FR3007278A1 - OXIDATION COLORING PROCESS USING A COMPOSITION COMPRISING A 2- OR 3-AMINOINDOLIZINE OXIDATION BASE AND METAL CATALYSTS - Google Patents

Abstract

The subject of the invention is a process for dyeing keratinous fibers, comprising the use of one or more metal catalysts and of a composition (A) comprising: one or more oxidizing agents, and at least one base of oxidation chosen from 2- or 3-aminoindolizine of formula (I) in which R1 to R7, independently, represent a hydrogen atom, a C1-C4 alkyl radical, an optionally substituted phenyl radical or a C1-alkoxy radical; -C4, a halogen atom, a carboxylic radical (-COOH or -alkyl-COOH), a carboxamide radical (CONRR '), a nitrile radical (-CN), a sulphone radical (-SO2R), a sulphoxide radical ( -SORR '), a sulfoamide radical (-SO2NRR'), an alkylcarbonyl radical (-CO-alkyl), an alkoxycarbonyl radical (-CO-O-alkyl), a benzoyl radical (-CO-phenyl or - alkyl-CO- phenyl optionally substituted on the phenyl group), and the compounds 1, bisindolizine of formula (I); R4 to R7 may form in pairs adjacent to an optionally substituted 5- or 6-membered ring, unsaturated or unsaturated and capable of containing a heteroatom; with the additional proviso that R2 or R3 represents an amino radical (NH2).

Description

The present invention relates to a process for dyeing keratinous fibers comprising one or more metal catalysts. For a long time, many people have been known to use a method for dyeing keratinous fibers. seek to change the color of their hair and in particular to hide their white hair.

It is known to obtain so-called "permanent" or oxidation 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 initially 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 with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-amines and meta-aminophenols. diphenols and certain heterocyclic compounds such as indole compounds. The variety of molecules involved in the oxidation bases and couplers allows a rich palette of colors to be obtained.

The permanent dyeing process therefore consists in applying bases or a mixture of bases and couplers to the keratinous fibers with hydrogen peroxide (H 2 O 2 or hydrogen peroxide) as an oxidizing agent, to be allowed to diffuse and then to rinse off. fibers. The resulting dyes have the advantage of being permanent, powerful, and resistant to external agents, including light, weather, washing, perspiration and friction. However, it is still sought to increase the efficiency of the reaction of oxidation dyes used during this process to improve their rise on keratin fibers. In fact, such an improvement would make it possible in particular to reduce the contents of the oxidation dyes present in the dyeing compositions, to reduce the exposure time on the keratinous fibers and / or to use other families of dyes having a low dyeing power, but which are able to present a good toxicological profile, to bring new shades or to lead to stubborn stains vis-à-vis external agents such as light or shampoos. In this respect, it has already been proposed to use cosmetic compositions containing metal catalysts during a dyeing process in order to accelerate the oxidation reaction of the dyes and to improve the intensity of the coloration on the keratinous fibers. .

However, the dye power obtained is not yet completely satisfactory and the colorations obtained are generally too selective, that is to say that these stains are not homogeneous along the keratin fiber. There is therefore a real need to propose a method for staining keratinous fibers used in the presence of an oxidizing agent which do not have the disadvantages of the existing processes, that is to say which are capable of leading to a satisfactory intensity of the oxidation dyes on the keratinous fibers while leading to low selective colorations.

This object is achieved by the present invention which has for object a method for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, comprising the use of one or more metal catalysts and a composition ( A) comprising: (a) at least one oxidizing agent, and (b) at least one oxidation base selected from the 2 or 3 aminoindolizine of formula (I) wherein R1 to R7, independently, represent a hydrogen atom a C1-C4 alkyl radical, an optionally substituted phenyl radical, a C1-C4 alkoxy radical, a halogen atom, a carboxylic radical (-COOH or -alkyl-COOH), a carboxamide radical (CONRR '), a nitrile radical (-CN), a sulphone radical (-SO2R), a sulphoxide radical (-SOR), a sulphonamide radical (-SO2NRR '), an alkylcarbonyl radical (-CO-alkyl), an alkoxycarbonyl radical (-00- O-alkyl), a benzoyl radical (-CO-phenyl or -alkylCO-phenyl optionally substituted phenyl), and 1,1 'bisindolizine compounds of formula (I); R4 to R7 may form in pairs adjacent to an optionally substituted 5- or 6-membered ring, unsaturated or unsaturated and capable of containing a heteroatom; with the additional proviso that R2 or R3 represents an amino radical (NH2).

The subject of the invention is also a hair dyeing composition comprising one or more oxidation bases of formula (I) and at least 10% of fatty substances, preferably at least 20%, and the use of this composition for the coloring of keratinous fibers, especially the hair.

The dyeing method according to the invention makes it possible to lead to satisfactory color intensity on the keratinous fibers while being selectively selective, that is to say to homogeneous stains along the keratin fiber. In addition, the method according to the present invention makes it possible to lead to powerful and chromatic colorations. Moreover, the dyeing method according to the invention makes it possible to improve the intensity of the coloration on the keratin fibers as compared to a dyeing process. conventional. In the process of the invention, the metal catalyst (s) may constitute or be part of a composition (B) which may be mixed with the composition (A) before the mixture is applied to the keratinous fibers or may be separately applied to the keratin fibers. or in post treatment with or without intermediate rinsing. It should be noted that the composition (B) may consist solely of the metal catalyst (s). The present invention also relates to a multi-compartment device comprising a first compartment containing a composition (B) comprising one or more metal catalysts, a second compartment containing a composition (A ') comprising one or more oxidation dyes of formula (I) , and a third compartment containing a composition (C) comprising one or more oxidizing agents. According to a particular embodiment, one or more fatty substances are present in at least one of the compositions (A ') or (C) such that after mixing the compositions (A') and (C) the fat content is greater than or equal to 10% by weight relative to the total weight of the mixture of compositions (A) and (C). According to a particular embodiment, the device comprises a fourth compartment comprising a composition (D) comprising one or more fatty substances, said composition (D) being to be mixed with the compositions (A) and (C), the fat content preferably being greater than or equal to 10% by weight relative to the total weight of the mixture of compositions (A), (C) and (D), the compositions (A) or (C) possibly containing one or more fatty substances . Other characteristics and advantages of the invention will emerge more clearly on reading the description and examples which follow. In what follows, and unless otherwise indicated, the boundaries of a domain of values are included in this field. The expression "at least one" is equivalent to the expression "one or more".

In the card according to the invention, the term "C1-C4 alkyl radical" means a linear or branched, saturated radical comprising from 1 to 4 carbon atoms, a C1-C4 alkoxy radical is a radical -O-Alkyl, a radical carboxylic acid is a radical -COOH or -alkyl-COOH; a carboxamide radical is a -CONRR 'radical in which R and R' can be a hydrogen atom, an alkyl or phenyl radical; a sulphone radical is a radical -SO2RR '; a sulphoxide radical is a radical -SOR, a sulphonamide radical is a radical -SO2NRR ', with R and R' as defined above, an alkylcarbonyl radical is a radical -CO-alkyl, an alkoxycarbonyl radical is a radical -CO -O- alkyl, a benzoyl radical is a -CO-phenyl radical or -alkyl-CO-phenyl with alkyl being as defined above and the phenyl groups may be substituted. The human keratinous fibers treated by the process according to the invention are preferably the hair.

