FR3007280A1 - OXIDATION COLORING PROCESS USING FATTY BODIES, METAL CATALYSTS, AND LESS OXIDATION BASES THAN COUPLERS - Google Patents

Abstract

The present invention relates to a process for the oxidation dyeing of keratin fibers using: one or more metal catalysts and a composition (C) comprising: optionally at least one oxidation base ii. at least one oxidation coupler, iii. at least one chemical oxidizing agent, the molar ratio (base) of oxidation on coupler (s) being less than 0.8 when one or more bases are present in the composition (C). The coloring process makes it possible to significantly improve the dyeing properties of the coloring in particular in terms of selectivity, chromaticity, intensity and color rise.

Description

The present invention relates to an oxidation dye composition comprising at least one fatty substance, at least one metal catalyst, and at least one oxidation dyeing composition comprising at least one metal catalyst, at least one coupler and optionally at least one oxidation base with an oxidation base molar ratio on a coupler of less than 1. It also relates to a process for the oxidation dyeing of keratin fibers using said composition, and a device with several compartments. For a long time, many people have been trying 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 and meta-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. As mentioned above, the oxidation coloration is carried out with oxidation bases and optionally couplers. When there is a mixture of base (s) and coupler (s), the bases are in an amount equal to or greater than the coupler. Until now oxidation dyeing without the use of oxidation bases and using only couplers, or by using more couplers than bases, does not give complete satisfaction, particularly in terms of power and the rise of color. . Moreover, oxidation dyeing processes using a pretreatment step from a composition containing metal derivatives of manganese / cerium type and oxidation dyeings are known. The pretreatment compositions generally consist of water-alcohol mixtures (see, for example, VVO 2003/011237, VVO 97/022008), or in the presence of oil (VVO 93/18738). However, the colors obtained are not always satisfactory in particular in terms of color variety, white hair coverage, chromaticity, color intensity and / or selectivity. This object (s) is (are) achieved by the present invention which relates to a process for the oxidation dyeing of keratinous fibers, in particular human keratinous fibers such as the hair, comprising the implementation of one or more metal catalysts and a composition (C) comprising: i. optionally at least one oxidation base ii. at least one oxidation coupler, iii. at least one chemical oxidizing agent, the molar ratio (base) of oxidation on coupler (s) being less than 0.8 when one or more bases are present in the composition (C). The subject of the invention is also a ready-to-use cosmetic composition (F) resulting from the mixture of (A) and (C) as defined above. The composition (F) comprises: i) at least one fatty substance in an amount greater than 25% by weight relative to the total weight of the composition (A), preferably in an amount greater than or equal to 35% by weight; and ii) at least one metal catalyst; iii) optionally at least one oxidation base preferably chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases preferably comprising at least two nitrogen atoms and their salts; addition; iv) at least one coupler; v) at least one chemical oxidizing agent; and it being understood that: the composition (F) comprises at least one alkaline, organic or inorganic agent and the molar ratio of the amount of oxidation base (s) to the amount of coupler (s) is less than 0, 8.

The coloring process and the composition (F) make it possible to significantly improve the dyeing properties of the coloration, in particular in terms of selectivity, that is to say to homogeneous colorations along the keratin fiber, chromaticity, the intensity and the rise of the color. In addition, the method according to the present invention makes it possible to lead to powerful and chromatic colorations. The use of a composition containing at least one catalyst, especially in pretreatment before oxidation dyeing and in particular rich in fatty substances, ie greater than 10%, makes it possible to a clear improvement of the coloring properties especially in terms of the rise of dyes on keratin fibers, power and chromaticity and selectivity of the color, even in the absence of oxidation base. Moreover, the dyeing method according to the invention makes it possible to improve the intensity of the coloration on the keratin fibers with respect to a conventional dyeing process.

The present invention also relates to a multi-compartment device comprising a first compartment containing a composition (A) comprising at least one metal catalyst, a second compartment containing a composition (B) comprising i) optionally one or more oxidation base, preferably selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases preferably comprising at least two nitrogens and their addition salts, ii) one or more couplers and iv ) one or more alkaline agents, organic or inorganic, it being understood that the molar ratio of oxidation base to coupler is less than 0.8; and a third compartment containing a composition (D) comprising one or more chemical oxidizing agents. According to a particular embodiment, the device comprises a fourth compartment comprising a composition (E) comprising one or more fatty substances, said composition (E) being to be mixed with the compositions (B) and (D), the fat content being greater than or equal to 10%, preferably greater than or equal to 25% by weight relative to the total weight of the mixture of the compositions (A), (B) and (D), the compositions (B) or (D) being able or not contain 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". The composition (A) used in the invention comprises i) at least 25% fats and ii) at least one metal catalyst. i) The fat (s): According to one particular embodiment of the invention, the composition (A) or the composition (C) as defined above comprise at least one fatty substance. Preferably, the composition (A) i.e. the composition comprising at least one metal catalyst comprises at least one fatty substance. 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 for the alkanes at 06-016, the latter are linear, branched, possibly cyclic. By way of example, mention may be made of hexane, dodecane, undecane, tridecane 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®. According to a particular embodiment, the fatty substances used in the process of the invention are chosen from volatile linear alkanes. By "one or more volatile linear alkane (s)" is meant indifferently "one or more volatile linear alkane (s) oil (s)". A volatile linear alkane suitable for the invention is liquid at ambient temperature (approximately 25 ° C.) and at atmospheric pressure (101 325 Pa or 760 mmHg). By "volatile linear alkane" suitable for the invention is meant a linear alkane, capable of evaporating on contact with the skin in less than one hour, at ambient temperature (25 ° C.) and at atmospheric pressure (101 ° C. Pa), liquid at ambient temperature, especially having an evaporation rate ranging from 0.01 to 15 mg / cm 2 / min, at ambient temperature (25 ° C.) and under atmospheric pressure (101,325 Pa). Preferably, the volatile linear alkanes that are suitable for the invention have an evaporation rate ranging from 0.01 to 3.5 mg / cm 2 / min, better still from 0.01 to 1.5 mg / cm 2 / min, at room temperature. ambient (25 ° C) and under atmospheric pressure (101,325 Pa). More preferably, the volatile linear alkanes that are suitable for the invention have an evaporation rate ranging from 0.01 to 0.8 mg / cm 2 / min, preferably from 0.01 to 0.3 mg / cm 2 / min. and still more preferably from 0.01 to 0.12 mg / cm 2 / min, at ambient temperature (25 ° C.) and under atmospheric pressure (101,325 Pa).

The rate of evaporation of a volatile alkane according to the invention (and more generally of a volatile solvent) can in particular be evaluated by means of the protocol described in VVO 06/013413, and more particularly by means of the protocol described below. after. Is introduced into a crystallizer (diameter: 7 cm) placed on a balance in a chamber of about 0.3 m3 regulated temperature (25 ° C) and humidity (relative humidity 50%), 15 g of hydrocarbon solvent volatile. The volatile hydrocarbon solvent is allowed to evaporate freely, without stirring, providing ventilation by a fan (PAPST-MOTOREN, reference 8550 N, rotating at 2700 revolutions / minute) arranged in a vertical position above the crystallizer containing the volatile hydrocarbon solvent, the blades being directed to the crystallizer, at a distance of 20 cm from the bottom of the crystallizer. The mass of volatile hydrocarbon solvent remaining in the crystallizer is measured at regular time intervals.

