FR2954113A1 - AGENT FOR COLORING AND / OR DECOLOURING KERATINIC FIBERS INTO TWO OR MORE PARTS, IN THE FORM OF EMULSION. - Google Patents

Abstract

The present invention relates to a dyeing and / or bleaching agent for keratin fibers, comprising: a water-in-oil inverse emulsion (A), comprising: -30 to 70% by weight relative to the weight of the inverse emulsion (A) one or more oils containing no carboxylic acid function, water, - one or more surfactants having an HLB value of greater than or equal to 8, one or more basifying agents, - oil-in-water emulsion (B) comprising: -water, -one or more oils containing no carboxylic acid function, -one or more oxidizing agents, the total amount of said oils contained in the mixture of emulsions ( A) and (B) representing at least 20% by weight relative to the total weight of said mixture. The present invention also relates to a method for dyeing and / or bleaching keratinous fibers using such an agent, as well as a kit containing it.

Description

B09-4709FR GD / VC OA 09 615 Société Anonyme known as L'OREAL Agent for coloring and / or bleaching of keratinous fibers into two or more parts, in the form of an emulsion. Invention of: Agent for staining and / or bleaching keratin fibers into two or more parts in the form of an emulsion.

The present invention relates to an agent in two or more parts, intended for the coloration and / or the bleaching of keratinous fibers, in particular human keratinous fibers such as the hair. The subject of the present invention is also a process for dyeing and / or bleaching keratin fibers, using the agent according to the invention. The present invention finally relates to a multi-compartment device containing the coloring and / or bleaching agent according to the invention. For a long time, many people seek to change the color of their hair, including discoloration, or on the contrary to color for example to hide their white hair. To color human keratin fibers, essentially two types of colorations have been developed.

The first type of coloration is so-called permanent or oxidation coloration, which uses dye compositions containing oxidation dye precursors, generally known as oxidation bases. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers. The variety of molecules involved in the oxidation bases and couplers allows a rich palette of colors to be obtained. The second type of staining is so-called semipermanent staining or direct staining, which consists in applying to the keratin fibers direct dyes, which are colored and coloring molecules having an affinity for said fibers, to be paused and then rinsed. In order to perform these stains, the direct dyes generally employed are chosen from nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane direct dyes. This type of process does not require the use of an oxidizing agent to develop the coloring. However, it is possible to implement such an agent, in order to obtain a brightening effect with the coloring. We then speak of a direct or semi-permanent coloration in lightening conditions. The permanent or semipermanent coloring processes in lightening conditions therefore consist in using, with the dyeing composition, an aqueous composition comprising at least one oxidizing agent, under alkaline pH conditions in the vast majority of cases. This oxidizing agent has the role of degrading the melanin of the hair, which, depending on the nature of the oxidizing agent present, leads to a more or less pronounced lightening of the fibers. Thus, for relatively low lightening, the oxidizing agent is generally hydrogen peroxide. When greater lightening is desired, it is customary to use peroxygenated salts, such as, for example, persulfates, in the presence of hydrogen peroxide.

In order to improve the performance of the processes for staining and / or decolouring human keratin fibers, and to limit the inconveniences associated with the use of alkaline agents and oxidizing agents, it has been proposed to use in the compositions dyeing a substantial amount of one or more fats.

However, the incorporation into these compositions of a sufficient amount of fat is problematic, especially when the dye composition is formulated in the form of a conventional oil-in-water emulsion. Indeed, these formulations are thermodynamically unstable, and their viscosity changes over time, especially if the amount of fat is important. The Applicant has now discovered that the fact of using an alkaline composition in the form of a water-in-oil inverse emulsion, in the presence of certain surfactants, made it possible to incorporate a large quantity of oily compounds into the compositions applied to the fibers, while preserving the stability of these compositions. In addition, it has been observed that the possible addition of an oil thickener to the system made it possible to stabilize said system in the form of an inverse emulsion. The formulation of the coloring composition in inverse emulsion makes it possible to better protect the dyes, generally water-soluble, therefore present in the droplets of the aqueous phase. As a result, said dyes do not undergo oxidation by oxygen in the air. This formulation thus leads to obtaining more intense and more chromatic colorations. The subject of the invention is therefore a dyeing and / or bleaching agent for keratin fibers, comprising: a water-in-oil inverse emulsion (A) comprising: 30 to 70% by weight relative to the weight of the emulsion ( A) one or more oils containing no carboxylic acid function, - water - one or more surfactants having an HLB value of greater than or equal to 8, one or more alkalinizing agents, - a direct emulsion oil in water (B) comprising: - water, - one or more oils containing no carboxylic acid function, - one or more oxidizing agents, the total amount of said oils contained in the mixture of the inverse emulsion (A ) and the direct emulsion (B) representing at least 20% by weight relative to the total weight of said mixture.

When the agent according to the invention is intended for dyeing keratinous fibers, the inverse emulsion (A) further comprises one or more oxidation dyes and / or one or more direct dyes. Conversely, when the agent according to the invention is intended for the sole bleaching of the keratinous fibers, the emulsions (A) and (B) do not comprise a direct dye or an oxidation dye precursor (bases and couplers) or, if present, their total content does not exceed 0.005% by weight relative to the weight of each composition. Indeed, at such a content, only the composition would be tinted, that is to say, one would not observe staining effect of keratin fibers. The coloring and / or bleaching agent according to the present invention does not change or little over time when mixing the inverse emulsion (A) and the direct emulsion (B), or the application sequence of these two emulsions on keratinous fibers. I1 thus has a very good efficiency, especially in terms of quality and homogeneity of the coloration and / or discoloration. In addition, when it is intended for the coloration, the agent according to the invention is particularly effective in terms of the power of the coloration obtained, as well as that of the chromaticity, and the selectivity of the coloration of the same fiber, or between differently sensitized fibers. When it is intended for discoloration, the agent according to the invention has lightening performance equivalent to or even greater than those obtained with the existing compositions, in particular with those based on ammonium hydroxide. The agent according to the invention also has the advantage of limiting the release of aggressive odor during its preparation, or its application to the fibers.

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 human keratinous fibers treated by the process according to the invention are preferably the hair. By emulsion in the sense of the present invention is meant true emulsions, to distinguish microemulsions, which are thermodynamically stable systems unlike true emulsions. The size of the droplets of the dispersed phase of the emulsions of the invention is preferably between 10 nm and 100 μm and preferably between 200 nm and 50 μm.

This is the average diameter D (3.2) measurable, in particular using a laser granulometer. The inverse emulsion (A) and the direct emulsion (B) can be prepared by conventional emulsion preparation methods, well known to those skilled in the art.

The inverse emulsion (A) is in the form of a water-in-oil emulsion, wherein the aqueous phase is dispersed in a fatty phase. Preferably, the inverse emulsion (A) comprises from 40 to 70%, better still from 45 to 65% relative to the weight of the inverse emulsion (A) of one or more oils containing no carboxylic acid function. In an alternative, the amount of water varies from 5 to 70%, better from 10 to 50% of the total weight of the emulsion (A). In another variant, the aqueous phase comprising water and optionally compounds which are soluble in water at room temperature and at atmospheric pressure can range from 10 to 70%, better still from 15 to 50%, of the total weight of the emulsion. (AT). According to the present invention, the inverse emulsion (A) comprises one or more basifying agents.

The basifying agent may in particular be a mineral or organic base. Preferably, the basifying agent is chosen from ammonia, alkali carbonates, alkanolamines and their derivatives, sodium or potassium hydroxides, and the compounds of formula (I) below:

Wherein W is a C1-C6 alkylene radical optionally substituted by a hydroxyl group or a C1-C6 alkyl radical; Rx, Ry, Rz and Rt, identical or different, represent a hydrogen atom, a C1-C6 alkyl or C1-C6 hydroxyalkyl, C1-C6 aminoalkyl radical.