The dyeing process according to the present invention uses one or more metal catalysts. Metallic catalysts are compounds which comprise in their structure one or more metals. The metals are selected from transition metals, rare earth metals and their alloys. In particular, the metals are selected from transition metals and rare earth metals. Among the transition metals, there may be mentioned manganese, iron, cobalt, copper, zinc, platinum, nickel, titanium, silver, zirconium, chromium, molybdenum, tungsten, platinum, gold, vanadium and among these especially manganese. Among the rare earth metals, mention may be made of cerium. Thus, the metal catalysts are especially catalysts based on transition metals and rare earth metals, and more particularly catalysts based on manganese, vanadium or cerium.

The metal catalysts used may be chosen from metal salts, metal oxides, metal complexes and their mixtures and their solvates including hydrates. For the purpose of the present invention, metal complexes are understood to mean systems in which the metal ion, ie the central atom, is bonded to one or more electron donors, called ligands, via chemical bonds. Preferably, the metal catalysts used in the dyeing process are chosen from metal salts. For the purposes of the present invention, the term "metal salts" means salts derived from the action of an acid on a metal. Preferably, the metal catalysts used in the dyeing process are chosen from transition metal salts, such as manganese salts, and rare earth metal salts, such as cerium salts, and mixtures thereof. . The metal salts may be inorganic or organic salts. The inorganic metal salts may be chosen from halides, carbonates, sulphates and phosphates, especially hydrated or non-hydrated halides. According to another preferred variant, the metal salts are of oxidation state II and have two ligands derived from (poly) hydroxyacid. By "(poly) hydroxyacid" is meant any carboxylic acid which comprises a hydrocarbon chain, linear or branched, saturated or unsaturated, preferably saturated and / or linear, comprising from 1 to 10 carbon atoms and from 1 to 9 hydroxyl groups, and comprising from 1 to 4 carboxyl groups -C (O) -OH, at least one of said functions -C (O) -OH is in the form carboxylate -C (O) -O- complexed with the metal atom, preferably Mn (II). More particularly, the metal salt is complexed by two carboxylate groups such as that of formula (II): RC (O) -O-M-O-C (O) -R '(II) as well as its solvates such as hydrates and their enantiomers Formula (II) in which: - M represents a metal (II) or metal2 + of oxidation state 2, - R and R ', which may be identical or different, represent a (C 1 -C 6) (poly) hydroxyalkyl group. The organic metal salts may be chosen from organic acid salts such as citrates, lactates, glycolates, gluconates, acetates, propionates, fumarates, oxalates and tartrates, especially gluconates. Preferably, the metal catalysts are chosen from organic acid salts of transition metals, especially of manganese, and inorganic salts of rare earth metals, in particular cerium. More preferably, the metal catalysts are chosen from manganese gluconate and cerium heptahydrate chloride, in particular manganese gluconate. Composition B may contain exclusively the metal catalyst (s). This composition may also contain other compounds. This composition B may be anhydrous or aqueous. The metal catalysts after mixing with the composition C may be present in a content ranging from 0.001 to 10% by weight, preferably in a content ranging from 0.001 to 1% by weight, better still from 0.01 to 0.5% by weight. weight relative to the total weight of the final composition after mixing with the oxidant (s). As indicated above, the dyeing method of the invention uses a composition (I) which comprises one or more fatty substances.

The term "fatty substance" means an organic compound which is insoluble in water at ordinary room temperature (25 ° C.) and at atmospheric pressure (760 mmHg) (solubility less than 5% and preferably greater than 1%, more preferably at 0.1%). They have in their structure at least one hydrocarbon chain comprising at least 6 carbon atoms or a chain of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same conditions of temperature and pressure, such as for example chloroform, ethanol, benzene, petroleum jelly or decamethylcyclopentasiloxane.

These fatty substances are neither polyoxyethylenated nor polyglycerolated. They are different from fatty acids because salified fatty acids are generally soluble soaps in aqueous media. The fatty substances are in particular chosen from hydrocarbons and C6-C16 or more than 16 carbon atoms and in particular alkanes, oils of animal origin, oils of vegetable origin, glycerides or fluorinated oils of origin synthetic, fatty alcohols, esters of fatty acid and / or fatty alcohol, non-silicone waxes, silicones. It is recalled that for the purposes of the invention, the alcohols, esters and fatty acids more particularly have one or more linear or branched hydrocarbon groups, saturated or unsaturated, comprising 6 to 30 carbon atoms, which are optionally substituted, in particular by one or more hydroxyl groups (in particular 1 to 4). If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise. As regards the C6-C16 alkanes, the latter are linear, branched, optionally cyclic. By way of example, mention may be made of hexane, dodecane and isoparaffins, such as isohexadecane and isodecane. The linear or branched hydrocarbons having more than 16 carbon atoms may be chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes and hydrogenated polyisobutene such as Parleam®. Among the animal oils there may be mentioned perhydrosqualene. Among triglycerides of plant or synthetic origin, mention may be made of liquid triglycerides of fatty acids containing from 6 to 30 carbon atoms, for instance triglycerides of heptanoic or octanoic acids or else, for example, sunflower, corn, soy, squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado, jojoba oil, shea butter oil triglycerides of caprylic / capric acids such as those sold by Stearineries Dubois or those sold under the names Miglyole 810, 812 and 818 by Dynamit Nobel; Among the fluorinated oils, mention may be made of perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, sold under the names FLUTEC® PC1 "and" FLUTEC® PC3 "by BNFL Fluorochemicals, perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names "PF 5050 °" and "PF 5060 °" by the company 3M, or the bromoperfluorooctyl sold under the name FORALKYL® by Atochem, nonafluoro-methoxybutane and nonafluoroethoxyisobutane, perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name "PF 5052®" by the company 3M.The fatty alcohols that can be used in the cosmetic composition (I) are saturated or unsaturated, linear or branched, and comprise from 6 to 30 carbon atoms and more particularly from 8 to 30 carbon atoms. tylique, stearyl alcohol and their blend (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol.

The wax or waxes that may be used in the composition (A) are chosen in particular from Carnauba wax, Candelila wax, and Alfa wax, paraffin wax, ozokerite, vegetable waxes. such as olive wax, rice wax, hydrogenated jojoba wax or absolute waxes of flowers such as the essential wax of blackcurrant flower sold by the company BERTIN (France), animal waxes such as beeswax , or modified beeswax (cerabellina); other waxes or waxy raw materials that can be used according to the invention are, in particular, marine waxes, such as the one sold by SOPHIM under the reference M82, and polyethylene or polyolefin waxes in general. With regard to the fatty acid esters and / or fatty alcohols, advantageously different from the triglycerides mentioned above, mention may be made in particular of saturated or unsaturated, linear or branched C1-C26 aliphatic or monohydric acid or poly acid esters and of saturated or unsaturated, linear or branched C 1 -C 26 aliphatic mono- or polyalcohols, the total number of carbon of the esters being more particularly greater than or equal to 10. Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isoketyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso) stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methyl ricinoleate acetyl; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate; , styryl, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.

Still in the context of this variant, it is also possible to use esters of C 4 -C 22 di or tricarboxylic acids and of C 1 -C 22 alcohols and esters of mono di or tricarboxylic acids and di, tri, alcohols. C2-C26 tetra or pentahydroxy. These include: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate, tridecyl erucate; triisopropyl citrate; triisotearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate, propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisanonate; and polyethylene glycol distearates. Among the esters mentioned above, it is preferred to use ethyl, isopropyl, myristyl, cetyl, stearyl palmitates, ethyl-2-hexyl palmitate, 2-octyldecyl palmitate, sodium myristates and the like. alkyls such as isopropyl, butyl, cetyl, 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate and isononyl isononanate, cetyl octanoate.