The evaporation profile of the solvent is then obtained by plotting the curve of the amount of product evaporated (in mg / cm 2) as a function of time (in min). Then we calculate the evaporation rate that corresponds to the tangent at the origin of the curve obtained. The evaporation rates are expressed in mg of volatile solvent evaporated per unit area (cm 2) and per unit of time (minute).

According to a preferred embodiment, the volatile linear alkanes that are suitable for the invention have a non-zero vapor pressure (also called saturated vapor pressure) at ambient temperature, in particular a vapor pressure ranging from 0.3 Pa to 6000. Pa. Preferably, the volatile linear alkanes that are suitable for the invention have a vapor pressure ranging from 0.3 to 2000 Pa, better still from 0.3 to 1000 Pa, at ambient temperature (25 ° C.). More preferably, the volatile linear alkanes that are suitable for the invention have a vapor pressure ranging from 0.4 to 600 Pa, preferably from 1 to 200 Pa, and even more preferably from 3 to 60 Pa, at room temperature (25 ° C.). ° C).

According to one embodiment, a volatile linear alkane suitable for the invention may have a flash point in the range of from 30 to 120 ° C, and more particularly from 40 to 100 ° C. The flash point is in particular measured according to the ISO 3679 standard. According to one embodiment, the volatile linear alkanes that are suitable in the invention can be linear alkanes comprising from 7 to 15 carbon atoms, preferably from 8 to 14 carbon atoms. carbon and better from 9 to 14 carbon atoms. More preferably, the volatile linear alkanes that are suitable in the invention may be linear alkanes comprising from 10 to 14 carbon atoms, and even more preferentially from 11 to 14 carbon atoms.

A volatile linear alkane suitable for the invention may advantageously be of plant origin. Preferably, the volatile linear alkane or the mixture of volatile linear alkanes present in the composition according to the invention comprises at least one carbon isotope 140 (carbon 14). In particular, the isotope 140 may be present in a ratio in number of isotopes 140/120 (or ratio 140/120) greater than or equal to 1.10-16, preferably greater than or equal to 1.10-15, more preferably greater than or equal to 7.5.1014, and better still or equal to 1.5.10-13. Preferably, the ratio 140/120 is from 6.10-13 to 1.2.10-12. The amount of isotopes 140 in the volatile linear alkane or the mixture of volatile linear alkanes can be determined by methods known to those skilled in the art such as the Libby counting method, liquid scintillation spectrometry or the accelerator mass spectrometry (Accelerator Mass Spectrometry). Such an alkane can be obtained, directly or in several stages, from a vegetable raw material such as an oil, a butter, a wax, etc. By way of example of alkanes which are suitable for the invention, mention may be made of the alkanes described in patent applications VVO 2007/068371 and WO2008 / 155059. These alkanes are obtained from fatty alcohols, themselves obtained from coconut oil or palm oil.

As examples of linear alkanes that are suitable for the invention, mention may be made of n-heptane (O), n-octane (O), n-nonane (O), n-decane (O10), n-undecane (C11), n-dodecane (012), n-tridecane (013), n-tetradecane (014), npentadecane (O15), and mixtures thereof. According to a particular embodiment, the volatile linear alkane is selected from n-nonane, n-undecane, n-dodecane, n-tridecane, n-tetradecane, and mixtures thereof. According to a preferred embodiment, mention may be made of the mixtures of n-undecane (C11) and n-tridecane (013) obtained in Examples 1 and 2 of Application WO2008 / 155059. Mention may also be made of n-dodecane (O12) and n-tetradecane (O14) sold respectively under the references PARAFOL 12-97 and PARAFOL 14-97 by the company Sasol, as well as their mixtures. One embodiment is to use a single volatile linear alkane. Alternatively, it is possible to use a mixture of at least two distinct volatile linear alkanes, differing from each other by a number of carbon atoms of at least 1, in particular differing from each other by a carbon number of 1 or 2. According to one embodiment, a mixture of at least two different volatile linear alkanes having from 10 to 14 carbon atoms and differing from each other by a carbon number of at least 1 is used. mention may in particular be made of mixtures of linear volatile alkanes 010/011, 01 1/012, or 012/013.

According to another embodiment, use is made of a mixture of at least two different volatile linear alkanes having from 10 to 14 carbon atoms and differing from each other by a carbon number of at least 2. As examples, mention may in particular be made of volatile linear alkane mixtures 010/012, or 012/014, for a number of carbon n even and the mixture C11 / 013 for an odd number of carbon n.

According to a preferred embodiment, a mixture of at least two volatile linear alkanes having from 10 to 14 distinct carbon atoms and differing from each other by a carbon number of at least 2, and in particular a mixture of carbon atoms, is used. 011/013 volatile linear alkanes or a mixture of 012/014 volatile linear alkanes. Other mixtures combining more than 2 volatile linear alkanes according to the invention, such as, for example, a mixture of at least 3 volatile linear alkanes having from 7 to 15 distinct carbon atoms and differing from each other by a number of carbon of at least 1, can be used in the invention. In the case of mixtures of two volatile linear alkanes, said two volatile linear alkanes preferably represent more than 95% and more preferably more than 99% by weight of the mixture. According to one particular embodiment of the invention, in a mixture of volatile linear alkanes, the volatile linear alkane having the smallest carbon number is predominant in the mixture.

According to another embodiment of the invention, a volatile linear alkane mixture is used in which the volatile linear alkane having the largest carbon number is predominant in the mixture. By way of examples of mixtures which are suitable for the invention, mention may be made in particular of the following mixtures: from 50 to 90% by weight, preferably from 55 to 80% by weight, and still more preferably from 60 to 75% by weight, Volatile linear alkane with n from 7 to 15 - from 10 to 50% by weight, preferably from 20 to 45% by weight, preferably from 24 to 40% by weight, of volatile linear Cn + alkane x with x greater than or equal to 1, preferably x = 1 or x = 2, with n + x between 8 and 14, relative to the total weight of the alkanes in said mixture. In particular, said mixture of volatile linear alkanes may contain, in addition: less than 2% by weight, preferably less than 1% by weight of branched hydrocarbons, and / or less than 2% by weight, preferably less of 1% by weight of aromatic hydrocarbons, and / or less than 2% by weight, preferably less than 1% by weight and preferably less than 0.1% by weight of unsaturated hydrocarbons, said percentages being expressed relative to to the total weight of the mixture. More particularly, the volatile linear alkanes suitable in the invention can be used in the form of a n-undecane / n-tridecane mixture. In particular, a mixture of volatile linear alkanes comprising: from 55 to 80% by weight, preferably from 60 to 75% by weight of volatile linear C1 1 alkane (n-undecane) and from 20 to 60% by weight; 45% by weight, preferably 24 to 40% by weight of volatile linear alkane in O13 (n-tridecane), relative to the total weight of the alkanes in said mixture. According to a particular embodiment, the mixture of alkanes is a nundecane / n-tridecane mixture. In particular, such a mixture can be obtained according to Example 1 or Example 2 of the application VVO 2008/155059.

According to another particular embodiment, the n-dodecane sold under the reference PARAFOL 12-97 is used by SASOL. According to another particular embodiment, n-tetradecane sold under the reference PARAFOL 14-97 is used by SASOL.

