2) 10 More particularly, the ODPs of the invention are of formula (A) and preferably chosen from dyes of the following formulas: formula (III), comprising in its structure the bicycle of formula (A2), R4 OH and its tautomeric and / or mesomeric forms 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: ## STR1 ## wherein R1, R2, R3, R4, R5 and R6, which may be identical or different, represent a hydrogen atom, a hydroxyl group or a group; optionally substituted alkyl, optionally substituted alkoxy, or an optionally substituted acyloxy group; and formula (IV), comprising in its structure the bicycle of formula (AI): ORi2 ORi3 R14 OR16 5 R18 (IV) 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 C 1 -C 4 alkoxy radical. With regard to orthodiphenols of formula (III) as defined above, these can be found in two tautomeric forms (111a) and (111b): ## STR2 ## The alkyl radicals mentioned above in the preceding definitions of the substituents are hydrocarbon radicals, saturated, linear or branched, generally C 1 -C 20, particularly C 1 -C 8, preferably C 1 -C 6, such as methyl, ethyl, propyl, butyl, pentyl and hexyl.
[0029] The alkoxy radicals are alkyl-oxy radicals with the alkyl radicals as defined above, and preferably the alkoxy radicals are C 1 -C 10, such as methoxy, ethoxy, propoxy and butoxy. The alkyl or alkoxy radicals, when substituted, may be substituted by at least one substituent carried by at least one carbon atom selected from i) a halogen atom; or a group ii) hydroxy, iii) C1-2 alkoxy, iv) C1-10 alkoxycarbonyl, v) (poly) hydroxyalkoxy 02-04, vi) amino, vii) 5 or 6 membered heterocycloalkyl, viii) heteroaryl optionally 5-membered or 6-membered cationic group, preferably imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical, preferentially methyl; ix) an amino radical substituted with one or two identical or different C1-C6 alkyl radicals optionally carrying at least: a) a hydroxyl group; b) an amino group optionally substituted by one or two C1-C6 alkyl radicals; 03 optionally substituted, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, 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, preferably imidazolium, and optionally substituted with a radical (01-04) alkyl 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 bearing at least one hydroxyl group and the radical R is a C1-C2 alkyl radical; xi) a carbamoyl radical ((R) 2N-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; 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 bearing 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 radicals R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group; xiv) a carboxylic radical in acid or salt form (preferably with an alkali metal or ammonium, substituted or unsubstituted); xv) a cyano group; (xvi) a nitro group; xvi) a carboxy or glycosylcarbonyl group; xvii) a phenylcarbonyloxy group optionally substituted by one or more hydroxyl groups; xviii) a glycosyloxy group; and xix) a phenyl group optionally substituted with one or more hydroxy groups. 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.
[0030] Among the ODPs of the hematoxylin / haematin and brazilin / braziline type, there may be mentioned, for example, hematoxylin (Natural Black 1 according to the INCI name) and braziline (Natural Red 24 according to the denomination). INCI), 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. The ODPs of formula (III) can be used in the form of extracts. The following plant extracts (genus and species) can be used: Haematoxylon campechianum, Haematoxylon brasiletto, Caesalpinia echinata, Caesalpinia sappan, Caesalpinia spinosa, and Caesalpina Brasiliensis. The extracts are obtained by extraction of various parts of plants, such as, for example, the root, the wood, the bark or the leaf.
[0031] According to a particular embodiment of the invention, the ODP or ODPs are of formula (I) natural and are derived from logwood, pernambuc 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, R14 and R17 denote, independently of one another, a hydrogen atom or an alkoxy radical, preferably methoxy.
[0032] Preferably R 18 and R 15 independently of one another are hydrogen, hydroxy or alkoxy, preferably methoxy. A particularly preferred first family of ODPs suitable for the present invention is that of the dyes of formula (II) above for which R12, R15, R16, R17, R19 and R20 each represent a hydrogen atom. R11 and R13 are each methyl and R14 is methoxy. 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: R11 and R13 each represent a methyl radical, R17 represents the methoxy radical. A preferred dye of this second family is that for which, in addition, R19 represents a methyl radical, R20, R12, R14, R18 and R16 each represent a hydrogen atom, and R15 represents the hydroxyl radical (santarubine A).
[0033] 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). The ODP or ODPs of formula (IV) may be used in the form of extracts. Redwood plant extracts can be used, generally comprising the Asian and West African wood 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 Baphia nitida. These woods can still be called padauk, sandalwood (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 Concentrate. SL 709C by the company COPIAA or 10 by means of a solvent extraction of sandalwood powder such as the product sold under the trade name Sandalwood Powder SL PP by the same company COPIAA. We can also mention the hydroalcoholic extract of Sandalwood powder red ALBAN MULLER company. Extracts also suitable for the present invention can 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 to obtain a powdery extract particularly suitable for the implementation of the present invention.
[0034] 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. 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. The natural extracts of ODPs according to the invention can be in the form of powders or liquids. Preferably, the extracts are in powder form. In particular, the ODPs of the invention are comprised of catechin, quercetin, brazilin, haematein, hematoxylin, chlorogenic, caffeic, gallic acids, catechol, gallic acid, L DOPA, pelargonidine, cyanidine, (-) -Epicatechin, (-) - Epigallocatechin, (-) - Epigallocatechin 3-gallate (EGCG), (+) - Catechin, lsoquercetin, Pomiferin, esculetin, 6,7-Dihydroxy-3- (3-hydroxy-2,4) - dimethoxyphenyl) coumarin. Santalin AC, Mangiferine, Butein, Maritimetine, Sulfuretine, Robtein, Betanidine, Pericampylinone A., Theaflavin, Proanthocyanidin A2, Proanthocyanidin B2, Proanthocyanidin C1, Procyanidins DP 4-8, Tannic Acid, Purpurogalline, 5,6-Dihydroxy-2-methyl 1,4-Naphthoquinone, Alizarin, Vedelolactone, 40 Variegatic Acid, Gomphidic Acid, Xerocomic Acid, Carnosol, and natural extracts 3037241 containing. Preferably, the ODPs of the invention are chromenic or chromanic and are chosen from haematein, hematoxylin, brasiline, brasiline, santaline A. By "carboxylate" is meant carboxylic acid salt.
[0035] 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 their entirety or partially. In particular, with regard to plants, the extracts are derived from fruits including citrus fruits, vegetables, trees and 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. 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. Among the fruit extracts, mention may be made of extracts of apple, grapes (in particular grape seeds), or extracts of beans and / or pods of cocoa.
[0036] Vegetable extracts include potato extracts, onion peels. Among the extracts of wood of trees, one can quote the extracts of bark of pine, extracts of logwood. It is also possible to use mixtures of plant extracts.