The composition may also comprise, as fatty ester, esters and diesters of C 6 -C 30, preferably C 12 -C 22, fatty acid sugars. It is recalled that "sugar" is understood to mean oxygenated hydrocarbon compounds which have several alcohol functions, with or without an aldehyde or ketone function, and which contain at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides. Suitable sugars include, for example, sucrose (or sucrose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose, lactose, and their derivatives. especially alkyls, such as methyl derivatives such as methylglucose. The esters of sugars and fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of C 6 -C 30, preferably C 12 -C 22 fatty acids, linear or branched, saturated or unsaturated. If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise. The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters and mixtures thereof. These esters may be for example oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonates, or mixtures thereof, such as in particular the mixed oleo-palmitate, oleostearate and palmito-stearate esters. More particularly, the mono- and di-esters are used, and especially the mono- or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, sucrose, glucose or methylglucose. By way of example, mention may be made of the product sold under the name Glucatee DO by the company Amerchol, which is a methylglucose dioleate. Mention may also be made, by way of examples, of esters or mixtures of esters of fatty acid sugar: the products sold under the names F160, F140, F110, F90, F70, SL40 by the company Crodesta, respectively denoting sucrose palmito-stearates of 73% monoester and 27% di- and tri-ester, 61% monoester and 39% di-, tri- and tetraester, 52% monoester and 48% monoester; % di-, tri- and tetraester, 45% monoester and 55% di-, tri- and tetraester, 39% monoester and 61% di-, tri-, and tetra. -ester, and sucrose mono-laurate; the products sold under the name Ryoto Sugar Esters, for example referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% di-triester-polyester; the sucrose mono-di-palmito-stearate marketed by Goldschmidt under the name Tegosofte PSE.

The silicones that can be used in the cosmetic composition (I) of the present invention are volatile or cyclic, linear or branched, volatile or non-volatile organic silicones with a viscosity of 5 × 10 -6 to 2.5 m 2 / s. at 25 ° C and preferably 1.10-5 to 1m2 / s.

The silicones that can be used in accordance with the invention can be in the form of oils, waxes, resins or gums. Preferably, the silicone is chosen from polydialkylsiloxanes, in particular polydimethylsiloxanes (PDMS), and organomodified polysiloxanes comprising at least one functional group chosen from poly (oxyalkylene) groups, amino groups and alkoxy groups. Organopolysiloxanes are further defined in Walter Noll's "Chemistry and Technology of Silicones" (1968), Academie Press. They can be volatile or nonvolatile.

When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60 ° C. and 260 ° C., and even more particularly from: (i) cyclic polydialkylsiloxanes containing from 3 to 7, preferably from 4 to 5 silicon atoms. It is, for example, octamethylcyclotetrasiloxane sold in particular under the name VOLATILE SILICONE® 7207 by UNION CARBIDE or SILBIONE ° 70045 V2 by RHODIA, decamethylcyclopentasiloxane marketed under the name VOLATILE SILICONE® 7158 by UNION CARBIDE, and SILBIONE ® 70045 V5 by RHODIA, as well as their mixtures. Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the VOLATILE® SILICONE FZ 3109 marketed by UNION CARBIDE, of the formula: ## STR1 ## The cyclic polydialkylsiloxane mixtures with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and tetramethylsilylpentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy, can also be mentioned. -1,1 '- (hexa-2,2,2', 2 ', 3,3'-trimethylsilyloxy) bis-neopentane; (ii) linear volatile polydialkylsiloxanes having 2 to 9 silicon atoms and having a lower viscosity or equal to 5.10-6 m 2 / s at 25 ° C. It is, for example, decamethyltetrasiloxane marketed in particular under the name "SH 200" by Toray Silicone, silicones entering this class are also described in the article. could published in Cosmetics and Toiletries, Vol 91, Jan. 76, p. 2732 - TODD & BYERS "Volatile Silicone fluids for cosmetics".

Non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the above organofunctional groups and mixtures thereof are preferably used.

These silicones are more particularly chosen from polydialkylsiloxanes, among which may be mentioned mainly polydimethylsiloxanes with trimethylsilyl end groups. The viscosity of the silicones is measured at 25 ° C. according to ASTM 445 Appendix C.

Among these polydialkylsiloxanes, mention may be made, without limitation, of the following commercial products: SILBIONE® oils of the 47 and 70 047 series or the MIRASIL® oils marketed by RHODIA, such as, for example, the 70 047 V 500 000 oil; the oils of the MIRASIL® series marketed by RHODIA; the oils of the 200 series of Dow Corning, such as DC200 having a viscosity of 60,000 mm 2 / s; - VISCASIL® oils from GENERAL ELECTRIC and some oils from SF series (SF 96, SF 18) from GENERAL ELECTRIC. Mention may also be made of polydimethylsiloxanes with dimethylsilanol end groups known under the name of dimethiconol (CTFA), such as the oils of the 48 series from the company RHODIA. In this class of polydialkylsiloxanes, mention may also be made of the products sold under the names "ABIL WAX® 9800 and 9801" by GOLDSCHMIDT, which are polydialkyl (C 1 -C 20) siloxanes. The silicone gums that can be used in accordance with the invention are in particular polydialkylsiloxanes, preferably polydimethylsiloxanes having high average molecular weights of between 200,000 and 1,000,000 used alone or in a mixture in a solvent. This solvent may be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane or their mixtures. More particularly useful products according to the invention are mixtures such as: - mixtures formed from an end-hydroxylated polydimethylsiloxane or dimethiconol (CTFA) and a cyclic polydimethylsiloxane also called cyclomethicone (CTFA) such as the product Q2 1401 marketed by Dow Corning; mixtures of a polydimethylsiloxane gum and a cyclic silicone such as the product SF 1214 Silicone Fluid from the company General Electric, this product is an SF 30 gum corresponding to a dimethicone, having a number average molecular weight of 500,000 solubilized in oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane; mixtures of two PDMSs of different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from the company General Electric. The product SF 1236 is the mixture of an SE 30 gum defined above having a viscosity of 20 m 2 / s and an SF 96 oil with a viscosity of 5 × 10 -6 m 2 / s. This product preferably comprises 15% of SE gum and 85% of an SF 96 oil. The organopolysiloxane resins that can be used in accordance with the invention are crosslinked siloxane systems containing the units: R25iO2 / 2, R35i01 / 2, R5iO3 / 2 and 5i0412 wherein R represents an alkyl having 1 to 16 carbon atoms. Among these products, those that are particularly preferred are those in which R denotes a C1-C4 lower alkyl group, more particularly methyl. Among these resins may be mentioned the product sold under the name "Dow Corning 593" or those sold under the names "Silicone Fluid SS 4230 and SS 4267" by the company General Electric and which are silicones of dimethyl / trimethyl siloxane structure. Mention may also be made of the trimethylsiloxysilicate type resins sold in particular under the names X22-4914, X21-5034 and X21-5037 by the company Shin-Etsu.

The organomodified silicones that may be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.