According to yet another embodiment, a mixture of n-dodecane and n-tetradecane is used. 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 Miglyol® 810, 812 and 818 by the company Dynamit Nobel; Among the fluorinated oils, mention may be made of perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, sold under the names "FLUTECO PC1" and "FLUTECO P03" by BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names "PF 50500" and "PF 50600" by the company 3M, or bromoperfluorooctyl sold under the name "FORALKYLO" by the company Atochem; nonafluoro-methoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives, such as 4-trifluoromethyl perfluoromorpholine sold under the name "PF 50520" by the company 3M. The fatty alcohols that can be used in the cosmetic compositions of the invention are saturated or unsaturated, linear or branched, and contain from 6 to 30 carbon atoms and more particularly from 8 to 30 carbon atoms. For example, cetyl alcohol, stearyl alcohol and their mixture (cetylstearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol or linoleic alcohol may be mentioned; . The wax or waxes that may be used in the cosmetic compositions of the invention 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 waxes bees, or modified beeswaxes (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 aliphatic mono or poly acid esters, linear or branched in Cl-026 and saturated or unsaturated aliphatic mono- or polyalcohols, linear or branched in Cl-026, 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 dihydroabiethyl behenate; octyldodecyl behenate; isoketyl behenate; cetyl lactate; alkyl lactate at 012015; 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 within the context of this variant, it is also possible to use the esters of di or tricarboxylic acids at 04-022 and of alcohols at Cl-022 and the esters of mono- or di-tricarboxylic acids and di-, tri-alcohols. tetra or pentahydroxy in 02-026. 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 6-030 fatty acid sugars, preferably 0-12-022. 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 of fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of linear or branched, saturated, linear or branched, 0-12-030 fatty acids, preferably 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 palmitostearate esters. More particularly, mono- and di-esters are used, and in particular 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 Glucate® 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 and 5L40 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-dipalmito-stearate marketed by Goldschmidt under the name Tegosoft @ PSE. The silicones that can be used in the cosmetic compositions of the present invention are volatile or non-volatile, cyclic, linear or branched silicones, modified or not with organic groups, having a viscosity of 5 × 10 -6 to 2.5 m 2 / s at 25.degree. ° C and preferably 1.10-5 to 1 m2 / 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: 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 formula: ## STR5 ## with D Examples of 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-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 the company Toray Silicone, silicones entering this class are also described in US Pat. HOUSEHOL e published in Cosmetics and Toiletries, Vol. 91, Jan. 76, p. 27-32 - 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 the ASTM 445 standard. 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 MIRASIL oils ® marketed by RHODIA such as, for example 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 the company GOLDSCHMI DT which are polydialkyl (C1-C20) 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 30 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, R35iO1 / 2, R5iO3 / 2 and 5i0412 in which 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 can 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 linear and / or branched polydimethyl / methylphenylsiloxanes, polydimethyl / diphenylsiloxanes having 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 containing alkyl groups in the form of -024 such as the products called dimethicone copolyol sold by the company Dow Corning under the name DC 1248 or the oils SILVVETO L 722, L 7500, L 77, L 711 of the company 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, C 1 -C 4 aminoalkyl groups; alkoxylated groups, such as the product marketed under the name "Silicone Copolymer F-755" by SVVS Silicones and Abil Wax® 2428, 2434 and 2440 by the company GOLDSCHMIDT. Preferably, the fatty substances do not comprise oxyalkylenated unit 02-03 or glycerolated unit. Preferably, the fatty substances are not fatty acids and in particular salified fatty acids or soaps which are water-soluble compounds. The fatty substances are advantageously chosen from hydrocarbons containing from 6 to 16 carbon atoms or more than 16 carbon atoms, and in particular alkanes, oils of vegetable origin, fatty alcohols, fatty acid esters and / or alcohol esters. 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 petroleum jelly, 06016 alkanes, volatile linear alkanes, polydecenes, liquid fatty acid esters and / or fatty alcohol esters, liquid fatty alcohols or their derivatives. mixtures. Better still, the fatty substance is chosen from petrolatum oil and alkanes at 06-016, polydecenes. The fatty substances are present in a content greater than 25% by weight, relative to the total weight of the cosmetic composition (A). The composition (A) has a fat content preferably ranging from 30 to 80% by weight, and even more particularly ranging from 35 to 75% by weight, better still from 40 to 70% by weight, and more particularly from 50 to 70% by weight. to 60% by weight relative to the total weight of the composition (A). According to an advantageous variant of the invention, the process of the invention uses the composition (C) which has a fat content preferably ranging from 10 to 90% by weight, and even more particularly ranging from 20 to 80% by weight. by weight, preferably from 20 to 50% by weight, relative to the total weight of the composition (C). According to an advantageous embodiment of the invention, the composition (F) comprises a fatty substance content preferably ranging from 10 to 90% by weight, and even more particularly ranging from 20 to 80% by weight, better still from 30 to 50% by weight. % by weight, and especially 40% by weight relative to the total weight of the composition (F). ii) The metallic catalyst (s) The dyeing method and the composition (F) according to the present invention use 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 mixtures thereof. 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.

According to one variant, the metal salts are inorganic and may be chosen from halides, carbonates, sulphates and phosphates, in particular 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 -O (O) -OH, at least one of said functions -O (O) -OH is in the carboxylate form -O (O) -O-complexed with the metal atom, preferably Mn (II). More particularly, the metal salt is complexed with two carboxylate groups, such as that of formula (I): R-O (O) -O-M-O-O (O) -R '(I), as well as its solvates such as the hydrates and their enantiomers Formula (I) in which: -M represents a metal (II) or metal2 + of oxidation state 2, -R and R ', which may be identical or different, represent a (01-06) (poly) hydroxyalkyl group . In particular, 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. According to a particular embodiment of the invention, manganese is not an oxide but a manganese salt. The organic metal salts may be more particularly chosen from salts of organic acids such as citrates, lactates, glycolates, gluconates, acetates, propionates, fumarates, oxalates and tartrates, in particular gluconates. More preferably, the metal catalysts are chosen from manganese gluconate and cerium heptahydrate chloride, in particular manganese gluconate.

Preferably, the metal catalyst (s) are chosen from compounds of formula (I) and more particularly represents manganese gluconate. The metal catalysts when in the form of composition (A) 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 relative to the total weight of the composition. The composition (A) may contain exclusively the metal catalyst (s) associated with one or more fatty substances. According to another variant, this composition (A) contains other compounds than the metal catalyst (s) such as the additional ingredients see "Additional ingredients or adjuvants" below.

This composition (A) may be anhydrous or aqueous, preferably aqueous. The composition (C) used in the invention is a ready-to-use composition and comprises i) at least one oxidation base; ii) optionally at least one coupler; iii) at least one chemical oxidizing agent; and iv) at least one organic or inorganic alkaline agent. This composition (C) can be anhydrous or aqueous, preferably aqueous Composition (B) of the device of the invention comprises oxidation dyes i) and ii) as defined above.