[0037] 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 walnut. More preferably, the ODP (s) of the invention is (are) chosen from: - haematein, brasiline, gallic acid, tannic acid, when the dyeing process does not does not use chemical oxidizing agent; or else - hematoxylin, brasiline, gallic acid, tannic acid, when the dyeing process uses a chemical oxidizing agent 40 The natural extracts according to the invention can be in the form of powders or 3037241 46 liquids. Preferably, the extracts of the invention are in the form of powders. Preferably, the dye (s) of natural origin, is / are present in the dye composition Cii) in a total content ranging from 0.001% to 10% by weight, preferably from 0.001 to 5% by weight. total of the composition Cii). As regards the pure dyes, in particular the pure ODPs, the content in the composition or compositions containing them (preferably the dye composition Ci 1) 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 (s) (preferably the dye composition Ci 1)) containing the extracts as such is preferably between 0.1 and 20% by weight of each of these compositions, and better between 0.5 and 10% by weight of the compositions containing them According to the invention, the synthetic direct dye (s), and / or dyes of natural origin, and / or the extract (s) (s) ( s) natural (s) used present (s) present in the dye composition Cii) is preferably from 0.001% to 20% by weight of the total weight of the composition (s) containing them. d) the organic liquid compound (s) having a Hansen solubility parameter value SH greater than 0 and less than 16 MPa The coloring composition Cii) used in the process according to the invention Comprises at least one liquid organic compound having a Hansen solubility parameter 6H greater than 0 and less than 16 MPa1 / 2. In the context of the present invention, such a compound is also called a hydrotrope compound. For the purposes of the present invention, the term "hydrotrope compound" is intended to mean a compound capable of increasing the solubility of the hydrophobic compounds in the aqueous phases. Said liquid compounds more preferably have a Hansen solubility parameter 6H of between 5 and 15.8 MPa1 / 2, more preferably between 8 and 15.8 MPa1 / 2, and better still between 8 and 15 MPa1 / 2.
[0038] These compounds are liquid at 25 ° C and at atmospheric pressure (760 mm Hg, 1.013 × 10 5 Pa). The compound or compounds having a Hansen solubility parameter value 6H, as defined above, are for example described in the reference work "Hansen solubility parameters A user's handbook, Charles M. Hansen", 3037241 47 CRC Press, 2000 , pages 167 to 185, or in the book "Handbook of Solubility Parameters and Other Cohesion Parameters", CRC, Press, pages 95 to 121 and pages 177 to 185. This value of the solubility parameter 6H is related to the formation of hydrogen bonds. It can be recalled that there are three major types of interactions in organic compounds, nonpolar interactions, permanent dipole-dipole interactions and hydrogen bonding interactions, the latter being the subject of the parameter defining the hydrotropic compound. present in the composition implemented according to the invention.
[0039] In particular, the book "Handbook of Solubility Parameters and Other Cohesion Parameters", CRC Press, pages 95 to 121 and pages 177 to 185, gives the equation 6H = (z_zuhA /) 1/2 where, zUh (in J .mo1-1) describes the contributions of the functional group considered in the hydrogen bond-related solubility parameters (values in table 14, page 183), this parameter zUh being also described in the book "The relation between surface tension and solubility". parameter in liquids, Bagda, E, Farbe Lack, 84, 212, 1978; and V is the volume of the molecule. It should be noted that the solubility parameter value 6H is usually given for a temperature of 25 ° C and at atmospheric pressure (760 mm Hg, ie 1.013 × 10 5 Pa). In particular, liquid organic compounds having a Hansen solubility parameter value of 6H greater than 0 and less than 16 MPa 1/2 are nonionic compounds. The liquid organic compound (s) having a Hansen solubility parameter value of 6H greater than 0 and less than 16 MPa1 / 2 may be chosen from: - alcohol ethers, in particular C 1 -C 4 ethers of alcohols in 05-030, preferably saturated, linear or branched, optionally interrupted by one or more non-adjacent ether functions; Aliphatic esters of C 1 -C 4 carboxylic acids and mono or polyhydroxylated C 3 -C 10 alcohols, interrupted by one or more non-adjacent ether functions; aromatic ethers, in particular at 06-010, of C1-C6 alkyl optionally bearing a hydroxyl group; C6-C10 aryl (C6-C10) alkyl (C1-C6) alkyl ethers; Optionally carrying a hydroxyl group, aryl-substituted alkanols, preferably for which the aryl part is at 06-010, advantageously at 06, and the alkyl part of the C 1 -C 4 alkanol this alkyl part. which can be terminated or interrupted by a heteroatom, preferably oxygen or a hydroxyl group, preferably such as benzyl alcohol; the lactones preferably of formula (iii), as well as their mixtures, with: (C1-12) n (iii) in which R 'represents a hydrogen, a linear or branched C1-C8 alkyl, a linear or branched hydroxyalkyl at Cl-04, n is 1, 2 or 3 and preferably R 'is hydrogen, linear or branched C1-C6 alkyl, linear or branched hydroxyalkyl C1-O2. As particularly advantageous examples of lactones, mention may be made of ybutyrolactone. Some liquid alkanols, for example pentanol, may also be mentioned. Preferably, the one or more liquid organic compounds having a Hansen solubility parameter value 6H greater than 0 and less than 16 MPa 1/2 are chosen from alcohols ethers, aliphatic esters, aromatic ethers, alkanols with aryl substituents and mixtures thereof.
[0040] Even more preferentially, the liquid organic compound or compounds according to the invention are chosen from dipropylene glycol monomethyl ether acetate, dipropylene glycol methyl ether and dipropylene glycol mono n-butyl ether (whose INCI name is PPG-2 BUTYL ETHER). ), tripropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, 3-phenyl-1-propanol, 2-phenyl -1-propanol, benzyl alcohol, benzyloxyethanol, phenoxyethanol, and mixtures of these compounds. The liquid organic compound (s) having a value of the Hansen solubility parameter δH greater than 0 and less than 16 MPa 1/2 is (are) even more preferably chosen from aryl-substituted alkanols and even more preferably benzyl alcohol. Preferably, the organic liquid compound (s) having a Hansen solubility parameter value of 6H greater than 0 and less than 16 MPa 1/2 represent a total content ranging from 0.5 to 35% by weight, preferably from 0.5 to 20% by weight, more preferably from 0.5 to 10% by weight relative to the total weight of the dye composition Cii). In one variant of the invention, the composition Ci also comprises one or more organic compound (s) having a Hansen solubility parameter value of 6H greater than 0 and less than 16 MPa 1 / 2. The preferences concerning the nature of the liquid organic compound having a Hansen solubility parameter value 6H greater than 0 and less than 16 MPa 1/2 are the same as those indicated in the context of the composition Cii).
[0041] In particular, the liquid organic compound (s) having a Hansen solubility parameter value of 6H greater than 0 and less than 16 MPa 1/2 is preferably selected from alcohols, aliphatic esters, ethers and the like. aromatic compounds, aryl-substituted alkanols and mixtures thereof. Preferably, the organic liquid compound (s) having a Hansen solubility parameter value of 6H greater than 0 and less than 16 MPa 1/2 represent a total content ranging from 0.1 to 35% by weight, preferably from 0.1 to 20% by weight, better still from 0.5 to 10% by weight relative to the total weight of the composition Ci).
[0042] Preferably, the organic liquid compound (s) having a Hansen solubility parameter value of 6H greater than 0 and less than 16 MPa 1/2 represent a total content ranging from 0.5 to 10% by weight relative to the total weight of the composition C1. E) the chemical oxidizing agent (s) According to one particular embodiment of the invention, the dyeing method also implements one or more chemical oxidizing agent (s). This embodiment is particularly preferred in the case where the dye composition Cii) used in the process according to the invention comprises at least one oxidation dye. 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) polymeric 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 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 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 to 10% by weight. , 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. When the process according to the invention uses at least one chemical oxidizing agent, this can be implemented by extemporaneously adding it to one of the compositions, preferably in the coloring composition Cii), just before application. of said composition on the keratinous fibers, or independently, in a third composition comprising no dye in an additional oxidation step.