Examples of such compounds of formula (I) include 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine. Particularly preferred alkalinizing agents are alkanolamines, and in particular mono-, di- and triethanolamines.

In a preferred variant of the invention, the basifying agent is monoethanolamine. According to a particular embodiment, the inverse emulsion (A) contains as alkalinizing agents at least one organic amine, preferably at least one alkanolamine. When the emulsion contains several alkaline agents including an alkanolamine and ammonia or a salt thereof, the organic amine or amines are preferably majority by weight relative to the amount of ammonia. According to a particular embodiment of the present invention, the inverse emulsion (A) does not contain ammonia.

According to one embodiment of the present invention, when the inverse emulsion (A) contains ammonia, it also contains one or more alkanolamines, and the weight amount of alkanolamine (s) in the inverse emulsion (A) is greater than the amount of ammonia in this same emulsion.

Generally, the inverse emulsion (A) has a content of basifying agents (s) ranging from 0.1 to 40% by weight, preferably from 0.5 to 20% by weight, relative to the weight of this emulsion. Preferably, the inverse emulsion (A) and / or the aqueous phase of the inverse emulsion (A) has a pH greater than or equal to 8, and more preferably a pH ranging from 8.5 to 11.5. This pH can also be adjusted to the desired value by the use, in addition to the basifying agent, of one or more acidifying agents.

Among the acidifying agents, mention may be made, for example, of mineral or organic acids such as hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids such as acetic acid, tartaric acid citric acid, lactic acid, sulphonic acids.

The inverse emulsion (A) according to the present invention further comprises one or more surfactants having a HLB greater than or equal to 8. The term HLB (Hydrophilic Lipophilic Balance) is well known to those skilled in the art. and denotes the hydrophilic-lipophilic balance of a surfactant. The HLB or hydrophilic-lipophilic balance of the surfactant (s) used according to the invention is the HLB according to GRIFFIN defined in J. Soc. Cosm. Chem. 1954 (Volume 5), pages 249-256. Non-limiting examples of HLB surfactants greater than or equal to 8 are in particular given in Mc Cutcheon's Emulsifiers & Detergents, 1998 International Edition, MC Publishing Company, chapter HLB Index. The surfactant or surfactants that can be used in the inverse emulsion (A) are preferably chosen from nonionic surfactants and anionic surfactants, and preferably from nonionic surfactants. The anionic surfactants are more especially chosen from salts, in particular alkali metal salts, in particular sodium salts, ammonium salts, amine salts such as the salts of amino alcohols or salts of alkaline earth metals, such as magnesium, following compounds: alkyl sulphates, alkyl ether sulphates, alkyl amido ether sulphates, alkyl aryl polyether sulphates, monoglyceride sulphates; alkylsulphonates, alkylamidesulfonates, alkylarylsulphonates, α-olefin-sulphonates, paraffin-sulphonates; alkylphosphates, alkyl ether phosphates; alkylsulfosuccinates, alkylethersulfosuccinates, alkylamide-sulfosuccinates; alkylsulfosuccinamates; alkylsulfoacetates; acylsarcosinates; acylisethionates and N-acyltaurates; salts of fatty acids such as oleic, ricinoleic, palmitic or stearic acids, coconut oil acid or hydrogenated coconut oil acid; salts of alkyl D galactoside uronic acids; acyl lactylates; salts of polyoxyalkylenated alkyl ether carboxylic acids, polyoxyalkylenated alkylarylether carboxylic acids, polyoxyalkylenated alkylamidoether carboxylic acids, in particular those containing from 2 to 50 ethylene oxide groups; - and their mixtures. It should be noted that the alkyl or acyl radical of these various compounds advantageously comprises from 6 to 24 carbon atoms, and preferably from 8 to 24 carbon atoms, and the aryl radical preferably denotes a phenyl or benzyl group. The nonionic surfactants are preferably chosen from oxyalkylenated or glycerolated surfactants which are preferably oxyalkylenated.

By oxyalkylenated nonionic surfactants is meant according to the invention nonionic surfactants which carry in their molecule one or more groups chosen from the following groups - CH2-CH2-O-, -CH2-CH2-CH2-O-, -CH2-CH (CH3) -O- or mixtures thereof.

The oxyalkylenated nonionic surfactants, whose HLB is greater than or equal to 8, may belong in a non-limiting manner to the following families: oxyethylenated alkylphenols, EO / PO condensates, oxyethylenated vegetable oils, oxyethylenated fatty alcohols, fatty acids and polyethylene glycols, esters of polyoxyethylenated fatty acids and sorbitol.