This composition (B) can be anhydrous or aqueous, preferably aqueous. The molar ratio base / coupler <0.8: The molar ratio of the amount of base (s) of oxidation on the amount of coupler (s) less than 0 8 is to be observed according to the invention in the composition and the process. It is understood that the dye composition of the invention contains at least one or more coupler (s), nevertheless it may not contain an oxidation base so that the base / coupler molar ratio is zero. Thus, the base / coupler molar ratio is between 0 inclusive and 0.8 inclusive. More particularly, the molar ratio ranges from 0 to 0.5 inclusive. The oxidation bases According to a particular embodiment of the invention, the coloring composition (C) comprises at least one oxidation base. Preferably, the oxidation base (s) are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols and ortho-aminophenols, the heterocyclic bases preferably comprising at least two nitrogen atoms and their addition salts and / or their solvates.

By way of example, the oxidation bases are chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases, in particular comprising at least 2 nitrogen atoms and their salts. addition, preferably paraphenylenediamines. Among the paraphenylenediamines, there may be mentioned, for example, para-phenylenediamine, paratoluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl paraphenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl-para-phenylenediamine, 4-amino-N, N-diethyl-3-methylaniline, N, N- bis - ([3-hydroxyethyl) paraphenylenediamine, 4-N, N-bis (13-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (13-hydroxyethyl) amino-2-chloroaniline, 213-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (p-hydroxypropyl) -paraphenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, p-hydroxyethyl) paraphenylenediamine, N - ([3,7-dihydroxypropyl paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl-para-phenylenediamine, 213-hydroxyethyloxy-para-phenylenediamine, 213-acetylaminoethyloxy-para-phenylenediamine, N- (p-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, hydroxyethylamino 5-amino toluene, 3-hydroxy 1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid. Among the para-phenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 213-hydroxyethyl paraphenylenediamine, 213-hydroxyethyloxy paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (p-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 213-acetylaminoethyloxy-para-phenylenediamine, and their acid addition salts are particularly preferred.

Among the bis-phenylalkylenediamines, mention may be made, for example, of N, N'-bis (p-hydroxyethyl) N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, N 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'-bis - (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts. Among the para-aminophenols, para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-chlorophenol, 4- amino 3-hydroxymethyl phenol, 4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- hydroxyethyl aminomethyl) phenol, 4-amino-2-fluoro phenol, and their addition salts with an acid. Among the ortho-aminophenols, there may be mentioned by way of example, 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-amino phenol, and their addition salts. Among the heterocyclic bases, those comprising at least two nitrogen atoms are preferred; pyridine derivatives, pyrimidine derivatives, and pyrazole derivatives, preferably pyrazoles, are preferred. 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-diaminopyridine, 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 [1,5-4-pyridines oxidation bases or their addition salts described for example in the patent application FR 2801308. A 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-Aminopyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridine-7-yl) -ethanol; (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diaminopyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-ylpyrazolo [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-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-Amino-pyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-aminopyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-aminopyrazolo [1,5-a] pyridin-7-ol, 2- (2-hydroxyethoxy) -3-amino-pyrazolo [1,5-a] pyridine and 2- (4-methylpiperazinium-1) yI) -3-amino-pyrazolo [1,5-a] pyridine; ; as well as 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 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-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino pyrazole 1-Benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl-pyrazole, 4,5-diamino-1-tert-butyl-3-methyl-pyrazole, 4, 5-diamino 1- (13-hydroxyethyl) 3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 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-m ethyl 1-isopropyl pyrazole, 4-amino 5- (2'-aminoethyl) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4- (13-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts. It is also possible to use 4-5-diamino-1- (pmethoxyethyl) pyrazole. Pyrazole derivatives that may also be mentioned include diamino N, N-dihydropyrazolopyrazolones and especially those described in application FR-A-2,886,136. that 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, 5Hpyrazolo [1,2-a] pyrazol-1-one, 2-amino- 3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol- 1-one, 2-aminopropyl-3- (pyrrolidin-1-yl) -6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 4,5-diamino-1 2-dimethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2-diethyl-1,2-dihydro-pyrazol-3-one, 4,5-diamino-1,2 di- (2-hydroxyethyl) -1,2-dihydro-pyrazol-3-one, 2-amino-3- (2-hydroxyethyl) amino-6,7-dihydro-1H, 5H-pyrazolo [1,2- a] pyrazol-1-one, 2-amino-3-dimethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2,3-diamino-5,6, 7,8-Tetrahydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one, 4-aminodo-1,2-diethyl -5- (pyrrolidin-1-yl) -1,2-dihydro-pyrazol-3-one, 4-amino-5- (3-dimethylamino-pyrrolidin-1-yl) -1,2-diethyl-1,2 dihydro-pyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one. It will be preferred to use 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and / or a salt thereof.

As heterocyclic bases, 4,5-diamino-1- (13-hydroxyethyl) pyrazole, pyrazolo [1,2-a] pyrazol-1-one derivatives in particular substituted by an amino group in 2 and 3, will preferably be used. such as 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2- (2-hydroxyethoxy) -3-amino-pyrazolo [1, 5-a] pyridine and 2- (4-methylpiperazinium-1-yl) -3-amino-pyrazolo [1,5-a] pyridine salts; and / or an addition salt thereof. Preferably, the oxidation base used will be a heterocyclic base and more particularly the pyrazole derivatives, more preferably the pyrazolo [1,2-a] pyrazol-1-one derivatives in particular substituted with an amino group at 2 and 3 such as 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and / or a salt thereof. According to another particular embodiment of the invention, the composition (C) does not comprise an oxidation base. And according to a particular embodiment, the method does not use an oxidation base. Couplers: The composition (C) comprises one or more couplers conventionally used for dyeing keratinous fibers. Preferably, the couplers are chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.

By way of example, mention may be made of 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene and 2,4-diamino-1- (G- hydroxyethyloxy) benzene, 2-amino 4- (G-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido-dimethylamino benzene, sesamol, 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- (G-hydroxyethyl) amino-3 , 4-methylene dioxybenzene, 2,6-bis- (G-hydroxyethylamino) toluene, 6-hydroxy indoline, 2,6-dihydroxy-4-methyl pyridine, 1-H 3 -methyl pyrazole 5-one, 1-phenyl-3-methyl-pyrazole-5-one, 2,6-dimethyl-pyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] -1, 2,4-triazole, 6-methyl pyrazolo [1,5-4-benzimidazole, their acid addition salts, and mixtures thereof. Preferably, the coupler (s) used in the process of the invention are chosen from meta-phenylenediamines such as 2,4-diamino-1- (G-hydroxyethyloxy) benzene. 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 oxidation base (s), if present, are each advantageously from 0.001% 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. (C) and ready-to-use composition.

The content of the coupler (s) is each advantageously from 0.001 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 (C) and the ready-to-use composition.

According to a particular embodiment of the invention, the composition (C) as defined above further comprises one or more direct dyes, synthetic or natural, chosen from ionic or nonionic species, preferably cationic or nonionic, or as the only dyes in addition to the oxidation dye (s).

As examples of suitable direct dyes, mention may be made of azo direct dyes; (poly) methine dyes such as cyanines, hemicyanins, and styryls; carbonyls; azinic; nitro (hetero) aryl; tri- (hetero) aryl methanes; porphyrins; phthalocyanines and natural direct dyes, alone or in mixtures.