[0043] According to another embodiment, the process according to the invention does not use a chemical oxidizing agent. According to a particular embodiment of the invention, the process according to the invention does not use hydrogen peroxide. Preferably, according to this embodiment, the process according to the invention does not use chemical oxidizing agent. According to this embodiment, the dye composition Cii) preferably comprises one or more dyes chosen from synthetic direct dyes and / or dyes of natural origin. F) the alkalinizing agent (s) According to one particular embodiment of the invention, the dyeing process may use one or more alkalinizing agent (s) f). Preferably, the alkalinizing agent (s) e) are in the dyeing composition with the dye (s) c) as defined previously. 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.
[0044] These alkalinizing agents are bases for increasing the pH of the composition (s) in which it is found. The basifying agent is a Bronsted, Lowry or Lewis base. It can be mineral or organic. Particularly the 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 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) 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, which are identical or different, represent a hydrogen atom, a (C1-C4) alkyl or hydroxy (C1-C4) alkyl radical, preferentially 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 hydroxides of sodium or potassium, c) the hydroxides of a metal such as hydroxides of Group III, IV, V and VI metals, d) 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 +, CO2), alkaline earth metal (Met2 +, CO2) of 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 (CiC6) alkyl group optionally substituted 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 + - wherein 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 hydrogen carbonate is then called dihydrogen carbonate (002, H20); and Met2 + (1-1CO3-) 2 with Met 'representing an alkaline earth metal.
[0045] 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 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] = Na2003, sodium hydrogencarbonate or sodium bicarbonate [144-55-8] = NaHCO3, and sodium dihydrogen carbonate = Na (HCO3) 2.
[0046] According to a particularly advantageous embodiment, the alkalinizing agent (s) (e) is (are) chosen from ammonia and alkanolamines such as monoethanolamine, preferably ammonia. According to a particularly advantageous embodiment, the alkalinizing agent (s) (e) is (are) chosen from ammonia, carbonates, bicarbonates, arginine and their mixtures. 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. Compositions: The compositions used in the process 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.
[0047] Additional organic solvents: As additional organic solvent (different from the organic liquid compound (s) having a Hansen solubility parameter value 6H greater than 0 and less than 16 MPa 1/2 ), for example, C 1 -C 4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers.
[0048] Preferably, the composition Ci) and / or the dyeing composition Cii) comprises at least one lower alkanols of Cl-04, such as ethanol and isopropanol. Preferably, the composition Ci) and / or the dye composition Cii) comprises ethanol.
[0049] The additional organic solvents (different from the organic liquid compound (s) having a Hansen solubility parameter value greater than 0 and less than 16 MPa 1/2) can be present in a total preferably between 1 and 40% by weight relative to the total weight of the dye composition Cii), and even more preferably between 5 and 30% by weight approximately.
[0050] 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, inorganic or organic thickeners and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, agents and the like. penetrants, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents, agents clouding.
[0051] Said adjuvants are preferably selected 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, one 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) used according to the process according to the invention may be in various galenic forms, such as a powder, a lotion, a mousse, a cream or a gel, or any other form suitable for 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 the ingredients a) to e) is acidic, ie has a pH below 7.0, preferably below 5. , 0, especially at a pH of from 0 to 4 inclusive, more preferably from 0.5 to 3.5, preferably from 1 to 3. Preferably, the composition Ci) is acidic (i.e. has a pH below 7.0), preferably has a pH below 5.0, particularly 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 is alkaline, is greater than 7, preferably between 8 and 12 and, more particularly, between 8 and 11 inclusive. particular embodiment of the invention, the composition i) containing the or the titanium salts a) and not containing alkalinizing agent e) have a pH of less than 7, and preferably less than 5, particularly at a pH between 0 and 4. The pH of these compositions can be adjusted to the desired value by means of alkalinizing agents as defined previously in e) or from acidifying agents usually used for 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 The method for dyeing the keratinous fibers of the invention implements i) at least one treatment step with a composition Ci), as defined above, ii) at least one step staining with a dye composition Cii), as defined above, iii) and optionally at least one intermediate rinsing step, said step being carried out between step i) and ii) or between step ii) and i), depending on the order in which said steps i) and ii) are implemented.
[0052] Thus, the process according to the invention implements at least two distinct stages, one of which is at least one treatment step and at least one staining step. According to a first embodiment of the invention, the treatment step with the composition Ci) is carried out after the coloration step with the composition Cii). According to a second embodiment of the invention, the treatment step with the composition Ci) is carried out before the step of coloring with the composition Cii). Preferably, according to one or other of these embodiments, the method according to the invention implements an intermediate rinsing step. Thus, the intermediate rinsing step iii) is carried out between the treatment step i) with the composition (Ci) and the staining step ii) with the composition (Cii), or between the staining step ii) with the composition Cii) and the treatment step i) with the composition Ci). Intermediate Rinse Step According to a preferred embodiment of the invention, the method according to the invention may comprise a step iii) of intermediate rinsing. According to this embodiment, said rinsing step is carried out between step i) and ii) or between step ii) and i), as a function of the order in which said steps are implemented i) and ii).
[0053] Particularly preferably, when intermediate rinsing step iii) is present, it is carried out with a composition comprising water. In particular, according to a preferred embodiment of the invention, said intermediate rinsing step iii) is carried out exclusively with water, without adding an additional compound. According to another embodiment, the composition used to carry out the rinsing step may also comprise one or more additional compounds. This means that according to a first particular embodiment of the invention, the method according to the invention comprises the implementation of a step of pretreatment of the keratinous fibers via the application thereto of a composition Ci) , preferably followed by a step of rinsing these fibers, preferably with water, and then carrying out a staining step via the application of a dye composition Cii) to the fibers, in which - the cosmetic composition Ci) comprises a) one or more salt (s) of titanium; especially preferably the titanium atom of said salt (s) is (are) of oxidation degree 2, 3 or 4 denoted Ti (II), Ti (III) or Ti (IV), of preferably Ti (IV); and b) optionally one or more carboxylic acid (s) of formula (I); and - the cosmetic composition Cii) comprises c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols. ; and d) at least one liquid organic compound having a Hansen solubility parameter value 6H greater than 0 and less than 16 MPa 1/2. In other words, according to this embodiment, the dyeing method according to the invention implements a pre-treatment step with the composition Ci) and then preferably a step of rinsing the fibers before the dyeing step. with the composition Cii). According to a second embodiment of the invention, the method according to the invention comprises the implementation of a step of treating the keratinous fibers via the application thereto of a dye composition Cii), followed by a step of rinsing these fibers, preferably with water, then of carrying out a post-treatment step via the application of a composition Ci) on the fibers, in which: cosmetic composition Ci) comprises a) one or more salt (s) of titanium; in particular preferably 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) and b) optionally one or more carboxylic acid (s) of formula (I); and - the cosmetic composition Cii) comprises c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and dyes of natural origin, preferably chosen from ortho-diphenols. ; and d) at least one liquid organic compound having a Hansen solubility parameter value 6H greater than 0 and less than 16 MPa 1/2.