In addition to the silicones described above, the organomodified silicones may be polydiarylsiloxanes, especially polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized with the organofunctional groups mentioned above. The polyalkylarylsiloxanes are especially chosen from polydimethyl / methylphenylsiloxanes, linear and / or branched polydimethyl / diphenylsiloxanes with a viscosity ranging from 1 × 10 -5 to 5 × 10 -2 m 2 / s at 25 ° C. Among these polyalkylarylsiloxanes, mention may be made by way of example of the products sold under the following names: SILBIONE® oils of the 70 641 series from RHODIA; - the RHODORSIL® 70 633 and 763 RHODIA series of oils; - DOW CORNING 556 COSMETIC GRAD FLUID oil from Dow Corning; the silicones of the PK series of BAYER, such as the product PK20; the silicones of the PN, PH series of BAYER, such as the PN1000 and PH1000 products; certain oils of the SF series of GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250 and SF 1265. Among the organomodified silicones, mention may be made of polyorganosiloxanes comprising: polyethyleneoxy and / or polypropyleneoxy groups optionally comprising C 6 alkyl groups; -C24 such as the products known as dimethicone copolyol marketed by the company Dow Corning under the name DC 1248 or the oils SILWET® L 722, L 7500, L 77, L 711 from UNION CARBIDE and alkyl (C12) -methicone copolyol sold by the company Dow Corning under the name Q2 5200; substituted or unsubstituted amine groups such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company Genesee or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amino groups are, in particular, C1-C4 aminoalkyl groups; alkoxylated groups, such as the product sold under the name "Silicone Copolymer F-755" by SWS Silicones and Abil Wax® 2428, 2434 and 2440 by the company GOLDSCHMIDT. The fatty substances are advantageously chosen from C 6 -C 16 hydrocarbons or more than 16 carbon atoms and in particular alkanes, vegetable oils, fatty alcohols, fatty acid esters and / or alcohol esters. fatty acids, silicones or their mixtures. Preferably, the fatty substance is an oil (a liquid compound at a temperature of 25 ° C. and at atmospheric pressure). Preferably, the fatty substance is chosen from liquid petrolatum, C6-C16 alkanes, polydecenes, liquid esters of fatty acid and / or fatty alcohol, liquid fatty alcohols or mixtures thereof. Better still, the fatty substance is chosen from petrolatum oil and C6-C16 alkanes, and polydecenes. Preferably, the fatty substances are present in a content greater than or equal to 10% by weight, relative to the total weight of the cosmetic composition (I), preferably at least 20%. Thus, according to one particular embodiment, the composition (A) has a fat content, preferably oils, preferably ranging from 10 to 70% by weight, and even more particularly ranging from 25 to 70% by weight, more preferably 25 to 60% by weight, and especially 30 to 60% by weight relative to the total weight of the composition (A). The invention uses an oxidation base of formula (A). By way of example of oxidation bases of formula (I), mention may be made of the following 2-aminoindozolines, their salts and their solvates: ## STR1 ## --- - N "------------ NH2 NH2 Me NH2 ----- -. ## STR13 ## 1-Indolizinecarbonitrile, 2-amino-6-bromo-1-indolizinecarbonitrile, 2-amino-5-methyl-1-indolizineacetic acid. , 2-amino-3- (4-methoxybenzoyl) -7-methyl-H 2 O -CH 2 -NH 2 NH 2 -, NH 2 - 1-Indolizineacetic acid, 2-amino-3-benzoyl-7-methyl-1-indolizineacetic acid, 2-amino-2-amino-1179448-21-5 1179390-33-0 amino-3- (4-chlorobenzoyl) -7-methyl-, ## STR1 ## NAc 1071698-46-8 63014-90-4 63014-83-5 2-Indolizinamine, 7-methyl-1-indolizinecarbonitrile, 2-amino-7-methyl-1-indolizinecarboxylic acid, 3-acety1-2-amino-7-methyl Ethyl ester NH 3 OH 2 O -CH 2 0 Me NH 2 Me NH 2 - Ph ---- .-- NH 2 I ,, -. ## STR2 ## 1-Indolizinecarbonitrile, 2-amino-3-benzoyl-7-methyl-1-methyl-3-benzoyl-7-methyl 1-Indolizineacetic acid, 2-amino-3- (4-methoxybenzoyl) -7-methyl-1-indolizineacetic acid, 2-amino-3-benzoyl-7-methyl-HCO 2 C-CH 2 CN MeOH NH 2 I - 1-Indolizineacetic acid, 2-amino-3- (4-chlorobenzoyl) -7-methyl-1-indolizinecarbonitrile, 2-amino-3- Benzoyl-7-methyl As oxidation bases of formula (I) of type 3 aminoindolizines, there may be mentioned: Me NH2 NH2 NH2 .. ,, ... NL______. CN ......., N .... '.L ......... CN Br' ..... 'N .......' ,,. CN - - ..,. Br 1284237-42-8 1284237-35-9 1284237-34-8 2-Indolizinecarbonitrile, 3-amino-5-methyl-2-indolizinecarbonitrile, 3-amino-8-bromo-2-indolizinecarbonitrile, 3-amino-6- bromo- NH2 Cl NH2 0 H02 C ---- N) ---------------- Ph I 0 ---- N ---- L--. --....... - OMe 1- Ph ---- ---- -, N ..z, - z ._ ,,, N CN NH2 Ne 1251003-06-1 905975-90 6-Indolizinecarboxylic acid, 3-amino-1-indolizinecarbonitrile, 3-amino-5-chloro-2-phenyl-8-indolizinecarboxylic acid, 3-amino-2-benzoyl-5-methyl-methyl Ester NH2 Bu2 Cl-. ## STR2 ## 2-6-Indolizinecarboxylic acid, 3-amino-2- (4-chlorophenyl) -ethyl ester 3-indolizinamine, 5-methyl-2-phenyl-3-indolizinamine, 2- (1,1-dimethylethyl) - and Pr- ## STR1 ## ## STR1 ## ethyl-3-indolizinamine, 2- (1-methylethyl) -1-indolizinecarboxylic acid, 3-amino-2-methyl-NH 2 0 NH 2 -, n-L-- --- I-OEt) ,,,,, ... ,,,, CN 0 .--- N "----- ... LPh --....... NMe 1360598-30- 6 1284237-37-1 2-Indolizinecarboxylic acid, 3-amino-1- (phenylsulfonyl) -ethyl ester 2-Indolizinecarbonitrile, 3-amino-1-methyl CN 0 0 ..-- ..- Me I N_ - Ph ..--- N_ I \ TH2 NH 2 NH 2 1284237-28-0 1284237-27-1 1284237-25-7 3-Indolizinamine, 2- (methylsulfonyl) -2-indolizinecarbonitrile, 3-amino-3-indolizinamine, 2- (phenylsulfonyl) -O NH 2 NH 2 -Bu-t --- / ---- --- N L. ..--- N ---- L ----. ## EQU1 ## wherein: ## STR2 ## 1251014-08-0 1-Propanone, 1- (3-amino-2-indolizinyl) -2,2-dimethyl-1-indolizinecarboxylic acid, 3-amino-ethyl ester 1-indolizinecarboxylic acid, 3-amino-NH 2 NH 2 --- ..% - N --- L --..------- Me ..--- N ---- L ---- "Me L- OMe --- Il NI - ,, -, ....., ..,) NAc - HC1 - ... N112 NAc 1195215-45-2 1195207-22-7 186358-06-5 Ethanone, 1- (3) -amino-2-methyl-1-indolizinyl) -, hydrochloride (1: 1 Ethanone, 1- (3-amino-2-methyl-1-indolizinyl) -2-indolizinecarboxylic acid, 3-amino-, methyl ester NH 2 NH 2 ## STR3 ## 2-Indolizinecarbonitrile, 3-amino-1- (2-oxo) -2-amino-1- 2-phenylethyl) -2-indolizinecarboxylic acid, 3-amino-1- (2-oxo-2-phenylethyl) -ethyl ester NH2 NH2 0 NH2 ..; N) ---- ---...------ Me OEt Ph --... C_ OEtN C_ OEt C_ OEt 40329-98-4 39203-49-1 39203-48-0 1-Indolizinecarboxylic acid, 3-amino -2-phenyl-, ethyl ester 1-Indolizinecarboxylic acid, 3-amino -2- methyl-, ethyl ester 1,2-indolizinedicarboxylic acid, 3-amino, 1,2-diethyl ester Me ..- Ph ----- N Ph ..---- I NH2 N NH2 - ,, .. ,, ........ ,, NNH2 39203-47-9 39203-46-8 3-Indolizinamine 39077-84-4 3-Indolizinamine, 2-methyl-3-Indolizinamine, 1, 2-diphenyl-Pho / O ----- N H N H 2 NH 2 NH 2 39077-83-3 3351-78-8 2-Indolizinecarboxamide, 3-amino-3-indolizinamine, 2- phenyl-2-indolizinecarboxylic acid, 3-amino-ethyl ester N / lei 2 N NH N / / NH 2 NH 2 2 -indolizinecarbonitrile, 3-amino-1,5-dimethyl-2-indolizinecarbonitrile, 3-amino-1,5 7-Trimethyl-1016230-66-2 Pyrrolo [1,2-alquinohne-2-carbonitrile, 1-amino N 0 1.N / / N / NH 2 NH 2 O -Glu NH 2 1284237-36-0 1284237-40-6 Pyrrolo [1,2-alquinohne-2-carboxylic acid, 1-amino-methyl ester Pyrrolo [2,1-alisoquinoline-2-carbonitrile, 3-amino pyrrolo [1,2-a]] Naphthyridine-8-carbonitrile, 9-amino- Preferably the radical R7 is a hydrogen atom. According to a particular embodiment, the oxidation base of formula (I) is preferably chosen from 3-aminoindolizine, preferably with R 7 representing a hydrogen atom. Preferably, the compounds of formula (I) are present in an amount of between 0.0001 and 10%, preferably between 0.01 and 5% by weight of the total weight of the composition (A). The invention comprises an oxidizing agent. Finally, the process is carried out with a composition (A) comprising one or more oxidizing agents.