Among the natural direct dyes that may be used according to the invention, lawsone, juglone, alizarin, purpurine, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine, orceins. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna. When they are present, the direct dye or dyes more particularly represent from 0.001 to 10% by weight of the total weight of the composition, and preferably from 0.005 to 5% by weight relative to the total weight of the composition (C). Compositions (B), (D) and ready-to-use composition (C) may also contain additional ingredients. The chemical oxidizing agents: More particularly, the chemical 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 (C) or (D).

Additional Ingredients or Adjuvants: According to a particular embodiment, the compositions (A), (B), (C) and / or (D) comprise 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 cosmetic compositions (A) and / or (C) comprise one or more nonionic surfactants. The content of surfactants in the compositions (A) and / or (C), more particularly represent from 0.1 to 50% by weight, preferably from 0.5 to 30% by weight relative to the weight of the composition under consideration. The compositions (A), (B), (C) and / or (D) may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, cationic, nonionic, amphoteric, zwitterionic or their mixtures; 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 an advantageous variant of the invention, the anhydrous composition (A) comprises 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. According to another variant of the invention, the composition (A) and / or (C) comprises one or more organic thickeners. Advantageously, the composition is in the form of a gel or a cream. The compositions (A) and / 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 cosmetic composition (C) is an aqueous composition.

Even more preferentially, the water concentration of the composition (C) can range from 10 to 90%, better still from 20 to 80% of the total weight of the composition. The compositions (A), (B), (C) and / or ( D) may optionally comprise one or more organic solvents. As organic solvent, there may be mentioned, for example, linear or branched alkanols, 02-04, 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 (s), if present, represent a content usually ranging from 1 to 40% by weight relative to the weight of the cosmetic composition (C), and preferably ranging from 5 to 30% by weight. The pH of the compositions (A), (B), (C) and / or (D) if they are aqueous varies from 2 to 13.

For the composition (A) it preferably ranges from 6.5 to 12, more preferably from 8 to 12. The pH is adjusted using additional acidifying or alkaline agents, such as those mentioned below. The alkaline agents: Preferably, the compositions (A) and / or (C), more preferably (A) and (C) comprise one or more alkaline agents, organic or inorganic, preferably organic. The inorganic alkaline agent (s) is (are) preferably chosen from ammonia, alkali carbonates or bicarbonates, such as sodium or potassium carbonates or bicarbonates, sodium or potassium hydroxides, or mixtures thereof. The organic alkaline agent (s) is (are) preferably chosen from organic amines whose pKb at 25 ° C. is less than 12, and preferably less than 10, and even more advantageously less than 6. It should be noted that this is pKb corresponding to the highest basicity function. In addition, the organic amines do not comprise a fatty chain, alkyl or alkenyl, comprising more than ten carbon atoms. The organic alkaline agent (s) are, for example, chosen from alkanolamines, ethoxylated and / or oxypropylenated ethylene diamines, amino acids and compounds of the following formula (III): ## STR2 ## which VV is a divalent C1-C6 alkylene radical optionally substituted by one or more hydroxyl groups or a C1-C6 alkyl radical, and / or optionally interrupted by one or more heteroatoms such as O, or NR '; Rx, Ry, Rz, Rt, R, and the same or different, represent a hydrogen atom, a C1-C6 alkyl or hydroxy-C1-C6 alkyl, or C1-C6 aminoalkyl radical. Examples of amines of formula (III) are 1,3-diaminopropane, 1,3-diaminopropanol, spermine and spermidine. By alkanolamine is meant an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C 1 -C 8 alkyl groups bearing one or more hydroxyl radicals. In particular, the organic amines chosen from alkanolamines, such as mono-, di- or trialkanolamines, comprising one to three identical or different C 1 -C 4 hydroxyalkyl radicals are suitable in the embodiment of the invention.

Among compounds of this type, mention may be made of monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N, N-dimethylethanolamine, 2-amino-2-methyl-1-propanol and triisopropanol. amine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris-hydroxymethylamino-methane.

More particularly, the amino acids that can be used are of natural or synthetic origin, in their L, D, or racemic form, and comprise at least one acid function chosen more particularly from the carboxylic, sulphonic, phosphonic or phosphoric acid functions. Amino acids can be in neutral or ionic form.

As amino acids that may be used in the present invention, mention may in particular be made of aspartic acid, glutamic acid, alanine, arginine, ornithine, citrulline, asparagine, carnitine and cysteine. , glutamine, glycine, histidine, lysine, isoleucine, leucine, methionine, N-phenylalanine, proline, serine, taurine, threonine, tryptophan, tyrosine and valine.

Advantageously, the amino acids are basic amino acids comprising an additional amine function optionally included in a ring or in a ureido function.

Such basic amino acids are preferably chosen from those corresponding to the following formula (IV), as well as their salts: ## STR2 ## Formula (V) in which R represents a group chosen from : NH; - (C1-12) 3NI-12; - (CH2) 21 \ 11-12; - (CH2) 2NHCONH2; and - (CH 2) 2 NH-C-NH 2 NH The compounds corresponding to formula (V) are histidine, lysine, arginine, ornithine, citrulline.

The organic amine may also be chosen from heterocyclic organic amines. In addition to the histidine already mentioned in the amino acids, mention may be made, in particular, of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole. The organic amine may also be selected from amino acid dipeptides. As amino acid dipeptides that may be used in the present invention, carnosine, anserin and whale may be mentioned in particular. The organic amine may also be chosen from compounds containing a guanidine function. As amino amines of this type which can be used in the present invention, mention may in addition be made of arginine already mentioned as amino acid, creatine, creatinine, 1,1-dimethylguanidine, 1,1 diethylguanidine, glycocyamine, metformin, agmatine, n-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid and 2 - ([amino (imino) methyl] amino acid) ethane-1-sulfonic acid. As hybrid compounds, mention may be made of the salts of the amines mentioned above with acids such as carbonic acid and hydrochloric acid.

In particular, guanidine carbonate or monoethanolamine hydrochloride can be used. Preferably, the alkaline agent (s) present in the composition of the invention are chosen from ammonia, alkanolamines, amino acids in neutral or ionic form, in particular basic amino acids, and preferably corresponding to those of formula ( III). Even more preferentially, the alkaline agent (s) are chosen from ammonia, alkanolamines, especially monoethanolamine (MEA). More preferably, the alkaline agent (s) are chosen from alkanolamines, in particular monoethanolamine (MEA).

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, the ready-to-use composition (C) can result from the mixing of a composition (B) comprising i) one or more oxidation bases, preferably chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases preferably comprising at least two nitrogen atoms and their addition salts, ii) optionally one or more couplers and a composition (D) comprising one or more oxidizing agents as defined previously. The compositions (B) and (D) are preferably aqueous. They may in particular be in the form of direct or inverse emulsions.