[0054] According to one 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; Wherein (A) is 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 (CiC6) alkylene group optionally substituted by one or more hydroxyl 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) of The process of the invention is (are) chosen from those of formula (PA), (IB), or the dihydroxybis (lactato) titaniumIV salt as defined above. According to a preferred embodiment of the invention, the dyeing method uses the application on said fibers of the composition Ci) as defined above, then a rinsing preferably with water of said fibers, and then the application 15 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 Ci) as defined above is between 5 minutes and 2 hours, more particularly between 15 minutes and 1 hour, preferably between 30 and 45 minutes. Preferably the pause of the composition Ci) on the keratin 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 compositions i) and ii) or ii) and i), at least one rinsing step is carried out in the process of the invention. According to a 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 a hydrogen peroxide. or more hydrogen peroxide generator system (s) as defined previously. When the composition Cii) comprises at least one oxidation dye and comprises at least one chemical oxidizing agent, it is also referred to as a "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 least one 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 Cii), 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 hour, more preferably break time is 15 to 30 minutes. Preferably the pause of the composition Cii) on the keratinous fibers is carried out at a temperature of between 20 ° C. and 50 ° C., preferably between room temperature (27 ° C.) and 40 ° C. 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 of between 0 and 4, more particularly 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 10 acid preferably less than 5, particularly at a pH inclusive between 0 and 4, more 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.
[0055] According to a particular embodiment of the invention, the coloring composition Cii) comprising the oxidation dye (s) as defined above further comprises one or more alkalinizing agents (f) as defined above, preferably ammonia. In particular, the pH of the composition comprising one or more alkalinizing agents, preferably the composition ii) is between 8 and 12, particularly between 8 and 11 After the application of the compositions Ci), the optional rinsing of the keratin fibers and the application of the composition Cii), and vice versa, the dyeing method of the invention can implement one or more shampoos, followed by one or more rinsing with water keratin fibers and optionally followed by drying by a 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 of 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. A particular embodiment of the invention relates to a coloring process which is carried out at room temperature (25 ° C).
[0056] 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.
[0057] The following examples serve to illustrate the invention without being limiting in nature. Example 1: Pre-treatment with a composition comprising a titanium salt prior to dyeing with a natural dye The following compositions were prepared from the following ingredients in the following proportions indicated in grams per 100 grams of composition: Treatment Ci): Ingredients Composition Ci) (% in g) Dihydroxybis (ammonium lactate) titanium (IV) at 50% by weight 10.3 Glycolic acid 15 SCLEROTIUM GUM sold under the reference AMIGEL by the company Alban Muller 1 Ethanol 10 Alcohol Benzyl 5 pH agent Qsp pH = 2 ± 0.3 Water qsp 100 Coloring composition Cii): Ingredients Coloring composition Cii) (% in g) Carbolic wood extract oxidized to 10% hatein 4 Ethanol 10 Benzyl alcohol 5 SCLEROTIUM GUM on the market under the reference AMIGEL by the company Alban Muller 1 pH agent Qsp pH = 2 ± 0.3 Water qs 100 3037241 The composition Ci) of pre-treatment with the titanium salt was applied s ur: - a lock of Caucasian hair 90% natural white (90 BN); - a lock of permed white hair (90 BP); a wick of 100% natural white Chinese hair (100 BN). During this pretreatment step, a bath ratio of 1 gram of composition is respected for 1 gram of treated lock. The composition Ci) is left for 15 minutes on each wick at 40 ° C, then each of the locks is rinsed with running tap water following the same experimental protocol.
[0058] The coloring composition Ci 1) is then applied to each wick and left for 30 minutes at 40 ° C. At the end of these exposure times, the locks stained according to the method of the invention were washed with the elixir multivitamin shampoo, rinsed and then dried in the helmet. Results of coloring Black locks were obtained with the locks of hair which had been pre-treated with the titanium salts, which are very intensely colored, which is confirmed by the colorimetric measurements below. In addition, it appears that the coloration is homogeneous with the process according to the invention. These results are confirmed with the measurements of L. a. The colorimetric measurements were performed using a Minolta CM3600D spectrocolorimeter (Illuminant D65, 10 ° angle, specular component included) in the CIELab system. In this system, L * represents clarity. The lower the value of L *, the darker and more powerful the coloration obtained. The rise of the color is represented by the color difference AE between the unstained wick and the colored wick: the higher the value of AE, the higher the rise in color. This value is calculated from the following equation (i): ## EQU1 ## ), L *, a * and b * represent the values measured on unstained locks of hair, and Lo *, ao * and bo * represent the values measured on locks of colored hair.
[0059] 3037241 61 The results L, and raised AE of the color are listed in the table below: Intense black bluish colorations were obtained, as shown by the 5 colorimetric measurements: Process Hair type * AE Color on hair rise Reference undyed hair before treatment 90 BN Caucasian 65.08 - - 90 Caucasian BP 65.02 - 100 BN Chinese 77.39 - Invention: Pre-treatment 90 BN 22.5 46.39 Black blue composition Ci) + rinse + Coloring composition Cii) 90 BP 23.29 45.33 100 BN Chinese 24.53 58.9 It appears from the above results that a very intense coloration was obtained with the dyeing method according to the invention since the value of L decreases sharply.
[0060] In addition, there is a good rise in the color E. Example 2: Pre-treatment with a composition comprising a titanium salt prior to dyeing with a natural dye The following compositions were prepared from the following ingredients in the following proportions: in gram per 100 grams of composition: Pre-treatment composition Ci): Ingredients Composition Ci) (% in g) Dihydroxybis (ammonium lactate) titanium (IV) at 50% by weight 10.3 Glycolic acid 15 SCLEROTIUM GUM marketed under the reference AMIGEL by the company Alban Muller 1 Ethanol Benzyl alcohol 5 pH agent Qsp pH = 2 ± 0.3 3037241 62 Water qsp 100 Coloring composition Cii): Ingredients Coloring composition Cii) (% in g) Campêche (HAEMATOXYLON CAMPECHIANUM POVVDER) to > 70% in hematoxylin marketed under the reference ABCOL HEMATOXYLIN - BSC CERTIFIED by Abbey COlor 4 Ethanol 10 Benzyl Alcohol 5 pH Agent Qsp pH = 2 ± 0.3 Water qs 100 5 Oxidizing Composition Ciii): Ingredients Oxidizing composition Ciii) (') / 0 in g) sodium bicarbonate 5 L-arginine 7 Hydrogen peroxide (50%) 1.7 Water qs 100 HYDROXYPROPYL STARCH PHOSPHATE sold under the name STRUCTURE ZEA by AKZO NOBEL 5 Agent pH Qsp pH = 10 ± 0.3 10 The composition Ci) of pretreatment with the titanium salt was applied to: - a lock of Caucasian hair 90% natural white (90 BN); - a lock of permed white hair (90 BP); a strand of 100% natural white Chinese hair (100 BN). During this pretreatment step, respecting a bath ratio of 10 grams composition i) for 1 gram of treated wick. The composition Ci) is left for 15 minutes on each wick at 40 ° C, then each of the locks is rinsed with running tap water following the same experimental protocol. The coloring composition Ci 1) is then applied to each wick and left for 30 minutes at 40 ° C. and then rinsed. The composition Ciii) is applied to each of the locks and left for 15 minutes at 40 ° C.