As commercial compounds, mention may be made of: Intrasol FA28 / 50/4 (HLB = 8.1) (STOCKHAUSEN) Serdox NOG 200 S (HLB = 8.5) (SERVO) Berol 26 (HLB = 8.9) ( BEROL NOBEL) Genapol 0-050 (HLB = 9) (HOECHST) Prox-onic LA-1/04 (HLB = 9.2) (PROTEX) Eumulgin 05 (HLB = 9.5) (HENKEL) Etocase 20 (HLB = 9.6) (CROAD) Antarox CO 520 (HLB = 10) (RHONE POULENC) Imbentin POA / 060 (HLB = 10) (KOLB) TO-55-EL (HLB = 10) (HEFTI) Atlas G-1086 (HLB) = 10.2) (ICI) Atlox 4878B (HLB = 10.5) (ICI) Berol 059 (HLB = 10.5) (BEROL NOBEL) Kessco PEG 600 Dilaurate (HLB = 10.5) (AKZO) Mergital LT6 ( HLB = 10.6) (HENKEL) Polychol 10 (HLB = 10.7) (CRODA) Prox-onic HR-025 (HLB = 10.8) (PROTEX) Tebenal NP6 (HLB = 10.9) (BOHME) Cremophor A6 (HLB = 11) (BASF) Genapol 0-080 (HLB = 11) (HOECHST) Genapol T-080 (HLB = 11) (HOECHST) Kotilen O / 3 (HLB = 11) (KOLB) Lutensol AP 7 ( HLB = 11) (BASF) Tween 85 (HLB = 11) (ICI) Tebecid S8 (HLB = 11.2) (BOHME) Berol 047 (HLB = 11.4) (BEROL NOBEL) Soprophor 860P (HLB = 11, 4) (RHONE POULENC) Dobanol 45-7 (HLB = 11.6) (SHELL) Prox-onic HR-030 (HLB = 11.7) ( PROTEX) Ethonic 1214-6.5 (HLB = 11.8) (ETHYL) Prox-onic OA-1/09 (HLB = 11.9) (PROTEX) Cremophor S9 (HLB = 12) (BASF) Imbentin AG / 128 / 080 (HLB = 12) (KOLB) Serdox NOG 440 (HLB = 12) (SERVO) Softanol 70 (HLB = 12.1) (BP CHEMICALS) Renex 707 (HLB = 12.2) (ICI) Simulsol 830 NP ( HLB = 12.3) (SEPPIC) Brij 76 (HLB = 12.4) (HCl) Tebenal T10 (HLB = 12.4) (BOHME) Volpo S-10 (HLB = 12.4) (CRDA) Eumulgin O10 ( HLB = 12.5) (HENKEL) Berol 199 (HLB = 12.6) (BEROL NOBEL) Triton N-87 (HLB 12.6) (ROHM AND HAAS) Polychol 15 (HLB = 12.7) (CRODA) Brij 56 (HLB = 12.9) (ICI) Simulsol 56 (HLB = 12.9) (SEPPIC) Cremophor A1 (HLB = 13) (BASF) Eumulgin 286 (HLB = 13) (HENKEL) Genapol T-110 (HLB = 13) (HOECHST) Sandoxylate FOL12 (HLB = 13) (SANDOZ) Bio soft HR 40 (HLB = 13.1) (STEPAN) Berol 046 (HLB = 13.5) (BEROL NOBEL) Eumulgin B1 (HLB = 13.5) ) (HENKEL) Dobanol 45-11 (HLB = 13.7) (SHELL) Aqualose W20 (HLB = 14) (WESTBROCK LANOLIN) Ethylan DP (HLB = 14) (HARCROS) Mergital OC12 (HLB = 14) (HENKEL) Simulsol 1230 NP (HLB = 14) (SEPPIC) Tagat R1 (HLB = 14) (GOLDSCHMIDT) Taga T H 2 (HLB = 14.2) (GOLDSCHMIDT) Tebecid RM20 (HLB = 14.4) (BOHME) Imbentin AG / 168/150 (HLB = 14.5) (KOLB) Prox-onic LA-1/012 ( HLB = 14.5) (PROTEX) Etoch 60 (HLB = 14.7) (CRODA) Radiasurf 7157 (HLB = 14.9) (OLEOFINA) Genapol T-180 (HLB = 15) (HOECHST) Montanox 80 (HLB = 15) (SEPPIC) Serdox NJAD (HLB = 15) (SERVO) Tagat R60 (HLB = 15) (GOLDSCHMIDT) Berol 278 (HLB = 15.2) (BEROL NOBEL) Brij 78 (HLB = 15.3) (HCl Simulsol 98 (HLB = 15.3) (SEPPIC) Montanox 40 (HLB 15.6) (SEPPIC) Brij 58 (HLB = 15.7) (ICI) Aqualose L75 (HLB = 16) (WESTBROCK LANOLIN) Atlas G- 1471 (HLB = 16) (HERE) Berol 281 (HLB = 16) (BEROL NOBEL) Berol 292 (HLB = 16) (BEROL NOBEL) Nafolox 20-22 300E (HLB = 16) (CONDEA) Genapol C-200 (HLB = 16) (HOECHST) Myrj 51 (HLB = 16) (ICI) Simulsol PS 20 (HLB = 16) (SEPPIC) Tergitol 15 S 20 (HLB 16.3) (CARBIDE UNION) Synperonic PE P75 (HLB = 16.5 ) (ICI) Montanox 20 (HLB = 16.7) (SEPPIC) Myrjj 52 (HLB = 16.9) (ICI) Simulsol 3030 NP (HLB = 17) (SEPPIC) Imbentin AG / 168/400 (HLB = 17, 5) (KOLB) Rhodia Surf NP40 (HLB = 17.7) (RHONE POULENC) In cropol CS-50 (HLB = 17.9) (CRODA) OEG 90/50 Servirox (HLB = 18) (SERVO) Prox-onic HR-0200 (HLB = 18.1) (PROTEX) Berol 243 (HLB = 18, 2) (BEROL NOBEL) Imbentin N / 600 (HLB = 18.5) (KOLB) Antarox CO 980 (HLB = 18.7) (RHONE POULENC) Antarox CO 987 (HLB = 18.7) (RHONE POULENC) Berol 08 (HLB = 18.7) (BEROL NOBEL) Brij 700 (HLB = 18.8) (ICI) Prox-onic NP-0100 (HLB = 19) (PROTEX) Rs-55-100 (HLB = 19) (HEFTI) Imbentin AG / 168S / 950 (HLB = 20) (KOLB) Synperonic PE F87 (HLB = 24) (ICI) Alkasurf BA-PE80 (HLB = 26.1) (RHONE POULENC) Synperonic PE F38 (HLB = 30.5) (ICI) Of these, the oxyethylenated fatty alcohols, whose HLB is greater than or equal to 8 are preferred. The concentration of these surfactants of HLB greater than or equal to 8 is preferably between 1 and 20%, more preferably from 1 to 15% by weight, and more preferably from 2 to 10% by weight, relative to the total weight of the HLB. inverse emulsion (A).

The inverse emulsion (A) according to the invention comprises one or more oils containing no carboxylic acid function contained in the continuous phase of the inverse emulsion and the direct emulsion (B) according to the invention comprises one or more oils. containing no carboxylic acid function contained in the dispersed phase of the direct emulsion. The term "oils" means an organic compound which is insoluble in water at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa) (solubility in water of less than 5% by weight and of preferably 1% even more preferably 0.1%).

These compounds 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 oils are soluble in organic solvents under the same conditions of temperature and pressure, such as for example chloroform, ethanol or benzene. In addition, the oils are liquid at ordinary temperature (25 ° C.) and at atmospheric pressure (760 mmHg, ie 1.013 × 10 5 Pa). The term "oil containing no carboxylic acid function" denotes an oil which does not contain a "COOH" or "COO" group. According to a preferred embodiment of the invention, the oil or oils which do not contain a carboxylic acid function used in the emulsion (A). ) and in the emulsion (B), which are identical or different, and may be chosen in particular from hydrocarbons, non-silicone oils of animal, vegetable, mineral or synthetic origin, fatty alcohols, fatty acid esters and / or or fatty alcohol, silicones, and mixtures thereof. It is specified that within the meaning of the invention, the fatty alcohols and fatty acids, present in particular in the esters, more particularly have one or more hydrocarbon groups, linear or branched, saturated or unsaturated, comprising 6 to 30 carbon atoms, optionally substituted, in particular with 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.

More particularly, the liquid hydrocarbons are chosen from: linear or branched C6-C16 lower alkanes, which may be cyclic. By way of example, mention may be made of hexane, undecane, dodecane and tridecane, isoparaffins such as isohexadecane, isododecane and isodecane. linear or branched hydrocarbons of animal or synthetic mineral origin of more than 16 carbon atoms, such as liquid paraffins, liquid petroleum jelly, polydecenes, hydrogenated polyisobutenes such as Parleam®, squalane.