It may also result from the mixture of three compositions, the first two being the compositions (B) and (D) above and the third composition being a composition (E) comprising at least one fatty substance as defined above; This composition (E) can be anhydrous or aqueous. It is preferably anhydrous. Usually, the pH of the oxidizing composition (D), when aqueous, is acidic ie less than 7. Methods of the invention: According to a particular embodiment of the invention, the oxidation dyeing process of keratinous fibers of the invention implements the following steps: a) a step of treating said fibers by applying to said fibers a cosmetic composition (A) comprising: i) at least one metal catalyst; b) optionally a washing, rinsing, drying and / or spinning step; c) a step of staining by application to said fibers of a cosmetic composition (C) comprising: i) optionally at least one oxidation base preferably chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, the heterocyclic bases preferably comprising at least two nitrogen atoms and their addition salts; ii) at least one coupler; iii) at least one chemical oxidizing agent; and it being understood that: the composition (A) and / or (C) comprises at least one alkaline, organic or mineral agent; the molar ratio of the amount of oxidation base (s) relative to the amount of coupler (s) is less than or equal to 0.8; steps a), b) and c) can be carried out successively a), then b) then c), or else c), then b) then a), or else a) and c) can be carried out together followed by b) and - the composition (A) and / or the composition (C) contain i) at least one fatty substance, preferably in an amount greater than or equal to 10%, particularly greater than or equal to 25%, more preferably in a greater amount than or equal to 35% by weight relative to the total weight of the composition (A) or (C), preferably the composition (A) comprises at least one fatty substance. . According to a particular embodiment of the invention, the dyeing method implements steps a), b) and c) as defined above with steps c) and then b) then a) carried out successively. According to a particular embodiment of the invention, the dyeing method implements steps a), b) and c) as defined above with steps a) and c) carried out together followed by step b). According to another particularly advantageous embodiment of the invention, the staining method implements the steps carried out successively a), then b) and then c).

More particularly, the process for the oxidation dyeing of keratin fibers uses: a) a step of pretreatment of said fibers by applying to said fibers a cosmetic composition (A) comprising: i) at least one fatty substance in a quantity greater than 25% by weight relative to the total weight of the composition (A), preferably in an amount greater than or equal to 35% by weight; and ii) at least one metal catalyst; b) optionally a washing, rinsing, drying and / or spinning step; c) followed by a step of coloring by applying to said fibers a cosmetic composition (C) comprising: i) optionally at least one oxidation base preferably chosen from para-phenylenediamines, bis-phenylalkylenediamines, para aminophenols, ortho-aminophenols, heterocyclic bases preferably comprising at least two nitrogen atoms and their addition salts; ii) at least one coupler; iii) at least one chemical oxidizing agent; and it being understood that: the composition (A) and / or (C) comprises at least one alkaline, organic or inorganic agent and the molar ratio of the amount of oxidation base to the amount of coupling is less than 0, 8. According to one variant of the present invention, the composition comprising the metal catalysts or composition (A) is applied to the dry or moist keratinous fibers, and then a coloring composition (C) as defined above is applied. According to one variant, the compositions (B) and (D) as defined above are mixed in order to produce the composition (C) ready for use and then the mixture made is applied to the keratin fibers, dry or wet. there is no intermediate rinse.

The exposure time of the composition comprising the metal catalysts or composition (A) on the keratinous fibers can vary from 5 to 15 minutes, and preferably is 10 minutes. In particular, the composition comprising the metal catalysts or composition (A) is applied to the keratin fibers and allowed to stand for 10 minutes at room temperature. Preferably, the composition comprising the metal catalysts or composition (A) is vaporized on the keratinous fibers. In addition, the coloring composition (C) 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. 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 comprising the metal catalysts or composition (A) is applied to the keratin fibers, dry or wet, successively and without intermediate rinsing, and the fibers are then dried at a temperature ranging from room temperature to 60.degree. ° C, preferably at 60 ° C, then the composition (C) as defined above is applied, then optionally washed, rinsed and / or dried said fibers.

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, ie after the application of the composition (C) as defined above, the human keratinous fibers are preferably rinsed with water, optionally washed with a shampoo followed by rinsing with water. water, before being dried or allowed to dry. At the end of the treatment i.e. after the application of the composition (C) as defined above, the keratinous fibers are generally dried with a helmet at a temperature ranging from 50 to 80 ° C. According to a particular embodiment of the invention, the process for dyeing keratinous fibers is carried out in at least three successive steps: [0103] In a first step of a composition comprising the metal catalysts or composition (A) as defined above comprising i) one or more metal catalysts chosen from transition metal salts, in particular organic acid salts of transition metals, and rare earth metal salts, in particular inorganic salts of rare earth metals, of preferably the manganese salts; ii) at least 35% fat, preferably the fatty substance (s) being chosen from fatty substances which are liquid at ambient temperature and at atmospheric pressure, in particular chosen from petrolatum oil, alkanes at 06-016, polydecenes liquid esters of fatty acid and / or fatty alcohol, liquid fatty alcohols or mixtures thereof; and optionally iii) at least one alkaline agent, in particular chosen from alkanolamines such as triethanolamine; - Then in a second time an intermediate rinse, and preferably spin with tissue or paper absorbent, - then in a third time is applied in a second time a ready-to-use cosmetic composition (C) comprising i) at least one oxidation base chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases preferably comprising at least two nitrogen atoms and their addition salts; ii) optionally at least one coupler; and iii) at least one chemical oxidizing agent; and iv) at least one alkaline agent, preferably an organic agent, in particular alkanolamines such as monoethanolamine (MEA). Said ready-to-use composition according to the invention (C) is prepared before use by extemporaneous mixing of an oxidation dyeing composition (B) comprising at least one oxidation base chosen in particular from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases preferably comprising at least two nitrogen atoms and their addition salts; ii) optionally at least one coupler and a composition comprising at least one chemical oxidation agent (composition (D) as defined above). Device Finally, the invention relates to a multi-compartment device comprising a first compartment containing a cosmetic composition (A) as defined above, a second compartment containing a cosmetic composition (B) as defined above, and a third compartment containing a composition (D) as defined above. According to a particular embodiment, the device comprises a fourth compartment comprising a composition (E) comprising one or more fatty substances, said composition (E) being to be mixed with the compositions (B) and / or (D), the content of fat being greater than or equal to 35% by weight relative to the total weight of the mixture of compositions (A) to (D). 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. EXAMPLES 1 / Staining method Step 1 (according to the invention): Brush application of the pretreatment composition containing a metal catalyst: Mn gluconate on natural Caucasian hair 90% whites. The ratio of bath composition / hair is 3/1 (w / w). The pause time is 10 minutes at 27 ° C Step 2 (according to the invention): Rinsing and then partial drying with an absorbent towel.