[0061] At the end of these exposure times, the locks stained according to the process of the invention and according to the comparative method were washed with the Elsève multi-vitamin shampoo, rinsed and then dried with a helmet. Staining Results With the hair strands pre-treated with the composition Ci) comprising the titanium salts, black locks were obtained which are very intensely colored, which is confirmed by the colorimetric measurements below. In addition, it appears that the coloration obtained is visually very homogeneous with the process according to the invention. These results are confirmed by the colorimetric measurements of L, and AE (color rise) with a Minolta CM3600D spectrophotometer (illuminant D65, 10 ° angle, specular component included) in the CIELab system, which are listed in the table below. below: Method Hair type * AE Color mounted on the hair Reference undyed hair before treatment 90 BN Caucasian 65.08 - - 90 BP Caucasian 65.02 - 100 BN Chinese 77.39 - Invention: Pre-treatment composition Ci) + rinse + Coloring composition Cii ) + rinse + Oxidizing composition Ciii) 90 BN 19.79 47.95 Black 90 BP 20.81 46.6 100 Chinese BN 22.54 59.41 It appears from the above results that a very intense coloration is obtained with the staining method according to US Pat. invention since the value of L decreases sharply. In addition we have a good rise of the color E.
[0062] EXAMPLE 3 The following compositions were prepared from the following ingredients in the following proportions indicated in grams per 100 grams of composition: - Pre-treatment composition Ci): Ingredients Composition Ci) (% in g) Dihydroxybis ( ammonium lactate) titanium (IV) at 50% by weight 10.3 Glycolic acid 15 Water qs 100 10 Coloring composition Cii): A dye composition Cii) according to the invention comprising at least one liquid organic compound having a value the Hansen solubility parameter 6H greater than 0 and less than 16 MPa 1/2, and a comparative comparative coloring composition Cii ') not comprising a liquid organic compound having a Hansen solubility parameter value 6H greater than 0 and less than 16 MPa 1/2. Ingredients Coloring composition Cii) (% in g) Invention Coloring composition Cii ') (/ o in g) Comparative except invention Carbolic wood extract oxidized to 10% hatein 4 4 Ethanol 15 15 Benzyl alcohol 5 0 Water Qsp 100 Qsp 100 pH agent qsp pH = 2 ± 0.3 qsp pH = 2 ± 0.3 The study covers three types of locks of hair: 20 - Caucasian 90% natural white (90 BN); - Caucasian 90% white permed (90 BP); - 100% natural whites (100 BN).
[0063] According to a first treatment method according to the invention Pi, these different locks are pre-treated with the composition Ci) comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair. During this pretreatment step, the composition Ci) is left for 20 minutes on each wick at 40 ° C., then each of the locks is rinsed with tap water and wrung out. The dye composition Cii) is then applied to each of the 3 locks at a rate of 3.33 g of composition per gram of hair and allowed to stand for 45 minutes at 40 ° C.
[0064] In parallel, according to a second method of comparative treatment outside the invention P2, the three different locks are pre-treated with the composition Ci) comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair. During this pretreatment step, the composition Ci) is left for 20 minutes on each wick at 40 ° C, then each of the locks is rinsed with running tap water and wrung out.
[0065] Then the comparative coloring composition Cii ') not comprising a liquid organic compound having a Hansen solubility parameter value 6H greater than 0 and less than 16 MPa 1/2 is then applied to each of the 3 locks at a rate of 3.33 g composition per gram of hair and left for 45 minutes at 40 ° C.
[0066] Finally, in parallel, according to a third method of comparative treatment outside the invention P3, the three different locks are not pre-treated with the composition Ci) but are only wetted. The coloring composition Cii) is then applied to each of the 3 locks at the rate of 3.33 g of composition per gram of hair and allowed to stand for 45 minutes at 40 ° C. At the end of the exposure time, all the locks are washed with Elsève multi-vitamin shampoo, rinsed and then dried with a helmet.
[0067] Staining Results: Visual Evaluation It can be seen that, according to the method of the invention P1 (pretreatment with the compositions composition C 1, rinsing and then treatment with the coloring composition C11), wicks which were intensely colored in black were obtained. . In the case of the non-invention comparative treatment P2 of the locks with the composition Ci, then rinsed and then stained with the composition Cii ', wicks of less intense coloring and stained in dark blue were obtained. Finally, in the case of the comparative treatment P3 of the locks, without pretreatment with the composition Ci), stained with the composition Cii), less intense locks were obtained and colored in brown. These results were confirmed by the following colorimetric measurements; Colorimetric measurements For each of the wicks, the colorimetric measurements of the parameters L * were carried out. at*. and b * and 4E * color rise with a Minolta CM3600D spectrophotometer (illuminant D65, 10 ° angle, specular component included, in the CIELab system).
[0068] In this system, L * represents clarity. The lower the value of L *, the darker and more powerful the coloration obtained. The rise in color is represented by the color difference ΔE between the unstained wick and the colored wick: the higher the value of AE, the greater the rise in color. This value is calculated from the following equation: E =) + (a * - ao *) 2 + (b * 25 In the previous equation, L *, a * and b * represent the values measured on wicks of unstained hair, and LO *, a0 * and b0 * represent the values measured on locks of colored hair The results obtained are as follows: * Type * AE * method Hair color mounted on hair Hair reference no 90 BN 74 , 37 - white dyed before Caucasian treatment 90 BP 77.5 - Caucasian 3037241 67 100 86.86 - BN Chinese Process P1 according to the invention: 90 BN 26.85 49.94 Black pre-treatment composition Ci) + Caucasian blue rinsing + Coloring composition Cii) 90 BP 28.8 49.7 Caucasian 100 BN 27.51 64.31 Chinese Comparative P3 process out of 90 BN 36.06 42.53 Copper brown invention: rinse then Caucasian coloring composition Cii) without pre-treatment 90 BP 37.91 43.67 Caucasian 100 BN 42.03 49.16 Chinese Comparative P2 process out of 90 BN 30.23 47.27 Blue f Invention: Caucasian pre-treatment composition Ci) + rinse + Comparative coloring composition C'ii) 90 BP 31 84 46 88 Caucasian 100 BN 31 28 62 19 Chinese It appears from the above results that we have obtained with the process according to the invention P1 according to the invention (Pretreatment composition Ci) + rinsing + Coloring composition Cii)) a very intense coloration with the dyeing process according to the invention 5 since the value of L decreases strongly compared with to that of unstained natural hair. In addition, there is a very good rise in the color E. With the comparative method P3 not implementing a pre-treatment with the composition Ci), as well as with the comparative method P2 implementing a coloring composition Cii ' ) not comprising a hydrotrope solvent, there was obtained in both cases a staining significantly less powerful in terms of color intensity and in terms of color rise than with the method according to the invention P1.
[0069] EXAMPLE 4 The following compositions were prepared from the following ingredients in the following proportions indicated in grams per 100 grams of composition: - Pretreatment Composition Ci): Ingredients Composition 1 Ci) (% in g) Acid Glycolic 15 g Dihydroxybis (ammonium lactate) titanium (IV) at 50% by weight 10.3 g Water qs 100 g pH agent Qsp pH = 2 ± 0.3 - Coloring composition Cii): ingredients Composition 2 Cii) (% in g) Indigo carmine 4g Indigotine 85% marketed by LCVV Sensient Ethanol 24 g Benzyl alcohol 10 g Water qs 100 g pH agent Qsp pH = 2 ± 0.3 Protocol The study deals with locks of Caucasian hair 90% natural white (90 BN ).