In a preferred variant, the liquid hydrocarbon or hydrocarbons are chosen from paraffin oils and vaseline oil. Preferably, the silicone is chosen from liquid polydialkylsiloxanes, in particular liquid polydimethylsiloxanes (PDMS), and liquid polyorganosiloxanes comprising at least one aryl group. These silicones can also be organomodified. The organomodified silicones that may be used are liquid silicones, as defined above, and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group. 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 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, the dodecamethylcyclopentasiloxane marketed under the name of SILSOFT 1217 by MOMENTIVE PERFORMANCE MATERIALS and their mixtures. Mention may also be made of cyclocopolymers of the dimethylsiloxane / methylalkylsiloxane type, such as the VOLATILE® SILICONE FZ 3109 sold by UNION CARBIDE, of the formula: ## STR1 ## also mention mixtures of cyclic polydialkylsiloxanes with organic compounds derived from silicon, such as the mixture of octamethylcyclotetrasiloxane and CH3 1 CH3 with D ': C8Hn ùSiùO tetratrimethylsilylpentaérythritol (50/50) and the mixture of octaméthylcyclotétrasiloxane and oxy -1,1 '- (hexa-2,2,2', 2 ', 3,3'-trimethylsilyloxy) bis-neopentane, the linear volatile polydialkylsiloxanes having 2 to 9 silicon atoms and having a viscosity of less than or equal to This is, for example, decamethyltetrasiloxane sold in particular under the name "SH 200" by Toray Silicone, silicones in this class are also described in US Pat. article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, p. 27-32 - TODD & BYERS "Volatile Silicone fluids for cosmetics". The viscosity of the silicones is measured at 25 ° C. according to ASTM 445 Appendix C. Non-volatile polydialkylsiloxanes can also be used. These non-volatile silicones are more particularly chosen from polydialkylsiloxanes, among which may be mentioned mainly polydimethylsiloxanes with trimethylsilyl end groups. Among these polydialkylsiloxanes, mention may be made, without limitation, of the following commercial products: SILBIONE® oils of the 47 and 70 047 series or the MIRASIL® oils marketed by RHODIA, such as, for example, the 70 047 V 500 000 oil; the oils of the MIRASIL® series marketed by RHODIA; the oils of the 200 series of Dow Corning, such as DC200 having a viscosity of 60,000 mm 2 / s; - VISCASIL® oils from GENERAL ELECTRIC and some oils from SF series (SF 96, SF 18) from GENERAL ELECTRIC. Mention may also be made of polydimethylsiloxanes with dimethylsilanol end groups known under the name of dimethiconol (CTFA), such as the oils of the 48 series from the company RHODIA. Among the silicones containing aryl groups, there are polydiarylsiloxanes, in particular polydiphenylsiloxanes, and polyalkylarylsiloxanes. By way of example, mention may be made of the products sold under the following names: SILBIONE® oils of the 70 641 series from RHODIA; . RHODORSIL® 70 633 and 763 RHODIA series of oils; . DOW CORNING 556 COSMETIC GRAD FLUID oil from DOW CORNING; . silicones of the PK series from BAYER, such as the product PK20; certain oils of the SF series of GENERAL ELECTRIC such as SF 1023, SF 1154, SF 1250, SF 1265. The liquid fatty esters are preferably the liquid esters of saturated or unsaturated, linear or branched C 1 -C 26 aliphatic mono or polyacids and saturated or unsaturated, linear or branched C 1 -C 26 aliphatic mono or polyalcohols, the total number of carbon atoms of the esters being greater than or equal to 10. Preferably, for the monoalcohol esters, at least one of the alcohol or the acid from which the esters of the invention are derived is branched. Among monoesters of monoacids and monoalcohols, mention may be made of ethyl and isopropyl palmitates and of alkyl myristates such as isopropyl myristate, ethyl, isocetyl stearate and ethyl isononanoate. -2-hexyl, isodecyl neopentanoate, isostearyl neopentanoate. It is also possible to use esters of C 4 -C 22 di or tricarboxylic acids and of C 1 -C 22 alcohols and esters of monocarboxylic or tricarboxylic acids and of non-sugar alcohols di, tri, tetra or pentahydroxy with C 4 -C 4. C26. These include: diethyl sebacate; diisopropyl sebacate; di (2-ethylhexyl) sebacate; diisopropyl adipate; di-propyl adipate; dioctyl adipate, di (2-ethylhexyl) adipate; diisostearyl adipate; di (2-ethylhexyl) maleate; triisopropyl citrate; triisocetyl citrate; trisostearyl citrate trilactate glyceryl; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; neopentyl glycol diheptanoate; Diethylene glycol diisononate. The emulsions (A) or (B) may also comprise, as liquid fatty ester, esters and diesters of C 6 -C 30, preferably C 12 -C 22, fatty acid sugars. It is recalled that "sugar" means 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 alkylated, such as methylated derivatives such as methylglucose.

The esters of sugars and fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described above and of C 6 -C 30, preferably C 12 -C 22 fatty acids, linear or branched, saturated or unsaturated. If unsaturated, these compounds may comprise one to three carbon-carbon double bonds, conjugated or otherwise. The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters and mixtures thereof. These esters may be for example oleate, laurate, palmitate, myristate, behenate, cocoate, stearate, linoleate, linolenate, caprate, arachidonates, or mixtures thereof, such as in particular the mixed oleo-palmitate, oleostearate and palmito-stearate esters. More particularly, the mono- and di-esters are used, and especially the mono- or dioleate, stearate, behenate, oleopalmitate, linoleate, linolenate, oleostearate, sucrose, glucose or methylglucose. By way of example, mention may be made of the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.

Finally, it is also possible to use the natural or synthetic esters of mono, di or triacids with glycerol. Among these are vegetable oils. As vegetable oils or synthetic triglycerides that can be used in the emulsions that are useful for the agent according to the invention as liquid fatty esters, mention may be made, for example, of triglyceride oils of vegetable or synthetic origin, such as liquid triglycerides of fatty acids having from 6 to 30 carbon atoms, such as the triglycerides of heptanoic or octanoic acids or else, for example, sunflower, corn, soya, squash, grape seed, sesame, hazelnut, apricot, macadamia, arara, sunflower, castor, avocado, caprylic / capric acid triglycerides, such as those sold by Stearineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by Dynamit Nobel, jojoba oil, shea butter oil. Preferably, as esters according to the invention, liquid fatty esters derived from monoalcohols will be used. Myristate or isopropyl palmitate are particularly preferred.

Preferably, the liquid unsaturated fatty alcohols of the invention have from 8 to 30 carbon atoms. Liquid fatty alcohols may be unsaturated. These unsaturated liquid fatty alcohols have in their structure at least one double or triple bond. Preferably, the fatty alcohols of the invention have in their structure one or more double bonds. When several double bonds are present, they are preferably 2 or 3 and may or may not be conjugated. These fatty alcohols can be linear or branched. They may optionally comprise in their structure at least one aromatic cycle or not. Preferably, they are acyclic. More particularly, the liquid unsaturated fatty alcohols of the invention are chosen from oleic (or oleyl) alcohol, linoleic (or linoleyl) alcohol, linolenic (or linolenyl) alcohol and undecylenic alcohol.

Oleyl alcohol is particularly preferred. Liquid fatty alcohols may also be branched saturated fatty alcohols. More particularly, the liquid branched saturated fatty alcohols of the invention are selected from isostearyl alcohol and octyldodecanol. Preferably, the oil or oils containing no carboxylic acid function present in emulsions (A) and (B) do not comprise oxyalkylenated units or glycerolated units. Preferably, the oil or oils containing no carboxylic acid function present in emulsions (A) and (B) are non-silicone. According to a preferred embodiment, the oil or oils containing no carboxylic acid function present in emulsions (A) and (B) are chosen from hydrocarbons, non-silicone oils of animal, vegetable, mineral or synthetic origin. fatty alcohols, fatty acid esters and / or fatty alcohol esters, silicones and mixtures thereof; preferably from liquid petroleum jelly, polydecenes, esters of fatty acids and / or of liquid fatty alcohols, liquid fatty alcohols, and mixtures thereof; and more preferably from vaseline oil, polydecenes, liquid fatty alcohols and mixtures thereof. Even more preferentially, the oil which does not contain a carboxylic acid function is liquid petroleum jelly. The inverse emulsion (A) according to the present invention preferably comprises one or more oil thickeners (s). The thickening agent may be chosen from polymeric thickeners, non-polymeric agents, mineral thickeners, organic thickeners and mixtures thereof.