Step 3 (Invention and Comparative): Brush application of the blends of the coloring compositions. The ratio of mixing bath / hair is 10/1. 30 minutes break. At the end of this break time, the locks are washed with INOA Post shampoo, rinsed and then dried. The coloration obtained is evaluated using a MINOLTA CM2600D spectrocolorimeter. A composition (A) is prepared Ingredients (A) OCTYL-2 DODECANOL 78.5 ALKYL (C8 / C10 / C12 / C14 34/24/29/10) POLYGLUCOSIDE (1,4) IN 2 AQUEOUS SOLUTION, 53% UNPROTECTED (pH 11.5 by NaOH)) LAURYL ALCOHOL OXYETHYLENE (20) 2 POLYMER SMDI / POLYETHYLENE GLYCOL WITH DECYLATED TERMINATION IN HYDROGLYCOLIC SOLUTION 0.5 MANGANESE GLUCONATE, 2 H2O 0.4 DESIONIZED WATER Qs 100 * Quantity:% in g per 100 g composition (A) 3 / Preparation of the dye compositions (Cl) and (C2) from the compositions (B1) and (B2) and the oxidizing composition (D): A composition (B1) Ingredients (B1) is prepared ) * ACID ETHYLENE TETRACEOUS DIAMINE 0.2 OLEIC ALCOHOL OXYETHYLENE (10 0E) 1 CETYL PALMITATE 2 VITAMIN C: L-ASCORBIC ACID IN FINE POWDER 0.12 OLEIC ALCOHOL OXYETHYLENE (20 0E) 4 MIXTURE OF LINEAR ALKOLS IN C18 A C24 (C18 / C20 / C22 / C24: 4.6 7/58/30/6) ALCOHOL CONTENT> 95% SODIUM METABISULFITE POWDER 0.22 VASELINE OIL 60 DECYLIC ALCOHOL OXYETHYLENE (50E) 1.2 GLY CEROL 5 1-BETA-HYDROXYETHYLOXY-2,4-DIAMINO-BENZENE DICHLORHYDRATE 3.86 CARBOXYVINYL POLYMER SYNTHESIZED IN THE MIXTURE ETHYL ACETATE / CYCLOHEXANE 0.1 CETYLSTEARYLIC ALCOHOL (C16 / C18) OXYETHYLENE (60 OE) 0.01 ETHER Purified Myristyl Glycol MONOETHANOLAMINE 6.3 WATER DESIONISEE Qsp 100 * Quantity:% in g per 100 g of composition (B1) NB: Composition B1 does not contain any oxidation base. A composition (B2) Ingredients (B2) * ETHYLENE ACID TETRACEOUS DIAMINE 0.2 OLEIC ALCOHOL OXYETHYLENE (10 0E) 1 CETYL PALMITATE 2 VITAMIN C: L-ASCORBIC ACID IN FINE POWDER 0.12 ALCOHOL OLEIC OXYETHYLENE (20 0E ) 4 MIXTURE OF LINEAR C18 TO C24 ALCOHOLS 4.6 (C18 / C20 / C22 / C247 / 58/30/6) ALCOHOL CONTENT> 95% SODIUM METABISULFITE POWDER 0.22 VASELINE OIL 60 DECYLIC ALCOHOL OXYETHYLENE (50E) 1,2 GLYCEROL 5 1-BETA-HYDROXYETHYLOXY-2,4-DIAMINO-BENZENE DICHLORHYDRATE 1,1,10-2mol 2,3-DIAMINO-6,7-DIHYDRO-1H, 5H-PYRAZOLO [1,2-A] ] PYRAZOL-1-ONE DI M ETHAN ESU LFONATE 5.5.10-3mol CARBOXYVINYL POLYMER SYNTHESIZED IN THE MIXTURE ETHYL ACETATE / CYCLOHEXANE 0.1 CETYLSTEARYLIC ALCOHOL (C16 / C18) OXYETHYLENE (60 OE) MYRISTYL GLYCOL ETHER 0.01 MONOETHANOLAMINE PURE 5.6 WATER DESIONISEE Qsp 100 * Quantity:% in g per 100 g of composition (B2), unless otherwise stated Composition D Ingredients% in g POLY [DIMETHYLIMINIO DICHLORIDE -1,3- 0,25% PROPANEDIYL (SUN ETHYLIMINI0) -1,6-HEXANEDIYL] POLY DI-METHYL DI-ALLYL AMMONIUM CHLORIDE IN WATER AT 40% UNSTABILIZED 0.5% ACID DIETHYLENE TRIAMINE PENTACETIC, PENTASODIUM SALT IN AQUEOUS SOLUTION 40% 0.15% PEROXIDE HYDROGEN 50% SOLUTION (200 VOLU OXYGEN WATER) 12% TETRA-SODIUM PYROPHOSPHATE, 10 H2O 0.03% DISODIUM TIN HEXAHYDROXIDE 0.04% VASELINE OIL 20% CETYLSTEARYLIC ALCOHOL (C16 / C18 30/70) 6% VITAMIN E: DL-ALPHA-TOCOPHEROL 0.1% STEARYL ALCOHOL OXYETHYLENE (20%) 5% AMIDE COLZA ACIDS OXYETHYLENE (40E) PROTECTS 1,3% GLYCEROL 0,5% PHOSPHORIC ACID (PH) QSP pH DESIONIZED WATER (QS) Qsp 100% At the time of use, the mixture is mixed as follows: Mixture 1: 10 g of the composition (B1) and 10 g of the composition (D). Base / coupler molar ratio = 0 Mixture 2: 10 g of the composition (B2) and 10 g of the composition (D).

Molar ratio Base / coupler = 0.5. In parallel, 90% white natural locks of hair are treated with the coloring mixtures described above, without prior treatment with the composition (B). 4 / Results Obtained The color of the locks was evaluated in the CIE L * system. a * b *, using a MINOLTA CM2600D spectrocolorimeter (Illuminant D656, 10 ° angle, specular component included), in the CIELab system. The value of 4E corresponding to the rise gain of the color is calculated from the values of L * a * b * measured. 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.

The variation of the coloration or gain of the rise in color is the difference in color between the locks of natural white hair (BN) treated with the process of the invention, and the locks treated with the comparative method not implementing of metal catalysts, is measured by (4E) according to the following equation: AE =, \ 1 (L * -L0 *) 2 + (a * - ao *) 2 + (b * - bo *) 2 In this equation , L *, a * and b * represent the values measured on colored hair BN according to the invention and Lo *, ao * and bo * represent the values measured according to the comparative. The higher the value of 4E, the higher the color rise gain.

Results: Hair type L * ab * Gain on BN BN treated with mixture 1 (comparative: without treatment with metallic catalyst) 50.55 4.78 14.72 33.3 BN treated with pretreatment (A) then the mixture 1 (invention) 19.91 1.74 1.92 BN treated with mixture 2 (comparative: without treatment with metal catalyst) 26.53 11.85 10.6 BN treated with pretreatment (A) then mixture 2 ( 22,89 5,66 5,4 8,5 As shown in the table above, the presence of metal catalyst in the staining process significantly improves the power (L * significantly lower for the process according to the invention). the invention as the comparative) and the rise gain of the color. It should be noted that the molar ratio oxidation base / coupler <0.8 makes it possible to obtain very good coloring, and even in the absence of oxidation base (molar ratio oxidation base / coupler = 0) the rise and intensity of the color obtained with the coloring process are very satisfactory.