[0070] According to a first treatment method according to the invention Pi, these different locks are pre-treated with the composition Ci) comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair. During this pretreatment stage, the composition Ci) is left for 45 minutes on a wick at 40 ° C., then the wick is rinsed with tap water and wrung out. The dye composition Cii) is then applied to the wick at a rate of 3.33 g of composition per gram of hair and left for 45 minutes at 40 ° C. In parallel, according to a second method of comparative treatment outside the invention P2, the lock is not pre-treated with the composition Ci) but is only wetted. Then the dye composition Cii) is then applied to the wick at a rate of 3.33 g of composition per gram of hair and left for 45 minutes at 40 ° C.
[0071] After these exposure times, the lock is washed with Elsève multivitamin shampoo, rinsed and then dried with a helmet. Results of colorations The strands of colored hair were obtained according to the process of the invention, that is to say with the pretreatment with the titanium salts of very intensely colored locks while those which did not had the pre-treatment of titanium are faintly colored. These results are confirmed with the measurements of L. a. The colorimetric measurements were made using a Minolta CM3600D spectrocolorimeter (Illuminant D65, 10 ° angle, specular component included) in the CIELab system. In this system, L * represents clarity. The lower the value of L *, the darker and more powerful the coloration obtained. The rise in color is represented by the color difference ΔE between the unstained wick and the colored wick: the higher the value of AE, the higher the rise in color. This value is calculated from the following equation (i): ## EQU1 ## ), L *, a * and b * represent the values measured on unstained locks of hair, and Lo *, ao * and bo * represent the values measured on locks of colored hair. The results L, and raised AE of the color are listed in the table below: Intense black bluish colorations were obtained, as shown by the colorimetric measurements: 5 10 3037241 Method Hair L ab AE * rise Color Comparative process without pre-treatment with titanium salt: treatment directly with coloring composition BN 55.25 -12.41 0.19 21.87 Sky blue Process according to the invention with pre-treatment with titanium salt (composition 1 and then rinsing then application of the composition 2) BN 25.34 -5.97 -15.44 49.32 Sustained blue It is clear that the wick colored according to the process of the invention with the composition Ci) 1 then rinsed and then with the composition dye Cii) 2 is stained in a much more intense manner and with a color increase significantly greater than that obtained with the wick colored according to the comparative method without pretreatment with the composition comprising the salt of titanium, since the value of L greatly decreases according to the invention and the rise value of the color AE is higher according to the invention.
[0072] EXAMPLE 5 The following compositions were prepared from the following ingredients in the following proportions indicated per gram per 100 grams of composition: Pre-treatment composition C (i): identical to that of Example 4 (composition 1 Ci)) ingredients Composition 1 Ci) (% in g) Glycolic acid 15 g Dihydroxybis (ammonium lactate) titanium (IV) at 50% by weight 10.3 g Water qs 100 g pH agent Qsp pH = 2 ± 0.3 Coloring compositions C (ii): The following three coloring compositions C3, C4, and C5 were made, each comprising a different anionic direct dye: Ingredients Composition 3 Composition 4 Composition Ci (Ci) Ci (Ci) (g) ) (% in g) (% in g) Acid black 1 0.1 Acid Blue 62 - 0.1 - Acid Red 18 - - 0.1g Ethanol 15 15 15 Benzyl alcohol 5 5 5 Water qs 100 g qs 100 g qs 100 g pH pH 7 pH 7 pH 7 Protocol The study deals with locks of Caucasian hair 90% natural white (90 BN).
[0073] According to a first dyeing process according to the invention Pi, 3 locks are pre-treated with the composition 1 Ci) comprising the titanium salt in a proportion of 3.33 g of composition per gram of hair. During this pretreatment step, the composition Ci) is left for 15 minutes on each wick at 40 ° C, then each wick is rinsed with tap water and dewatered. Each of the coloring compositions Cii) 3, 4 and 5 is then applied separately to each of the 3 locks at a rate of 3.33 g of composition per gram of hair and left for 15 minutes at 40 ° C.
[0074] In parallel, according to a second method of comparative treatment excluding the invention P2, the three different locks are not pre-treated with the composition 1 Ci) but are preferably wetted. Then the coloring compositions Cii) 3, 4 and 5 are then applied separately, each on one of the 3 locks at a rate of 3.33g of composition per gram of hair and left for 15 minutes at 40 ° C. According to this staining method, there is therefore no pretreatment step of the locks with the composition 1 Ci). The following results are obtained according to the same evaluation protocol as that used in the previous example.
[0075] Acid dye Process L ab AE * Color mounted Acid Comparative process without pre- 52,18 -6,59 4,61 15.8 Green black 1 blue titanium salt treatment (application of light composition 3 comprising Acid black 1) Process according to the invention with pretreatment with titanium salt (composition 1 and then rinsing then application of composition 3 comprising Acid black 1) 25.03 -7.1 -8.01 44.08 Blue Acid Comparative process without precaution 57,28 -5,65 4,66 14.2 blue Blue 62 treatment with light titanium salt (application of composition 4 comprising Acid Blue 62) Process according to the invention with pre-treatment with titanium salt (composition 1 then rinsing then application of composition 4 comprising Acid Blue 62) 37.82 -8.31 -19.41 44.6 Sustained blue Acid Comparative process without pre-treatment with titanium salt (application of composition comprising Acid Red 18) 66,79 3 , 03 14.56 2.8 Beige Red 18 rosé Process according to the invention with 44.2 37.7 14.02 42.7 Ro pre-treatment with titanium salt (composition 1 and then rinsing then application of composition comprising Acid Red 18) It is clear that the wicks stained according to the process of the invention with the composition Ci) 1, then rinsed and then with the Coloring compositions C11) 3, 4 or 5 are stained much more intensely and with a color increase significantly higher than that obtained with the locks stained according to the comparative method, without pre-treatment with the composition 1 Ci) comprising the salt. of titanium, since the value of L greatly decreases according to the invention and the rising value of the color AE is higher according to the invention.

权利要求:
Claims (23)
[0001]
REVENDICATIONS1. A process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, wherein said fibers are treated in several steps, comprising: i) at least one step of treating said fibers with a cosmetic composition (Ci) comprising 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 coloring cosmetic composition (Cii) comprising c) one or more dyes chosen from oxidation dyes, synthetic direct dyes and the original dyes natural, preferably selected from ortho-diphenols; d) at least one liquid organic compound having a Hansen solubility parameter value 6H greater than 0 and less than 16 MPa 1/2; and e) optionally one or more chemical oxidizing agent (s), especially chosen from hydrogen peroxide or one or more hydrogen peroxide generator system (s). hydrogen; iii) optionally at least one step of intermediate rinsing said fibers, preferably with water, said step being implemented between step i) and ii) or between step ii) and i), depending on the order in which said steps i) and ii) are carried out,
[0002]
2. Staining process according to the preceding claim, characterized in that a) the salt (s) of titanium is (are) chosen (s), among the organic salt (s) of Ti (IV); more preferably chosen from 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 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 ".
[0003]
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 represents an integer inclusive 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; 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.
[0004]
4. Coloring process according to any one of the preceding claims, characterized in that a) the salt (s) of titanium is (are) chosen from those of formula (IB) below: 3037241 2- 75 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 by a 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 are identical or different, represent a heteroatom such as oxygen, sulfur or Rc-N amino 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 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 counter ion such as alkali (Na, K), alkaline earth (Ca) or organic metal cation such as ammonium, preferably ammonium.