By thickener is meant a compound that modifies the rheology of the medium in which it is incorporated. The oily medium thickener may be chosen from: - organophilic clays, - hydrophobic pyrogenic silicas - alkylated guar gums (with C1-C6 alkyl group), such as those described in EP-A-708114; oil-forming gelling polymers such as triblock or star polymers resulting from the polymerization or copolymerization of at least one monomer containing an ethylenic group, such as the polymers sold under the name Kraton; polymers having a weight average molecular weight of less than 100,000, comprising a) a polymeric backbone having hydrocarbon-based repeating units provided with at least one heteroatom, and optionally b) at least one pendant fatty chain and / or at least one terminal fatty chain optionally functionalized, having from 6 to 120 carbon atoms and being bonded to these hydrocarbon-based units, as described in applications WO-A-02/056847, WO-A-02/47619, the content of which is incorporated by way of reference ; in particular polyamide resins (especially comprising alkyl groups having from 12 to 22 carbon atoms) such as those described in US-A-5783657 whose contents are incorporated by reference. - The silicone polyamide resins as described in the application EP-A-1266647, in the French patent application filed under No. 0216039 whose content is incorporated by reference. Such thickeners are especially described in applications EP-A-1400234, the contents of which are incorporated by reference. The thickener may be an organic gelling agent, that is to say an agent comprising at least one organic compound. The organogellators may be selected from those described in WO-A-03/105788, the contents of which are incorporated by reference. More specifically, the polymeric thickener present in the emulsion useful for the agent according to the invention is an amorphous polymer formed by polymerization of an olefin. The olefin may in particular be an ethylenically unsaturated elastomeric monomer. As an example of an olefin, mention may be made of ethylenic carbide monomers, especially having one or two ethylenic unsaturations, having from 2 to 5 carbon atoms, such as ethylene, propylene, butadiene and isoprene. The polymeric thickening agent is capable of thickening or gelling the composition. By amorphous polymer is meant a polymer which does not have a crystalline form. The polymeric thickener may also be film-forming. The polymeric thickening agent may in particular be a diblock, triblock, multiblock, radial or star copolymer, or mixtures thereof. Such polymeric thickeners are described in US-A-2002/005562 and in US-A-5,221,534. Advantageously, the polymeric thickening agent is an amorphous block copolymer of styrene and olefin. The polymeric thickening agent is preferably hydrogenated to reduce residual ethylenic unsaturations after polymerization of the monomers. In particular, the polymeric thickening agent is a copolymer, optionally hydrogenated, with styrene blocks and with ethylene / C 3 -C 4 alkylene blocks. As the diblock copolymer, preferably hydrogenated, mention may be made of styrene-ethylene / propylene copolymers and styrene-ethylene / butadiene copolymers. Diblock polymers are in particular sold under the name Kraton® G1701E by Kraton Polymers. As the triblock copolymer, preferably hydrogenated, mention may be made of styrene-ethylene / propylene-styrene copolymers, styrene-ethylene / butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, styrene-butadiene-styrene copolymers . Triblock polymers are sold in particular under the names Kraton® G1650, Kraton® G1652, Kraton® D1101, Kraton® D1102 and Kraton® D1160 by Kraton Polymers. It is also possible to use a mixture of styrene-butylene / ethylene-styrene triblock hydrogenated copolymer and hydrogenated ethylene-propylene-styrene star polymer, such a mixture being in particular in isododecane. Such mixtures are for example sold by PENRECO under the trade names VERSAGEL® M5960 and VERSAGEL® M5670. Advantageously, a diblock copolymer such as those described above, in particular a diblock copolymer of styrene-ethylene / propylene, is used as polymeric thickening agent. More specifically, organophilic clays are clays modified with chemical compounds that make the clay swellable. Clays are already well known products per se, which are described for example in the book "Clay Mineralogy, S.

Caillère, S. Hénin, M. Rautureau, 2nd edition 1982, Masson ", the teaching of which is hereby incorporated by reference.Clays are silicates containing a cation which can be chosen from among the calcium, magnesium, aluminum, sodium, potassium, lithium and their mixtures.

Examples of such products include clays of the smectite family such as montmorillonites, hectorites, bentonites, beidellites, saponites, as well as the family of vermiculites, stevensite, chlorites . These clays can be of natural or synthetic origin. Preferably, the clays are used which are cosmetically compatible and acceptable with the keratin materials. The organophilic clay may be selected from montmorrilonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof, optionally modified. 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. The fumed silicas can be obtained by high temperature hydrolysis of a volatile silicon compound in an oxyhydrogen flame, producing a finely divided silica. This process makes it possible in particular to obtain hydrophilic silicas which have a large number of silanol groups on their surface. Such hydrophilic silicas are, for example, sold under the names "AEROSIL 130®", "AEROSIL 200®", "AEROSIL 255®", "AEROSIL 300®", "AEROSIL 380®" by the company Degussa, "CAB-O- SIL HS-5® "," CAB-O-SIL EH-5® "," CAB-O-SIL LM-130® "," CAB-O-SIL MS-55® "," CAB-O-SIL M -5® "by the company Cabot. It is possible to chemically modify the surface of said silica, by chemical reaction generating a decrease in the number of silanol groups. In particular, it is possible to substitute silanol groups with hydrophobic groups: a hydrophobic silica is then obtained.

The hydrophobic groups may be: trimethylsiloxyl groups, which are especially obtained by treatment of fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called "silica silylate" according to the CTFA (6th edition, 1995). They are for example sold under the references "AEROSIL R812®" by the company Degussa, "CAB-O-SIL TS-530®" by Cabot. - Dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treatment of fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl silylate" according to the CTFA (6th edition, 1995). They are for example sold under the references "AEROSIL R972®", "AEROSIL R974®" by the company Degussa, "CAB-O-SIL TS-610®", "CAB-O-SIL TS-720®" by the company Pooch.

The fumed silica preferably has a particle size that may be nanometric to micrometric, for example ranging from about 5 to 200 nm. The mineral thickener is preferably a hectorite or organomodified bentonite. More particularly, the thickening agent used is a modified distearyl dimethyl ammonium hectorite. Preferably, the mineral thickeners are associated with carbonates, such as, for example, propylene carbonate.

The thickening agent is preferably present in the inverse emulsion (A) in a total content ranging from 0.1 to 10% by weight relative to the total weight of the emulsion, preferably ranging from 0.5 to 7%. by weight, and more preferably ranging from 1 to 5% by weight. The direct emulsion (B) is in the form of an oil-in-water emulsion, i.e., a fat phase dispersed in an aqueous phase. The direct emulsion (B) preferably comprises 5 to 50%, more preferably 10 to 30% by weight relative to the total weight of the direct emulsion (B) of one or more oils containing no acid function. carboxylic acid as previously described.

According to the present invention, the direct emulsion (B) comprises one or more oxidizing agents. This oxidizing agent may be chosen from the oxidizing agents conventionally used for the bleaching and the oxidation dyeing of keratin fibers, and among which mention may be made of hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides. , peroxygenated salts such as persulfates, perborates and percarbonates of alkali or alkaline earth metals such as sodium, potassium, magnesium. One or more oxidation-reduction enzymes such as laccases, peroxidases and 2-electron oxidoreductases (such as uricase) may also be used as the oxidizing agent, optionally in the presence of their respective donor or cofactor.

The use of hydrogen peroxide is particularly preferred. This may advantageously be employed in aqueous solution (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 1 to 15% by weight relative to the total weight of the direct emulsion (B). Depending on the degree of discoloration desired, the oxidizing agent may also comprise one or more compounds chosen preferably from peroxygenated salts.

Preferably, the pH of the aqueous phase of the direct emulsion (B) is less than 7. This pH may be adjusted to the desired value by the use of one or more acidifying agents, which may be chosen especially from those previously described. The mixture of emulsions (A) and (B) contains an amount of oil (s) not containing a carboxylic acid function of at least 20% by weight, preferably between 20.5 and 75% by weight, by relative to the total weight of said mixture. Preferably, the mixture of emulsions (A) and (B) contains an amount of oil (s) not containing a carboxylic acid function of at least 25% by weight, more particularly between 25.5 and 75% by weight. weight, still more preferably at least 30% by weight, more particularly between 30.5 and 75% by weight, relative to the total weight of said mixture. The emulsions (A) and / or (B) according to the invention may also contain one or more additional fatty substances different from oils not containing a carboxylic acid function defined above, such as in particular solid fatty alcohols such as alcohol. cetyl alcohol, stearyl alcohol or mixtures thereof. These additional fatty substances are free of carboxylic acid function.

Advantageously, the inverse emulsion (A) is in the form of a gel or a cream. Advantageously, the direct emulsion (B) is in the form of a solution, an emulsion or a gel.

According to a first embodiment of the invention, the inverse emulsion (A) further comprises one or more oxidation dyes. In this case, the agent according to the invention is advantageously used for the oxidation dyeing of keratinous fibers.