More particularly, the oxidizing agent (s) is (are) chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts such as, for example, persulfates, perborates, peracids and their precursors, alkali or alkaline earth metal percarbonates and peracids and their precursors. Preferably, the oxidizing agent is hydrogen peroxide. This oxidizing agent is advantageously constituted by hydrogen peroxide, the concentration of which may vary, more particularly from 0.1 to 50% by weight, and even more preferably from 0.5 to 20% by weight, better still from 1 to 15% by weight. by weight relative to the composition (A). The process according to the present invention is carried out starting from a composition (A) comprising one or more oxidation dyes of formula (I) and additional oxidation dyes different from the oxidation dyes of formula (I) . The additional oxidation dyes are generally selected from oxidation bases and couplers. By way of example, the oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. The composition (A) may also comprise one or more couplers. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, monophenols, naphthalenic couplers, heterocyclic couplers and their addition salts. In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. The additional oxidation base or bases are each advantageously from 0.0001 to 10% by weight relative to the total weight of the composition, and preferably from 0.005 to 5% by weight relative to the total weight of the composition (A) . The content of the coupler (s), if they are (are) present, are each advantageously from 0.0001 to 10% by weight relative to the total weight of the composition, and preferably from 0.005 to 5% by weight relative to the total weight of the composition (A). According to a particular embodiment, the composition (A) comprises one or more nonionic surfactants, preferably oxyalkylenated.

According to a preferred embodiment of the invention, the surfactants are oxyalkylenated nonionic and selected from C8-C30 alcohols, oxyethylenated, saturated or unsaturated C8-C30 acid esters, linear or branched, and polyoxyethylenated sorbitol. Preferably, the composition (A) comprises one or more nonionic surfactants. The content of surfactants in the composition (A) is more particularly from 0.1 to 50% by weight, preferably from 0.5 to 30% by weight relative to the weight of the composition in question. The compositions (A) and / or (B) may also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof; mineral thickeners, and in particular fillers such as clays, talc; organic thickeners, with in particular the anionic, cationic, nonionic and amphoteric polymeric associative thickeners different from the polymers mentioned above; antioxidants; penetrants; sequestering agents; perfumes ; dispersants; film-forming agents; ceramides; preservatives; opacifying agents.

The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition in question.

According to one variant, the composition (A) may comprise one or more inorganic thickening agents chosen from organophilic clays. The organophilic clay may be selected from montmorrilonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. The clay is preferably a bentonite or a hectorite. These clays can be modified with a chemical compound chosen from quaternary amines, tertiary amines, amino acetates, imidazolines, amine soaps, fatty sulphates, alkyl aryl sulphonates, amine oxides, and mixtures thereof. As organophilic clays, mention may be made of quaternium-18 bentonites such as those sold under the names Bentone 3, Bentone 38, Bentone 38V by Rheox, Tixogel VP by United catalyst, Claytone 34, Claytone 40, Claytone XL by Southern Clay Company; stearalkonium bentonites such as those sold under the names Bentone 27 by Rheox, Tixogel LG by United Catalyst, Claytone AF, Claytone APA by Southern Clay; quaternium-18 / benzalkonium bentonite such as those sold under the names Claytone HT, Claytone PS by Southern Clay, Quaternium-18 Hectorites such as those sold under the names Bentone Gel DOA, Bentone Gel EC05, Bentone Gel EUG, Bentone IPP Gel, Bentone Gel ISD, Bentone Gel SS71, Bentone Gel V58, Bentone Gel V538 by Rhéox and Simagel M, Simagel SI 345 by Biophil.

When present, the mineral thickener is from 1 to% by weight based on the weight of the composition. Advantageously, the composition is in the form of a gel or a cream. The compositions (A '), (B) or (C) can be anhydrous or aqueous. More particularly, the term "anhydrous cosmetic composition" in the meaning of the invention is intended to mean a cosmetic composition having a water content of less than 5% by weight, preferably less than 2% by weight and even more preferably less than 1% by weight. % by weight relative to the weight of said composition. It should be noted that it is more particularly bound water, such as the water of crystallization of the salts or traces of water absorbed by the raw materials used in the production of the compositions according to the invention.

By aqueous composition is meant a composition comprising more than 5% by weight of water, preferably more than 10% by weight of water, and even more advantageously more than 20% by weight of water. Preferably, the composition (A) is an aqueous composition. Even more preferentially, the water concentration of the composition (A) can range from 10 to 90%, better still from 20 to 80% of the total weight of the composition. The compositions (A), (A '), (B) or (C) ) may optionally include one or more organic solvents. Examples of organic solvents that may be mentioned include linear or branched C 2 -C 4 alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof. The organic solvent or solvents, if present, represent a content usually ranging from 1 to 40% by weight relative to the weight of the composition containing them, and preferably ranging from 5 to 30% by weight. The pH of the compositions (A) and (B) if they are aqueous varies from 2 to 13. For the composition (A), it preferably varies from 6.5 to 12, better still from 8 to 12. The pH is adapted using additional acidifying or alkalizing agents, such as those mentioned below. Preferably, the composition (A) comprises one or more alkaline agents. By way of example, mention may be made of mineral amines such as ammonia or organic amines. In particular, organic amines chosen from alkanolamines, such as mono-, di- or trialkanolamines, comprising one to three identical or different C 1 -C 4 hydroxyalkyl radicals, in particular monoethanolamine, are particularly suitable.