[0005]
5. Coloring 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 salt, in particular those of formula next: 2- 0
[0006]
6. Coloring process according to claim 1, characterized in that a) the OH 0 0.1r0 2N H4 [H Ti CO N 0 OH 3037241 76 salt (s) titanium is (are) chosen (s) from inorganic salts (s) in particular from the inorganic salt (s) of Ti (II), Ti (III) or Ti (IV), preferably of Ti (III) or Ti (IV); preferably Ti (IV), preferably the titanium salt (s) a) is (are) chosen from titanium halides, titanium sulphates and titanium phosphates. 5
[0007]
7. Coloring process according to any one of the preceding claims, characterized in that a) the salt (s) of titanium is (are) present in the composition Ci) in a content ranging from 0.001% to 20% by weight relative to the total weight of the compositions Ci). 10
[0008]
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 or acids b) is (are) different from the carboxylic acids complexed with the Ti salts as defined in any one of claims 1 to 5, preferably the carboxylic acid (s) present in the composition Ci) is (are) chosen from glycolic acid, lactic acid, citric acid or a salt thereof. 20
[0009]
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 ranging from 0.1 to 20% by weight, relative to the total weight of the composition Ci). 25
[0010]
10. Coloring process 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, 5 and 3.5, more preferably between 1 and 3. 30
[0011]
11. The method of dyeing according to any one of the preceding claims, characterized in that the dye (s) present in the dye composition Cii) is (are) dye (s) preferably selected oxidation (s) ) among the oxidation bases, and optionally one or more couplers; the oxidation base (s) is (are) preferably chosen from para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts and the one or more coupler (s) is (are) preferably chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.
[0012]
12. The method of dyeing according to any one of claims 1 to 10, characterized in that the dye or dyes present in the dye composition Cii) is (are) synthetic direct dye (s) (s) ( s) preferably chosen from neutral, acidic or cationic nitro-benzene direct dyes, neutral, anionic or cationic azo direct dyes, neutral quinone, and in particular neutral, anionic or cationic anthraquinone direct dyes, azine direct dyes, polyarylmethane such as triarylmethanics, indoamines, polymethines such as styryls, porphyrins, metalloporphyrins, phthalocyanines, methine cyanines, and mixtures thereof.
[0013]
13. The method of dyeing according to claim 1, characterized in that the direct synthetic dye (s) is (are) anionic direct dye (s) (s) ( s) preferably selected from acidic nitro dyes, acidic azo dyes, acidic azine dyes, acidic triarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes and indigoids; each of these dyes having at least one cationic counterionic sulfonate or carboxylate group as defined above; preferentially alkali metal, alkaline earth metal or ammonium sulphonate or carboxylate and mixtures thereof; in particular, the direct anionic dye (s) are chosen from the direct dyes of formula (VI): ColOrn (Q +) '(VI) - Col ", represents the anionic part an anionic direct dye or "acid" dye comprising in its structure at least one sulphonate group and / or at least one carboxylate group and comprising m anionic charge (s): - m and n, identical or different, represent an integer inclusive between 1 and 10; Q +, which may be identical or different, represents a cationic, organic or inorganic counterion, preferably chosen from alkali or alkaline earth metal cations such as Na + or K +, provided that when a) , b) and c) are present in the same composition, then c) is different from an azo anionic direct dye comprising a 1,8-dihydroxynaphthalene-3,5-disulfonate group, in particular c) is (are) selected ( s) of the following anionic direct dyes: anionic azo dyes diaryl diques of formula (VII): formula (VII) in which: - R7, R8, R9, R10, R'7, R'8, R'9 and R'10, identical or different, represent an atom of hydrogen or a group selected from: i) alkyl, ii) alkoxy, iii) alkylthio, iv) hydroxy, v) mercapto, vi) nitro, vii) R ° -C (X) -X'-, R ° - X'-C (X) -, R °-X'-C (X) -X "- with R ° representing a hydrogen atom, an alkyl or aryl group; X, X 'and X ", which may be identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group; viii) (0) 2S (0 -) -, W with W as defined above for M or represents a cationic counter ion as defined above: ix) (O) C0--, W with W as defined above; x) R "-S (O) 2-, with R "representing a hydrogen atom, an alkyl group, an aryl group, (di) (alkyl) amino, aryl (alkyl) amino, preferably a phenylamino or phenyl group; xi) R - S (O) 2-X ' with R "representing an alkyl group, optionally substituted aryl, X 'as defined previously; xii) (di) (alkyl) amino; xiii) aryl (alkyl) amino optionally substituted with one or more groups selected from nitro; nitroso; (0) 2S (0 -) -, W and alkoxy with W as previously defined; xiv) optionally substituted heteroaryl; preferentially a benzothiazolyl group; xv) cycloalkyl; especially cyclohexyl, xvi) Ar-N = N- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups, (0) 2S (O -) -, W or phenylamino; or two contiguous groups R7 with R8 OR R8 with R9 OR R9 with R10 together form a fused group benzo A '; and R'7 with R'8 OR R'8 with R'9 OR R'9 with R'10 together form a fused group benzo B '; with A 'and B' optionally substituted with one or more groups selected from i) nitro; ii) nitroso; iii) (0) 2S (0 -) -, W; iv) hydroxy; (v) mercapto; vi) (di) (alkyl) amino; vii) R ° - C (X) -X'-; viii) R ° -X'-C (X) -; ix) R °-X'-C (X) -X "-; x) Ar-N = N- and xi) aryl (alkyl) amino optionally substituted, with W, R °, X, X ', X" and Ar as defined previously; it being understood that: - the formula (VII) comprises at least one sulfonate (O) 2S (O -) -, Q + or carboxylate (O) C (O -) -, Q + radical on one of the rings A, or B; preferentially alkali metal, alkaline earth metal or ammonium sulphonate or carboxylate; - that when a), b) and c) are present in the same composition then c) is different from an azo anionic direct dye comprising a 1,8-dihydroxynaphthalene 3,5-disulfonate group; the anthraquinone dyes of formula (IX): wherein R22, R23, R24, R25, R26 and R27, which may be identical or different, represent a hydrogen or halogen atom; or a group selected from i) alkyl, ii) hydroxy, iii) mercapto, iv) alkoxy, v) alkylthio, vi) aryloxy or optionally substituted arylthio, preferably substituted by one or more groups selected from alkyl and 10 (O) 2S (0 -) -, W with W as defined above, vii) aryl (alkyl) amino optionally substituted by one or more groups selected from alkyl and (0) 2S (O -) -, W with W as defined previously, viii) (di) (alkyl) amino, ix) (di) (hydroxyalkyl) amino, x) (O) 2S (O -) -, W with W as previously defined; Z 'represents a hydrogen atom or a group NR28R29 with R28 and R29, which are identical or different, represent a hydrogen atom or a group chosen from i) alkyl, ii) polyhydroxyalkyl such as hydroxyethyl, iii) aryl optionally substituted by one or more particularly alkyl groups such as methyl, n-dodecyl, n-butyl; (0) 2S (0 -) -, W with W as previously defined; R ° -C (X) -X'-, R ° -X'-C (X) -, R ° -X'-C (X) -X "- with R °, X, X 'and X" such As defined above, preferably R ° represents an alkyl group, iv) cycloalkyl; in particular cyclohexyl; - Z, represents a group selected from hydroxy and NR'28R'29 with R'28 and R'29, identical or different, represent the same atoms or groups as R28 and R29 as defined above; It being understood that formula (IX) comprises at least one sulfonate group (O) 2S (O -) -, Q +; the indigo dyes of formula (XIII): embedded image in which: R 53, R 54, R 55, R 56, R 57, R 58, R 59 and R 60, which are identical or different, represent a hydrogen atom; hydrogen or a group selected from i) alkyl; ii) alkoxy, alkylthio; iii) hydroxy, mercapto; iv) nitro, nitroso; y) R ° -C (X) -X'-, R °-X'-C (X) -, R °-X'-C (X) -X "-R54 6 (XIII) 58 3037241 80 with R ° representing a hydrogen atom, an alkyl or aryl group X, X 'and X ", identical or different, representing an oxygen atom, sulfur or NR with R representing a hydrogen atom or an alkyl group ; vi) (0) 2S (0 -) -, W with W representing a cationic counter ion; vii) (0) C0--, W with W as previously defined; - G represents an oxygen atom, sulfur or a NR group, with Re as defined above; especially G represents an oxygen atom; - R, and Rh, identical or different, represent a hydrogen atom or an alkyl group; It being understood that at least one of the groups R53, R54, R55, R56, R57, R58, R59 or R60 represents a sulfonate (O) 2S (O -) -, W or carboxylate (O) 0 (0-) group. ) -, W.