The oxidation dyes that may be used in the present invention are generally chosen from oxidation bases, optionally combined with one or more couplers. The oxidation bases may in particular be chosen from para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Among the para-phenylenediamines, 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 - ((3-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis - ((3-hydroxyethyl) amino 2-chloro aniline, 2- (3-hydroxyethyl paraphenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N - ((3-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine; N, N- (ethyl, (3-hydroxyethyl) paraphenylenediamine, N - ((3, γ-dihydroxypropyl) paraphenylenediamine, N- (4'-aminophenyl) paraphenylenediamine, N-phenyl paraphenylenediamine, 2- (3-hydroxyethyloxy) paraphenylenediamine, 2- (3-acetylaminoethyloxy) paraphenylenediamine, N - ((3-methoxyethyl) paraphenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl paraphenylenediamine, 2-hydroxyethylamino-5-amino toluene, 3-hydroxy-1- (4'-aminophenyl) pyrrolidine and their addition salts with an acid. Of the paraphenylenediamines mentioned above, paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylenediamine, 2-P-hydroxyethyl paraphenylenediamine, 2- (3-hydroxyethyloxy) paraphenylenediamine, 2,6-dimethyl paraphenylenediamine, 6-diethyl paraphenylenediamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) paraphenylenediamine, 2-chloro-para-phenylenediamine, 2- (3-acetylaminoethyloxy) para-phenylenediamine, and their addition salts with a Particularly preferred among the bis-phenylalkylenediamines are N, N'-bis - ((3-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1,3 amino-propanol, N, N'-bis - ((3-hydroxyethyl) N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N N, N'-bis ((3-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis (4-methylaminophenyl) tetramethyl) L-diamine, 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 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, mention may be made, for example, of 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2-aminophenol, and their addition salts. Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino pyridine, 2- (4-methoxyphenyl) amino-3-amino pyridine, 3,4-diamino pyridine, and their addition salts.

Other pyridinic oxidation bases useful in the present invention are the 3-amino pyrazolo [1,5-a] pyridines oxidation bases or their addition salts described for example in the patent application FR 2801308. By way of example, mention may be made of pyrazolo [1,5-a] pyridin-3-ylamine; 2-acetylamino pyrazolo [1,5-a] pyridin-3-ylamine; 2-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 3-aminopyrazolo [1,5-a] pyridin-2-carboxylic acid; 2-methoxy-pyrazolo [1,5-a] pyridin-3-ylamino; (3-amino-pyrazolo [1,5-a] pyridin-7-yl) -methanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-5-yl) -ethanol; 2- (3-Amino-pyrazolo [1,5-a] pyridin-7-yl) -ethanol; (3-Amino-pyrazolo [1,5-a] pyridin-2-yl) -methanol; 3,6-diamino-pyrazolo [1,5-a] pyridine; 3,4-diamino-pyrazolo [1,5-a] pyridine; pyrazolo [1,5-a] pyridine-3,7-diamine; 7-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; pyrazolo [1,5-a] pyridine-3,5-diamine; 5-morpholin-4-yl-pyrazolo [1,5-a] pyridin-3-ylamine; 2 - [(3-amino-pyrazolo [1,5-a] pyridin-5-yl) - (2-hydroxyethyl) amino] ethanol; 2 - [(3-aminopyrazolo [1,5-a] pyridin-7-yl) - (2-hydroxyethyl) amino] ethanol; 3-amino-pyrazolo [1,5-a] pyridin-5-ol; 3-amino-pyrazolo [1,5-a] pyridin-4-ol; 3-amino-pyrazolo [1,5-a] pyridin-6-ol; 3-aminopyrazolo [1,5-a] pyridin-7-ol; 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 WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, 2 , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and tautomeric forms, when tautomeric equilibrium exists. Among the pyrazole derivatives, mention may be made of the compounds described in DE 3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 as the 4.5 1-methyl pyrazole, 4,5-diamino 1 - ((3-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino 1- (4'-chlorobenzyl) pyrazole, 4, 5-diamino 1,3-dimethyl 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- (3-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methyl pyrazole, 4,5-diamino-1-ethyl-3- ( 4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-methyl-1-isopropyl pyrazole, 4-amino-5- (2'-aminoethyl) amino-1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl-3,4 , 5-triami no pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino 4 - ((3-hydroxyethyl) amino-1-methyl pyrazole, and their addition salts. It is also possible to use 4-5-diamino-1 - ((3-methoxyethyl) pyrazole.

Preferably, a 4,5-diaminopyrazole and even more preferably 4,5-diamino-1- (3-hydroxyethyl) pyrazole and / or one of its salts will be used. As pyrazole derivatives, mention may also be made of diamino N, N-dihydropyrazolopyrazolones and especially those described in application FR-A-2 886 136 such as the following compounds and their addition salts: 2,3-diamino-6 7-Dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol -1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one, 2-amino-3- (pyrrolidin-1-yl) 6,7-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, 7-4,5-diamino-3-methyl-1-phenyl pyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino pyrazole, dihydro-1H, pyrazolo [1,2-a] pyrazol-1-one, 2,3-diamino-5,6,7,8-tetra ydro-1H, 6H-pyridazino [1,2-a] pyrazol-1-one, 4-amino-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-lH, 5H-pyrazolo [1,2-a] pyrazol-lone. It will be preferred to use 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2-a] pyrazol-1-one and / or a salt thereof. As heterocyclic bases, 4,5-diamino-1- (3-hydroxyethyl) pyrazole and / or 2,3-diamino-6,7-dihydro-1H, 5H-pyrazolo [1,2- a] pyrazol-1-one and / or a salt thereof. The couplers that can be used in the present invention can be chosen from those conventionally used for dyeing keratinous fibers.

Among these couplers, there may be mentioned 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- (13- hydroxyethyloxy) benzene, 2-amino 4- (B-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-13-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- (13-hydroxyethyl) amino 3,4-methylenedioxybenzene, 2,6-bis (β-hydroxyethylamino) toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methylpyrazole-5-one, 1-phenyl-3-methyl-pyrazole-5-one, 2,6-dimethyl-pyrazolo [1,5-b] -1,2,4-triazole, 2,6-dimethyl [3,2-c] -1 , 2,4-triazole, 6-methyl pyrazolo [1,5-a] benzimidazole, their addition salts with an acid, and mixtures thereof.

In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. The oxidation base (s) may each advantageously represent an amount greater than 0.005 to 10% by weight relative to the total weight of the inverse emulsion (A), and preferably of an amount greater than 0.005 to 5% by weight relative to the total weight of this emulsion. The coupler (s), if they are present, may each advantageously represent an amount greater than 0.005 to 10% by weight relative to the total weight of the inverse emulsion (A), and preferably an amount greater than 0.005 to 5% by weight relative to the total weight of this emulsion. According to a second embodiment of the invention, the inverse emulsion (A) comprises one or more direct dyes. According to one embodiment, the inverse emulsion (A) may comprise one or more oxidation dyes and, as additional dye, a plurality of direct dyes. According to another embodiment, the inverse emulsion (A) does not comprise oxidation dyes, the agent according to the invention is then advantageously used for direct lightening of the keratin fibers. The direct dyes that may be used in the inverse emulsion (A) are more particularly chosen from ionic or nonionic species, preferably cationic or nonionic species.

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

More particularly, the azo dyes comprise a function -N = N- whose two nitrogen atoms are not simultaneously engaged in a ring. However, it is not excluded that one of the two nitrogen atoms of the sequence -N = N- is engaged in a cycle.