As indicated above, composition (A) may result from mixing a composition (A ') comprising one or more oxidation dyes as defined above and a composition (C) comprising one or more oxidizing agents as defined above. . The compositions (A ') and (C) are preferably aqueous. They may in particular be in the form of direct or inverse emulsions. It can also result from the mixture of three compositions, the first two being the compositions (A ') and (B) above and the third composition being a composition (D) comprising at least one fatty substance as defined above; This composition (D) can be anhydrous or aqueous. It is preferably anhydrous. Usually, the pH of the oxidizing composition (C), when it is aqueous, is less than 7. In a first variant of the invention, the keratinous fibers, dry or wet, are applied successively with or without intermediate rinsing. composition (A) and the composition (B), the composition (A) being able to result from the extemporaneous mixing of the compositions (A '), (C) and optionally (D). Preferably according to this second variant there is no intermediate rinsing. Preferably, the composition (B) is applied before the composition (A).

The exposure time of the composition (B) on the keratinous fibers can vary from 5 to 15 minutes, and preferably is 10 minutes. In particular, the composition (B) is applied to the keratin fibers and allowed to stand for 10 minutes at room temperature. Preferably, the composition (B) is vaporized on the keratin fibers. In addition, the composition (A) can be left in place on the keratinous fibers for a duration, in general, of the order of 1 minute to 1 hour, preferably of 5 minutes to 40 minutes, preferably for 35 minutes. .

The temperature during the process is typically between room temperature (between 15 and 25 ° C) and 80 ° C, preferably between room temperature and 60 ° C. According to a preferred embodiment, the composition (B) and then the composition (A) are applied to the keratinous fibers, dry or wet, successively and without intermediate rinsing, and then the fibers are dried at a temperature ranging from room temperature to 60.degree. ° C, preferably at 60 ° C. The drying step may last from 5 to 20 minutes, preferably from 5 to 15 minutes, and is in particular 10 minutes. At the end of the treatment, the human keratin fibers are optionally rinsed with water, optionally washed with a shampoo followed by rinsing with water, before being dried or allowed to dry.

At the end of the treatment, the keratinous fibers are generally dried with a helmet at a temperature ranging from 50 to 80 ° C. According to one embodiment, the method for dyeing keratinous fibers comprises the use of: (a) a composition (B) comprising one or more metal catalysts chosen from transition metal salts, in particular the salts of organic acid of transition metals, and salts of rare earth metals, in particular inorganic salts of rare earth metals, preferably manganese salts, (b) anhydrous composition (D) comprising one or more bodies fatty acids chosen from liquid petrolatum, C6-C16 alkanes, polydecenes, liquid fatty acid esters and / or fatty alcohol esters, liquid fatty alcohols or their mixtures, preferably in an amount greater than 35% (c) a cosmetic composition (A ') comprising one or more oxidation dyes of formula (I), (d) an oxidizing composition (C) comprising one or more oxidizing agents, and in which one applies on keratinous fibers, successively and without intermediate rinsing, the composition (B), the keratinous fibers are dried, then the composition resulting from the extemporaneous mixing of the compositions (A), (C) and (D) is applied to said fibers. According to a second embodiment, the compositions (A) and (B) are mixed, and then the mixture is applied to dry or moist keratinous fibers. The first variant is preferred. Finally, the invention relates to a multi-compartment device comprising a first compartment containing a composition (B) comprising one or more metal catalysts as defined above, a second compartment containing a composition (A ') comprising at least one oxidation base of formula (I) as defined above, and a third compartment containing a composition (C) comprising one or more oxidizing agents as defined above, preferably at least one fatty substance as defined above being present in at least one of the compositions (A ') or (C), preferably so that after mixing the compositions (A') and (C), the fat content is greater than or equal to 20% relative to the total weight of the mixture of the compositions (A). ) and (C). According to a particular embodiment, the device comprises a fourth compartment comprising a composition (D) comprising one or more fatty substances, said composition (D) being to be mixed with the compositions (A ') and (C), the body content of the mixture (A '), (C), (D) being preferably greater than or equal to 20% by weight relative to the total weight of the mixture of the compositions (A'), (C) and (D), the compositions (A ') or (C) may or may not contain one or more fatty substances. The device is suitable for carrying out the coloring process according to the present invention. The following examples serve to illustrate the invention without being limiting in nature. EXAMPLE 1 I. Compositions tested 1. Preparation of the composition based on metal salts The composition (B1) based on metal salts (the amounts are expressed as a percentage by weight). Composition 131 Laureth-2 2g Decyl glucoside 2g Vaseline oil (Mineral oil) 78.5g Copolymer PEG-150 / Decyl alcohol / SMDI (Aculyn 44 sold by Rohm & Haas 0.5g Manganese Gluconate (CAS No. 6485-39-8) 0.4g Water qs 100g 3. Preparation of an Al coloring composition The coloring composition is produced at the time of use, by mixing: 6.7 g of the composition Dl-2.7 g of the composition A'l-10 g of the composition Each of the compositions is described in the following tables, the amounts being expressed in% by weight unless otherwise indicated: Composition D1 Vaseline oil 64.5 Octy1-2-dodecanol 11.5 Modified hectorite distearyl dimethyl ammonium 3 Propylene carbonate 1 Sorbinic monolaurate oxyethylenated (4E) 11 Glycol Distearate 8 Oxyethylenated Lauryl Alcohol (20E) 1 Composition A'1 containing the oxidation base of formula (I) Amino-indolizine oxidation base of formula (I) 20.10-3 mol% 2 , 4-diaminophenoxyethanol, HCI 20.10 mol% Mon free ethanolamine 14.37g Sodium metabisulfite 0.7g L-ascorbic acid 0.25g EDTA 0.287g Propylene glycol 6.2g Ethanol 15g Hexylene glycol 3g Dipropylene glycol 3g Benzyl alcohol 5g Deionized water qsp100g Composition Cl (oxidizing agent) Hydrogen peroxide 50% solution 12 Petrolatum oil Cetyl stearyl alcohol (C16 / C18 30/70) 8 Cetyl stearyl alcohol oxyethylenated (330E) 3 Tetrasodium pyrophosphate, 10H20 0.03 sodium hexahydroxystannate 0.04 Diethylene triamine pentaacetic acid, pentasodium salt 40% aqueous solution 0.15 Chloride poly-dimethyl di-allyl ammonium in 40% unstabilized water 0.5 Poly "(dimethyliminio) -1,3-propane diyl (dimethyliminio) -1,6-hexanediyl] dichloride in a 60% aqueous solution 0.25 Phosphoric acid qsp pH Amides of oxyethylenated rapeseed acids (40E) 1.3 Vitamin E 0.1 Glycerol 0.5 Deionized water QSP 100 In composition A'1, the following oxidation bases were used: dyestuff Color structure Amino-indolizine tested 1N I -zz .......... '. ## STR2 ## ## STR2 ## ## STR2 ## NH2 N0 \ NH2 II. Procedure The composition (B1) based on metal salts is applied to strands of natural hair 90% white (BN) and locks of hair 90% white permed (BP). The bath / composition ratio is 1/1 (g / g), respectively. The exposure time is 10 minutes at room temperature. Then rinse the locks of hair and squeeze the locks. The coloring composition Al is then applied by brush to each of the locks. The "composition / wick" bath ratio is 1/1 (g / g), respectively. It is allowed to stand for 35 minutes at room temperature. Another wick is prepared without application of the composition (B1). At the end of this exposure time, the locks of hair are washed with the shampoo iN0A POST, rinsed and then dried with a helmet at a temperature of 60 ° C. III. Results The color of the locks was evaluated in the CIE L * a * b * system, using a Minolta CM3600D Spectrophotometer colorimeter. In this system L * a * b *, L * represents the intensity of the color, a * indicates the green / red color axis and b * the blue / yellow color axis. The lower the value of L *, the darker or more intense the color. at. Calculation of the power of the color (DE *) In the table below, the value of DE * is calculated from the values of L * a * b * according to the following equation (i): DE * = V ( L * - L o *) 2 + (a * - ao *) 2 + (b * - bo *) 2 (i) The color strength is measured from the L *, a * and b * values measured on strands of natural white hair after staining, or streaks of white hair permed after staining, and Lo *, ao * and bo * represent the values measured on locks of unstained natural white hair, respectively on unstained strands of white permanent hair . The higher the value of DE *, the more powerful is the coloration. The results in terms of rise are summarized in the following table. Oxidation base used hair L * a * b * DE * Oxidation base 1 without pre-treatment BN 47.0 1,4 11,8 19,4 BP 44,3 1,2 13,9 24,8 with pre-treatment (composition B1) BN 38.5 5.7 11.6 26.0 BP 28.4 6.1 9.2 40.2 Oxidation base 2 without pre-treatment BN 50.2 1.7 15.2 16.4 BP 46.6 1.4 15.2 22.5 with the pre-treatment (composition B1) BN 28.2 4.5 7.1 36.4 BP 25.4 3.6 5, 2 43.5 Oxidation base 3 without pre-treatment BN 51.8 2.7 16.1 15.1 BP 47.6 1.9 14.9 21.6 with the pre-treatment (composition 1) BN 28 , 2 4.5 6.9 36.5 BP 25.1 3.4 5.1 43.8 Oxidation base 4 without pre-treatment BN 51.4 2.0 14, 8 15.2 BP 47.7 1.8 14.5 21.4 with the pre-treatment (composition B1) BN 33.6 4.7 9.3 30.9 BP 29.2 3.4 6.7 39.4 Base of oxidation 5 without pre-treatment BN 51.4 1.5 15.2 15.2 BP 50.6 1.0 15.4 18.5 with the pre-treatment (composition B1) BN 29.7 4.7 7.7 34, 9 BP 27.2 4.2 6.7 41.5 Oxidation base 6 without pre-treatment BN 54.2 2.1 15.2 12.5 BP 50.1 3.2 16.6 19.4 with pre-treatment (composit ion B1) BN 344 4.9 8.8, 30.2 BP 27.3 4.5 6.8 41.3 We can see: Without pre-treatment, we obtain glints of ash-gray ash, With the pre-treatment with the composition B and then the application of the composition Ai, a pearly brown color is obtained with an improved power level compared to the process without treatment.