[0014]
14. A dyeing method according to any one of claims 1 to 10, characterized in that the dye (s) is / are chosen from dyes of natural origin, preferably chosen from orthodiphenols, and their mixtures.
[0015]
15. The method of dyeing according to the preceding claim, characterized in that the dye (s) is (are) chosen from aromatic ring orthodiphenols, whose aromatic ring is selected 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; and their mixtures. 25
[0016]
16. The method of dyeing according to any one of claims 14 and 15, characterized in that the dye (s) are chosen from orthodiphenol (s) of formula (II) following or one of its oligomers, tautomers, isomers optical, geometrical isomers, as well as its salts or its solvates such as hydrates: OH (II) in which: R1 to R4, identical or different, represent: i) a hydrogen atom, ii) 3037241 81 d halogen, or a group selected from iii) hydroxy, iv) carboxy, v) carboxylate of (CiC20) 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) (C1-C20) alkoxy, x1) (C1-C20) alkoxy (C1-C20) alkyl, xii) (C1-C20) alkoxyaryl, xiii) optionally substituted aryl, xiv) aryl, xv) substituted aryl, xvi) heterocycle clique, saturated or not, with or without a cationic or anionic charge, optionally substituted and / or optionally fused with a benzene aromatic ring, 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 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 the two hydroxy. 20
[0017]
17. The method of dyeing according to any one of claims 14 to 16, characterized in that the dye (s) are (s) orthodiphenol derivative (s) chosen (s) from: - flavanols such as catechin and gallate d epichatechin, flavonols such as quercetin, anthocyanidins such as cyanidin, delphinidin, petunidine, anthocyanins or anthocyanins such as myrtillin, 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; dihydroxyphenylalanine and its derivatives, 4,5-dihydroxyphenylalanine and its derivatives, dihydroxycinnamates such as caffeic acid and chlorogenic acid, orthopolyhydroxycoumarines, orthopolyhydroxyisocoumarines, orthopolyhydroxycoumaron orthopolyhydroxyisocoumarones, orthopolyhydroxychalcones, orthopolyhydroxychromones, quinones, hydroxyxanthones, 1,2-dihydroxybenzene and its derivatives, 1,2,4-trihydroxybenzene and its derivatives, , 2,3 trihydroxybenzene and its derivatives, - 2,4,5 trihydroxytoluene and its derivatives, - proanthocyanidins and in particular proanthocyanidins Al, A2, Bi, B2, B3 and Ci, - chromanics, and chromenics, - proathocyanines, 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.
[0018]
18. A dyeing process according to any one of the preceding claims, characterized in that the total content of dyes in the dye composition Cii) is between 0.001% and 10%, preferably between 0.001% and 5% and weight with respect to weight of the composition Cii).
[0019]
19. A dyeing process according to any one of the preceding claims, characterized in that the composition Cii) comprises e) 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) chosen from hydrogen peroxide. 35
[0020]
20. Staining process according to any one of the preceding claims, characterized in that the method uses f) one or more agent (s) basifying (s); preferentially the alkalinizing agent (s) e) is (are) in the dye composition Cii); preferably the agent (s) alkalinizing (e) 3037241 83 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) amino acids of basic preferences such as arginine, lysine, ornithine, citruline and histidine, and viii) the compounds of the following formula (II): Ra Rb N -W-N Rd (1 1) Formula (II) wherein 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 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. 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 an 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 preferably ammonia.
[0021]
21. A dyeing process according to any one of the preceding claims, characterized in that it comprises at least one intermediate rinsing step iii) of said fibers, preferably with water, the intermediate rinsing step iii) being put into operation. between step i) and step ii) or between step ii) and i) according to the order in which steps i) and ii) are implemented.
[0022]
22. A dyeing method according to any one of the preceding claims, characterized in that the treatment step i) implementing the application of the composition Ci) on the keratinous fibers is carried out first, then optionally followed by step iii) intermediate rinsing said fibers, preferably with water, followed finally the staining step ii) implementing the application of the composition Cii) on said fibers. 35
[0023]
23. A dyeing method according to any one of the preceding claims, characterized in that the pause time on the keratinous fibers of the composition Ci) is between 5 minutes and 2 hours, particularly between 15 minutes and 1 hour, preferably between 30 and 45 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; And in that the pause time on the keratinous fibers of the composition Cii) is between 1 minutes and 2 hours, preferably between 5 minutes and 1 hour, more preferably the pause time is between 15 and 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., preferably between room temperature (27 ° C.) and 40 ° C. 10

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FR2954134A1|2009-12-23|2011-06-24|Oreal|A COMPOSITION FOR COLORING KERATIN FIBERS COMPRISING AT LEAST ONE ORTHODIPHENOL DERIVATIVE, A CHEMICAL OXIDIZING AGENT AND AN ALKALINIZING AGENT,|FR3080284B1|2018-04-19|2020-05-15|L'oreal|KERATINIC FIBER COLORING PROCESS COMPRISING THE APPLICATION OF A CHROMENOL / CHROMEN-2-ONE DERIVATIVE, COMPOSITION AND DEVICE|

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FR3104420A1|2019-12-17|2021-06-18|L'oreal|Hair treatment process using at least one titanium salt, at least one natural dye and at least one carboxylic acid|

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FR3104964A1|2019-12-23|2021-06-25|L'oreal|HAIR COLORING PROCESS USING A METAL SALT AND A HENNA EXTRACT|

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优先权:

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申请号 | 申请日 | 专利标题

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FR1555395A|FR3037241B1|2015-06-12|2015-06-12|A CAPILLARY COLORING PROCESS USING A TITANIUM SALT, A COLOR, AND A PARTICULAR SOLVENT|FR1555395A| FR3037241B1|2015-06-12|2015-06-12|A CAPILLARY COLORING PROCESS USING A TITANIUM SALT, A COLOR, AND A PARTICULAR SOLVENT|

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PCT/EP2016/063367| WO2016198648A1|2015-06-12|2016-06-10|Hair dyeing process using a titanium salt, a dye and a particular solvent|