Claims (21)

REVENDICATIONS1. Process for the oxidation dyeing of keratinous fibers, in particular human keratinous fibers such as the hair, using: one or more metal catalysts and a composition (C) comprising: i. optionally at least one oxidation base ii. at least one oxidation coupler, iii. at least one chemical oxidizing agent, the molar ratio (base) of oxidation on coupler (s) being less than 0.8 when one or more bases are present in the composition (C). 2. Method according to the preceding claim which implements: a) a step of treating said fibers by applying to said fibers a cosmetic composition (A) comprising: i) at least one fatty substance, preferably in a quantity greater than or equal to at 10%, particularly greater than or equal to 25% more preferably in an amount greater than or equal to 35% by weight relative to the total weight of the composition (A); and ii) at least one metal catalyst; b) optionally a washing, rinsing, drying and / or spinning step; c) a step of staining by application to said fibers of a cosmetic composition (C) comprising: i) optionally at least one oxidation base preferably chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, the heterocyclic bases preferably comprising at least two nitrogen atoms and their addition salts; ii) at least one coupler; iii) at least one chemical oxidizing agent; and it being understood that: the composition (A) and / or (C) comprises at least one alkaline, organic or mineral agent; the molar ratio of the amount of oxidation base (s) to the amount of coupler (s) is less than or equal to 8; steps a), b) and c) can be carried out successively a), then b) then c), or else c), then b) then a), or else a) and c) can be carried out together followed by b); the composition (A) and / or the composition (C) contain i) at least one fatty substance, preferably in an amount greater than or equal to 10%, particularly greater than or equal to 25%, more preferably in an amount greater than or equal to 35% by weight relative to the total weight of the composition (A) or (C), preferably the composition (A) comprises at least one fatty substance. 3. Method according to the preceding claim wherein the composition comprising the metal catalyst (s) and / or the composition (C) comprise at least one fatty substance which are 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 fatty alcohol esters, silicones or mixtures thereof. 4. Method according to the preceding claim wherein the one or more fatty substances is an oil, i.e. a liquid compound at a temperature of 25 ° C and at atmospheric pressure; preferably, the fatty substance is chosen from mineral oils such as vaseline oil, Cs-Gis alkanes, polydecenes, liquid fatty acid esters and / or fatty alcohol esters, liquid fatty alcohols or their mixtures, more particularly the fatty substance is chosen from mineral oils such as liquid petrolatum and fatty alcohols such as octyldodecanol. 5. A process according to any one of the preceding claims wherein the coloring composition (C) comprises at least one fatty substance as defined in any of claims 2, 3 or 4. 6. Process according to any one of the preceding claims, in which the composition which comprises at least one metal catalyst or the composition (A) has a fat content preferably ranging from 30 to 80% by weight, and even more particularly ranging from from 35 to 75% by weight, better still from 40 to 70% by weight, and most particularly from 50 to 60% by weight relative to the total weight of the composition (A). 7. A process according to any one of the preceding claims wherein the composition (C) has a fat content preferably ranging from 10 to 90% by weight, and even more preferably from 20 to 80% by weight, more preferably 30 to 50% by weight, and most preferably 40% by weight relative to the total weight of the composition (C). 35 8. Process according to any one of the preceding claims, in which the metal catalyst or catalysts are chosen from metal salts, metal oxides and metal complexes, and mixtures thereof, in particular the complex or complexes are chosen from transition metal salts, salts and salts thereof. rare earth metals and their mixtures. 9. Process according to any one of the preceding claims, in which the metal catalyst (s) is (are) chosen from among the inorganic metal salts chosen from halides, carbonates, sulphates and phosphates, especially hydrated or non-hydrated halides. 10. Process according to any one of the preceding claims, in which the metal catalyst or catalysts are chosen from metal salts having a metal of oxidation state II and two ligands derived from (poly) hydroxy acid, particularly metal salts are complexed by two. carboxylate groups such as that of formula (I): RC (O) -O-M-O-C (O) -R '(I) as well as its solvates such as hydrates and their enantiomers Formula (I) in which: -M represents a metal (II) or metal2 + of oxidation state 2, preferably manganese, -R and R ', which may be identical or different, represent a (C1-C6) (poly) hydroxyalkyl group. 20 11. Process according to any one of the preceding claims, in which the metal catalyst (s) are metal salts of organic acid chosen from citrates, lactates, glycolates, gluconates, acetates, propionates, fumarates and oxalates. and tartrates, especially gluconates. 25 12. Method according to any one of claims 2 to 11 which implements successive steps a), then b) and then c). 13. A process according to any one of claims 2 to 12 which carries out a step b) of rinsing and wringing preferably with a tissue or an absorbent paper. 14. A process according to any one of the preceding claims wherein the composition (C) comprises i) at least one oxidation base selected from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases preferably comprising at least two nitrogen atoms and their addition salts, preferably the oxidation base (s) are chosen from heterocyclic bases and in particular pyrazole derivatives, more preferably pyrazolo derivatives [1,2- a] pyrazol-1-one in particular substituted with an amino group at 2 and 3 such as 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and or one of its salts. 15. Process according to any one of claims 1 to 13 which does not use an oxidation base. 16. Process according to any one of the preceding claims, in which the composition (C) comprises i) at least one coupler chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts; especially chosen from 1,3-dihydroxy benzene, 1,3-dihydroxy-2-methyl benzene, 4-chloro-1,3-dihydroxy benzene, 2,4-diamino-1- (11-hydroxyethyloxy) benzene, 2 4- (11-hydroxyethylamino) -1-methoxybenzene amino, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-11-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole , 2-amino-3-hydroxy pyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1-N- (11-hydroxyethyl) amino-3,4-methylene dioxybenzene, 6-bis (11-hydroxyethylamino) toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazole-5-one, 1-phenyl-3-methylpyrazole -one, 2,6-dimethyl pyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] 1,2,4-triazole, 6 methyl pyrazolo [1.5-4 benzimidazole, their addition salts with an acid, and mixtures thereof, preferably the coupler or couplers are chosen from meta-phenylenediamines such as 2,4-diamino-1- (11-hydroxyethyloxy) benzene ,. 17. A process according to any preceding claim wherein the composition (C) comprises at least i) at least one chemical oxidizing agent selected 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 chemical oxidizing agent is hydrogen peroxide. 18. Process according to any one of the preceding claims, in which the composition which comprises at least one metal catalyst or the composition (A) and / or (C) comprises at least one alkaline agent, organic or inorganic, preferably organic, and 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, especially monoethanolamine; 19. Method according to any one of claims 2 to 18 which implements: in a first step a composition (A) as defined in one of claims 2 to 11; and optionally iii) at least one alkaline agent as defined in claim 1 or 18, in particular chosen from alkanolamines such as triethanolamine; - Then in a second time an intermediate rinse, and spinning preferably with tissue or paper absorbent, - then in a third time is applied a ready-to-use cosmetic composition (C) comprising i) optionally at least one base of oxidation as defined in claims 1 or 14; ii) at least one coupler as defined in claims 1 or 15; and iii) at least one chemical oxidizing agent as defined in claims 1 or 17; and iv) at least one alkaline agent as defined in claims 1 or 18, preferably organic, in particular alkanolamines such as monoethanolamine. 20. A ready-to-use cosmetic composition (F) comprising: i) at least one fatty substance as defined in any one of claims 2 to 4, in an amount greater than 25% by weight relative to the total weight of the composition (F), preferably in an amount of greater than or equal to 35% by weight; and ii) at least one metal catalyst as defined in any one of claims 1 and 8 to 11; iii) optionally at least one oxidation base as defined in any one of claims 1, 14 or 15; iv) at least one coupler as defined in any one of claims 1 or 16 v) at least one chemical oxidizing agent as defined in claims 1 or 17 and it being understood that: - the composition (F) comprises at least one agent alkali, organic or inorganic and - the molar ratio of the amount of oxidation base (s) to the amount of coupler (s) is less than 0.8. 21. A multi-compartment device comprising a first compartment containing a composition (A) as defined in any one of claims 2 to 4, 6, 8 to 11, a second compartment containing a composition (B) closing i) optionally at least one oxidation base as defined in claims 1, or 14, ii) at least one oxidation coupler as defined in claims 1 or 15, or 16; and a third compartment containing a composition (D) comprising one or more chemical oxidizing agents as defined in claims 1 or 17.10