Claims (3)

CLAIMS I. A method for dyeing keratinous fibers, comprising the use of one or more metal catalysts and a composition (A) comprising: one or more oxidizing agents, and at least one oxidation base chosen from 2 or 3- aminoindolizine of formula (I) wherein R1 to R7, independently, represent a hydrogen atom, a C1-C4 alkyl radical, an optionally substituted phenyl radical or an alkoxy radical; C1-C4, a halogen atom, a carboxylic radical (-COOH or -alkyl-COOH), a carboxamide radical (CONRR '), a nitrile radical (-CN), a sulphone radical (-SO2R), a sulphoxide radical; (-SORR '), a sulfoamide radical (-SO2NRR'), an alkylcarbonyl radical (-CO-alkyl), an alkoxycarbonyl radical (-CO-O-alkyl), a benzoyl radical (-CO-phenyl or - alkyl-CO phenyl optionally substituted on the phenyl group), and the 1,1 'bisindolizine compounds of formula (1); R4 to R7 may form in pairs adjacent to an optionally substituted 5- or 6-membered ring, unsaturated or unsaturated and capable of containing a heteroatom; with the additional proviso that R2 or R3 represents a radieal amino (N112) .2. Process according to Claim 1, characterized in that the metal catalysts are chosen from metal salts, metal oxides and metal complexes, and mixtures thereof. 3. Method according to claims I or 2, characterized in that the metal catalysts are selected from transition metal salts, rare earth metal salts and mixtures thereof. 4. Process according to claims 2 or 3, characterized in that the metal salts are inorganic salts chosen from halides, carbonates, sulphates and phosphates, especially hydrated or non-hydrated halides. 5. Method according to claims 2 or 3, characterized in that the metal salts are organic acid salts selected from citrates, lactates, glycolates, gluconates, acetates, propionates, fumarates, oxalates and tartrates, especially gluconates. 6. Process according to any one of the preceding re-ndicati on in which the metal salts are the salts of formula (H) as well as its solvates such as hydrates and their enantiomers: RC (0) -O-MOC (0) -R (II) wherein: - M represents a metal (H) or metal2 + of oxidation state 2, - R and R ', which may be identical or different, represent a (C 1 -C 6) (poly) hydroxyalkyl group. 7. Process according to any one of the preceding claims, characterized in that the metal catalysts are chosen from organic acid salts of transition metals, in particular of manganese, and inorganic salts of rare earth metals, in particular of cerium. . 8. Process according to any one of the preceding claims wherein the composition comprises (A) at least one fatty substance, the amount of fatty substance being preferably at least 10% by weight of the total weight of the composition (A) .9. Process according to Claim 8, characterized in that the fatty substances are chosen from C 6 -C 16 hydrocarbons or more than 16 carbon atoms and in particular alkanes, vegetable oils, fatty alcohols, fatty acid and / or fatty alcohol, silicones or mixtures thereof. 10. Process according to claim 8, characterized in that the fatty substances are chosen from oils at ambient temperature and at atmospheric pressure. 11. Process according to claim 8, characterized in that the fatty substances are chosen from petrolatum oil, polydecenes, liquid fatty alcohols, esters of fatty acids or fatty alcohols, liquids or mixtures thereof. 12. Process according to any one of the preceding claims, characterized in that the fatty substances are present in a content ranging from 10 to 70% by weight, and even more particularly ranging from 25 to 70% by weight, better still from 25 to 60% by weight. % by weight, and more particularly from 30 to 60% by weight relative to the total weight of the composition (A) in a content greater than or equal to 20% by weight, relative to the total weight of the composition (A). 13. Method according to any one of the preceding claims, characterized in that the cosmetic composition (A) further comprises one or more surfactants, preferably nonionic oxyalkylenated. 14. Process according to any one of the preceding claims, characterized in that the oxidation base of formula (I) is chosen by 2-aminoindolizine. 15. The process as claimed in claim 1, in which the 2-aminoindolizines are chosen in each case as follows: ## STR2 ## ..., CN OMe 1216181-08-6 1216172-24-5 1179499-93-41-Indolizinecarhonitrile. 2-amino-6-bram-1-indolizinecarbonitrile, 2-amino-5-methyl-1-indolizineacetic acid, 2-amino-3- (4-methoxybenzoyl) -7-methyl-2-methyl-2-amino-2-oxo-2H-phenyl NH 2 ## STR1 ## 1179390-33-0 1-Indolizineose1ic acid, 2-andno-3-benzoyl-7- methyl 1-Indolizineacetic acid 2-amino-3- (4-cldorobanzoyl) -7-methyl-Me NH2 CN 0 ---- Me NH2 I --..... .. - "- ° And Me NH2 - ..... Ac 1071698-46-8 63014-90-4 63014-83-5 2-Indolizinamine, 7-methyl 1-Indolizinecarbonthile, 2-andno-7-onethyl 1-Indolizinecarboxylic acid 3-acetyl-2-atnino-7-methyl-, ethyl ester CN xo2c-C2mMdM2 Me NH2 -Ph ... "cO10 ONe-O, C-Ph g CH2-CO2H 63014-78 1179499-93-4 1179448-21-5 1-Indolizinecarbonitrile, 2-amino-3-beryl-7-ethyl-1-indolizineacetic acid 2-amine-3- (4-methoxybenzoyl) -7-methyl-1-indolizineacetic acid Acid, 2-ordno-3-benzanyl-7-methyl-HO2C-C112 CN NH2 Me NH2, and C11-C11H11Cl 1179390-33-0 63014-78-8 1-1ndolizineacetic acid. 2-amino-3- (4-chlorobenzoyl) -7-methyl-1-indolizinecarbonttrile, 2-amino-3-benzoyl-7-inethyl 16. Process according to any one of the preceding claims 1 to 12, characterized in that the oxidation base of formula (I) is chosen by 3-aminoindolizine. 17. The process according to claim 1 to 15 wherein the 3-aminoindolizines are selected from Me N112 NE2 N-I2 I CN CN CN N N + 1 1284237-42-8 1284237-35- 2-Indelizinecarbonityl, 3-amine-5-methyl-2-indolylcarbonitrile, 3-amine-8-bromo-2-indelizinecarbonitrile, 3-amine-6-bromo-mm 2 Cl NH 2 0 H02 Ph IL OMe Ophne2 e CN 1251003-06-1 905975-90-8 205048-40-4 6-Indelizinecarboxylic acid, 3-amine-1-indolecarbonitrile, 3-amino-5-chloro-2-phertyl 8-indolizinecarboxylic acid, 3-amino-2-benzoyl-5-methyl-, methyl ester. Me NH 2 Bu-t Ph ... - "NI H2 ........ -..., ^ I ( el Cl Bt0- 59603-94-0 39203-50-4 1368620-19-2 6-Indelienecarboxylic acid, 3-amine-2- (4-dderophenyl) ethyl ester 3-Indelizinamine, 5-methyl-2-phenyl 3-Indolizinamine, 2- (1,1-dimethylthethyl) - and Pr-i NH2 ... .-- - Me --- ', NH2 -...... NH2 - CO211 1368538- 58-2 1368518-77-7 1368323-09-4 3-Tedalizinamine, 2-ethyl-3-indelienamine, 2- (1-methylethyl) -1-indolizinecarboxylic acid acid, 3-amino-2-methyl-NH 2 O NH 2 O- and Phosphorus) e 1360598-30-6 1284237-37-1 2 -Indelizinecarboxylic acid, 3-amino-1- (phenylsulfonyl) -, ethyl ester 2-Indelizinecarbenitrile, 3-amino-1-methylCE 0 0 -..... I -... ... NE2 -.... '. NH 2 NE 2 1284237-28-0 1284237-27- 1284237-25-7 3-Indolizinamine 2-Onethyllutfonyn-2-indolizinecarhonitrile, 3-amina 3-indottzinamine, 2- (phenylsulfonyl) -NH 2 O. o NH 2 V- Bu- t ....., -..., ...-- -.... '. 1-Propanone, 1- (3-amino-2-indolizino) -O-propanediol, 2-ditnethyl 1-indolizinecarboxylic acid, 3-amino-ethyl ester 1-indazinecarboxylic acid, 3-amino-NH 2 NH 2 -Oe Me Me-tol-1-yl. HC1 ........ NH2 c 1195215-45-2 1195207-22-7 186358-06-5 Ethanone, 1- (3-atnino-2-methyl-1-indo8zinyl) -, hydrochloride (1: 1 Ethanone, 1- (3-amino-2-methyl-1-indolizinyl) -2-indolizinecarboxylic acid, 3-amino-, methyl ester NH 2 NH 2 O CH 2 O 3 O: OEt - O CH 2 - L Ph CH 2 - II Ph 117600-74-5 117600-73-4 2-Indolizinecarbortitrile, 3-amitto-1- (2-oxo-2-phenylethyl) -2-n-dolizinecarboxylic acid, 3-amino-1- (2-ono) 2-phenylethoxy-ethyl ester NH 2 NE 12 0 NH 2 Me LOE t Ph ..'..- - .., .......- DI -......., ..- -... .. -..... -......_ -...... C- CIE t C.- OEt C- OEt 40329-98-4 39203-49-1 39203-48-0 1 -Indolizinecarboxylic acid, 3-amine-2-methyl-ethyl ester 1,2-Indolizinedicarboxylic acid, 3-amino-, 1,2-diethyl ester 1-IndetrineoeerbsecYl 3-amino-2-phenyl-ethyl ester-3-amino-2-ethyl-1-yl. dl] Ph -..., ... 111-12 NH2 -..., '. N112 39203-47-9 39203-46-8 3-Indolizinatnine 39077-84-4 3-Indolizinamine, 2-tnetityl-3-1odolizioamine, 1,2-diphenyl-Ph I ° _0Et 0 ...-- ... ## STR5 ## 2-Indolizinecarboxylic acid, 3-andno-, ethyl ester ... "--NN = N - -, N NH 2 NH 2 NN / = N NH 2 2 -indolizine acrylonitrile, 3-amino-1, 5-dnethyl-2-indolizinecarbonitrile, 3-atnino-1,5,7-tritnethyl-1016230-66-2 pyrrolo [1,2-alquinoline-2-corbonitrile, 1-andno .... "o = IN er] N / = NN NH2 IN NFI, * NH2 0- 1284237-36-0 1284237-40-6 186358-10-1 Pyrrols: 42.1 - esoquinoline-2-carbonitrile, 3-andno Pyrrolo [1,2-a] [1,8) aethyridine-8-carbonttrile, 9-amino-pyrrolo [1,2-alquinoline-2-carboxylic acid, 1-amino-, ethyl ester 18. A process according to any one of the preceding claims, characterized in that that the oxidizing agent is hydrogen peroxide. 19. Process according to any one of the preceding claims, characterized in that a composition (B) comprising said metal catalyst (s) and the composition (A) is mixed and then the mixture is applied to the keratin fibers, dry or wet. 20. Process according to any one of claims 1 to 17, characterized in that a composition (B) comprising said metal catalyst (s) and the composition is applied to the keratin fibers, dry or wet, successively with or without intermediate rinsing. (A), preferably without intermediate rinsing, preferably the composition (B) is applied before the composition (A). 21. Method according to any one of the preceding claims, characterized in that the composition (A) results from the mixture of 2 or 3 compositions, at least one composition (A ') comprising one or more oxidation dyes and a composition (C). ) comprising one or more oxidizing agents and optionally a composition (D) comprising one or more fatty substances. 22. Staining composition comprising at least one oxidation base of formula (I) as defined in any one of the preceding claims, at least 10% of fatty substances; preferably oil, preferably at least 20% and an oxidizing agent.