The dyes of the family of methines are more particularly compounds comprising at least one sequence chosen from> C = C <and -N = C <whose two atoms are not simultaneously engaged in a ring. It is however specified that one of the nitrogen or carbon atoms of the chains can be engaged in one cycle. More particularly, the dyes of this family are derived from methine, azomethine, mono- and di-arylmethane compounds, indoamines (or diphenylamines), indophenols, indoanilines, carbocyanines, azacabocyanines and their isomers, diazacarbocyanines and their isomers, tetraazacarbocyanines, hemicyanines. As regards the dyes of the carbonyl family, mention may be made, for example, of the dyes chosen from acridone, benzoquinone, anthraquinone, naphthoquinone, benzanthrone, anthranthrone, pyranthrone, pyrazolanthrone, pyrimidinoanthrone, flavanthrone, idanthrone, flavone, (iso) violanthrone, isoindolinone, benzimidazolone, isoquinolinone, anthrapyridone, pyrazoloquinazolone, perinone, quinacridone, quinophthalone, indigo, thioindigo, naphthalimide, anthrapyrimidine, diketopyrrolopyrrole, coumarin. As regards the dyes of the family of cyclic azines, there may be mentioned in particular azine, xanthene, thioxanthene, fluorindine, acridine, (di) oxazine, (di) thiazine, pyronine. The nitro (hetero) aromatic dyes are more particularly nitrobenzene or nitro pyridinic direct dyes.

With regard to porphyrin or phthalocyanine dyes, it is possible to use cationic or non-cationic compounds, optionally comprising one or more metals or metal ions, for example alkali and alkaline earth metals, zinc and silicon.

By way of example of particularly suitable direct dyes, mention may be made of the nitro dyes of the benzene series; azo direct dyes; azomethines; methinic; azacarbocyanines such as tetraazacarbocyanines (tetraazapentamethines); quinone direct dyes and in particular anthraquinone, naphthoquinone or benzoquinone dyes; direct azine dyes; xanthenics; triarylmethanics; indoamines; indigoids; phthalocyanines, porphyrins and natural direct dyes, alone or in mixtures.

These dyes may be monochromophoric dyes (that is to say comprising only one dye) or polychromophoric, preferably di- or tri-chromophoric dyes; the chromophores which may be identical or different, of the same chemical family or not. It should be noted that a polychromophoric dye comprises several radicals each derived from an absorbing molecule in the visible range between 400 and 800 nm. In addition, this absorbance of the dye does not require any prior oxidation thereof, or association with other (s) species (s) chemical (s). In the case of polychromophoric dyes, the chromophores are connected to each other by means of at least one linker which may or may not be cationic. Preferably, the linker is a linear, branched or cyclic C1-C20 alkyl chain, optionally interrupted by at least one heteroatom (such as nitrogen, oxygen) and / or by at least one group comprising (CO, SO2), optionally interrupted by at least one heterocyclic ring which may or may not be condensed with a phenyl ring and comprising at least one quaternized nitrogen atom engaged in said ring and optionally at least one other heteroatom (such as oxygen, nitrogen or sulfur), optionally interrupted by at least one unsubstituted or substituted phenyl or naphthyl group, optionally at least one quaternary ammonium group substituted by two optionally substituted C1-C15 alkyl groups; the linking arm does not comprise a nitro, nitroso or peroxo group.

If the heterocycles or aromatic rings are substituted, they are substituted for example by one or more C 1 -C 8 alkyl radicals optionally substituted with a hydroxyl, C 1 -C 2 alkoxy, C 2 -C 4 hydroxyalkoxy, acetylamino or amino group substituted by one or two C 1 -C 4 alkyl radicals, optionally bearing at least one hydroxyl group or both radicals which can form, with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle, optionally comprising another identical heteroatom or different from nitrogen; a halogen atom; a hydroxyl group; a C1-C2 alkoxy radical; a C2-C4 hydroxyalkoxy radical; an amino radical; an amino radical substituted with one or two identical or different C 1 -C 4 alkyl radicals optionally bearing at least one hydroxyl group. Among the benzene direct dyes that may be used according to the invention, the following compounds may be mentioned in a nonlimiting manner: 1,4-diamino-2-nitrobenzene, 1-amino-2-nitro-4-B-hydroxyethylaminobenzene-1-amino -2-Nitro-4-bis ((3-hydroxyethyl) -aminobenzene -1,4-bis (β-hydroxyethylamino) -2-nitrobenzene-1-B-hydroxyethylamino-2-nitro-4-bis - ((3-hydroxyethylamino ) -benzene-l, 3-hydroxyethylamino-2-nitro-4-aminobenzene-1- (3-hydroxyethylamino-2-nitro-4- (ethyl) (3-hydroxyethyl) aminobenzene-1-amino-3-methyl- 4- (3-hydroxyethylamino-6-nitrobenzene-1-amino-2-nitro-4- (3-hydroxyethylamino) -5-chlorobenzene-1,2-diamino-4-nitrobenzene-1-amino-2- (3-hydroxyethyl) amino 5-Nitrobenzene -1,2-bis - ((3-hydroxyethylamino) -4-nitrobenzene-1-amino-2-tris- (hydroxymethyl) methylamino-5-nitrobenzene-1-hydroxy-2-amino-5- nitrobenzene - 1-Hydroxy-2-amino-4-nitrobenzene - 1-Hydroxy-3-nitro-4-aminobenzene - 1-Hydroxy-2-amino-4,6-dinitrobenzene

1- (3-hydroxyethyloxy-2- (3-hydroxyethylamino) -5-nitrobenzene

- 1-Methoxy-2- (3-hydroxyethylamino-5-nitrobenzene

1- (3-hydroxyethyloxy-3-methylamino-4-nitrobenzene -1- (3-yl) dihydroxypropyloxy-3-methylamino-4-nitrobenzene

1- (3-hydroxyethylamino-4- (3-yl) dihydroxypropyloxy-2-nitrobenzene

1- (3-yl-dihydroxypropylamino-4-trifluoromethyl-2-nitrobenzene

1- (3-Hydroxyethylamino-4-trifluoromethyl-2-nitrobenzene -1- (3-hydroxyethylamino-3-methyl-2-nitrobenzene)

- 1-13-aminoethylamino-5-methoxy-2-nitrobenzene

- 1-Hydroxy-2-chloro-6-ethylamino-4-nitrobenzene

- 1-Hydroxy-2-chloro-6-amino-4-nitrobenzene

- 1-Hydroxy-6-bis - ((3-hydroxyethyl) -amino-3-nitrobenzene -1- (3-hydroxyethylamino-2-nitrobenzene

1-Hydroxy-4- (3-hydroxyethylamino-3-nitrobenzene.

Among the azo, azomethine, methine or tetraazapentamethine direct dyes that may be used according to the invention, mention may be made of the cationic dyes described in patent applications WO 95/15144, WO 95/01772 and EP 714954; FR 2189006, FR 2285851, FR-2140205, EP 1378544, EP 1674073.

Thus, mention may be made, in particular, of the following dyes of formulas (I) to (IV) below, and preferably the compounds of formulas (I) and (III) below: R'3 Ri ADDN (I) x-R2 R3

in which :

D represents a nitrogen atom or the group -CH,

R1 and R2, identical or different, represent a hydrogen atom; a C 1 -C 4 alkyl radical which may be substituted with a -CN, -OH or -NH 2 radical or form, with a carbon atom of the benzene ring, an optionally oxygenated or nitrogen-containing heterocycle, which may be substituted by one or more C 1 -alkyl radicals; -C4; a 4'-aminophenyl radical,

R3 and R'3, which may be identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a cyano, a C1-C4 alkyl or a C1-C4 alkoxy radical; or acetyloxy,

X - represents an anion preferably chosen from chloride, methyl sulfate and acetate,

A represents a group chosen from structures A1 to A18, preferably A1, A4, A7, A13 and A18, as follows: R4 A11 Al2 +/- \ R4 N \ / A4 lN N + NN + R4 R4 4 Al A2 A3 R4 NN + R4 N-N + R4 N R4 A5 R4 A8 R4 A9 R4 A13 A14 A15 R4 R4 R4 / N + Ra N + N 1 N, SN, SN R4 A16 A17 A18 in which R4 represents a C1-C4 alkyl radical which may be substituted by a hydroxyl radical and R5 represents a C1-C4 alkoxy radical; R9 in which:

R6 represents a hydrogen atom or a C1-C4 alkyl radical, R7 represents a hydrogen atom, an alkyl radical which may be substituted by a -CN radical or by an amino group, a 4'-aminophenyl radical or form with R 6, an optionally oxygenated and / or nitrogenous heterocycle which may be substituted with a C 1 -C 4 alkyl radical,

R8 and R9, which may be identical or different, represent a hydrogen atom, a halogen atom such as bromine, chlorine, iodine or fluorine, a C1-C4 alkyl radical or a C1-C4 alkoxy radical, a radical -CN,

X - represents an anion preferably chosen from chloride, methyl sulfate and acetate,

B represents a group chosen from the following structures B1 to B6: RioV-R10, Rio N N + N N + R1, R12 B1 B2 B3 R6 / NR,) IR N + • R10 B4 B5 B6 in which R10 represents an alkyl radical C1-C4, R11 and R12, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical; Wherein R13 represents a hydrogen atom, a C1-C4 alkoxy radical, a halogen atom such as bromine, chlorine, chlorine, and the like; iodine or fluorine, R14 represents a hydrogen atom, a C1-C4 alkyl radical or forms, with a carbon atom of the benzene ring, an optionally oxygenated heterocycle and / or substituted by one or more C1-C4 alkyl groups; R15 represents a hydrogen or halogen atom such that bromine, chlorine, iodine or fluorine, R16 and R17, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl radical; , D1 and D2, which may be identical or different, represent a nitrogen atom or the -CH group, m = 0 or 1, preferably 1, it being understood that when R13 represents an unsubstituted amino group, then D1 and D2 represent simultaneously a group -CH and m = 0, X - represents an anion preferably chosen from chloride, methyl sulphate and fate and acetate, 5E represents a group chosen by structures E1 to E8, more particularly E1, E2 and E7, as follows: R'11N + El OH o E3 o E4 R 'NON + N + NR' R 'E7 E8 and in which R 'represents a C1-C4 alkyl radical;

when m = 0 and D1 represents a nitrogen atom, then E can also designate a group of structure E9 following: R 'i

E9 / N + 1 R 'wherein R' represents a C1-C4 alkyl radical. G n N N (IV) in which:

the symbol G represents a group chosen from the following structures G1 to G3: ## STR1 ## wherein R18 denotes a C1-C4 alkyl radical or a phenyl radical; which may be substituted by a C1-C4 alkyl radical or a halogen selected from chlorine, bromine, iodine and fluorine; R19 denotes a C1-C4 alkyl radical or a phenyl radical; R20 and R21, which may be identical or different, represent a C1-C4 alkyl radical or a phenyl radical, or together form in G1 a benzene ring substituted with one or more C1-C4 alkyl, C1-C4 alkoxy or NO2 radicals, or together form in G2 a benzene ring optionally substituted with one or more C1-C4 alkyl, C1-C4 alkoxy or NO2 radicals; R20 may further denote a hydrogen atom; Z represents an oxygen atom, sulfur atom or a group - NR19; M represents a group -CH, -CR (R denoting C1-C4 alkyl), or -NR22 (X-) r; K represents a group -CH, -CR (R denoting C1-C4 alkyl), or -NR22 (X-) r; P represents a group -CH, -CR (R denoting C1-C4 alkyl), or -NR22 (X-) r; r is zero or 1; R22 represents an O atom, a C1-C4 alkoxy radical, or a C1-C4 alkyl radical; R23 and R24, which may be identical or different, represent a hydrogen or halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4 alkyl radical or a C1-C4 alkoxy radical; NO2; X represents an anion preferably selected from chloride, iodide, methyl sulfate, ethyl sulfate, acetate and perchlorate; with the proviso that, if R22 is O, then r is zero; if K or P or M denote -N-C1-C4 alkyl X, then R23 or R24 is preferably different from a hydrogen atom; if K denotes -NR22 (X-) r, then M = P = -CH, -CR; if M denotes -NR22 (X-) r, then K = P = -CH, -CR; if P denotes -NR22 (X-) r, then K = M and denote -CH or -CR; if Z denotes a sulfur atom with R 21 denoting C 1 -C 4 alkyl, then R 20 is different from a hydrogen atom; if Z denotes -NR22 with R19 denoting C1-C4 alkyl, then at least one of the radicals R18, R20 or R21 of the group of structure G2 is different from a C1-C4 alkyl radical; symbol J represents: - (a) a group of structure J 1 following structure J 1 in which R 25 represents a hydrogen atom, a halogen atom chosen from chlorine, bromine, iodine and fluorine, a C1-C4alkyl, C1-C4alkoxy, -OH, -NO2, -NHR28, -NR29R30, -NH4C1-C4alkyl, or form with R26 a 5- or 6-membered ring containing or not containing one or a plurality of heteroatoms selected from nitrogen, oxygen or sulfur; R 26 represents a hydrogen atom, a halogen atom selected from chlorine, bromine, iodine and fluorine, a C 1 -C 4 alkyl radical, C 1 -C 4 alkoxy radical, or form with R27 or R28 a ring 5- or 6-membered or non-containing one or more heteroatoms selected from nitrogen, oxygen or sulfur; R27 represents a hydrogen atom, an -OH radical, a -NHR28 radical, a -NR29R30 radical; R28 represents a hydrogen atom, a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical, a C2-C4 polyhydroxyalkyl radical, a phenyl radical; R29 and R30, which may be identical or different, represent a C1-C4 alkyl radical, a C1-C4 monohydroxyalkyl radical or a C2-C4 polyhydroxyalkyl radical; (b) a 5- or 6-membered nitrogenous heterocyclic group capable of containing other heteroatoms and / or carbonyl groups and which may be substituted by one or more C 1 -C 4 alkyl, amino or phenyl radicals, and in particular a group of following structure J2 / R3, wherein R31 and R32, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or a phenyl radical; Y 3 Y denotes the radical -CO- or the radical ùC =; n = 0 or 1, with when n denotes 1, U denotes the radical -CO-. In the structures of the dyestuffs (I) to (IV) defined above, the C 1 -C 4 alkyl or alkoxy group preferably denotes methyl, ethyl, butyl, methoxy or ethoxy.

Among the dyes of formulas (I) and (III), the following compounds are preferred: ## STR1 ## ## STR1 ## where: ## STR1 ## Examples of azo direct dyes are the following dyes, described in the COLOR INDEX INTERNATIONAL 3rd edition: - Disperse Red 17 - Basic Red 22 - Basic Red 76 15 - Basic Yellow 57 - Basic Brown 16 - Basic Brown 17 - Disperse Black 9.

1- (4'-Aminodiphenylazo) -2-methyl-4bis - ((3-hydroxyethyl) aminobenzene may also be mentioned Among the quinone direct dyes, the following dyes may be mentioned - Disperse Red 15 - Solvent Violet 13 - Disperse Violet 1 - Disperse Violet 4 - Disperse Blue 1 - Disperse Violet 8 - Disperse Blue 3 - Disperse Red 11 - Disperse Blue 7 - Basic Blue 22 - Disperse Violet 15 - Basic Blue 99 as well as the following compounds: - 1-N-methylmorpholiniumpropylamino- 4-hydroxy-anthraquinone-1-aminopropylamino-4-methylaminoanthraquinone-1-aminopropylaminoanthraquinone-5- (3-hydroxyethyl-1,4-diaminoanthraquinone-2-aminoethylaminoanthraquinone-1,4-bis - ((3-yl-dihydroxypropylamino) -anthraquinone Among the azine dyes, mention may be made of the following compounds: - Basic Blue 17 - Basic Red 2. Among the triarylmethane dyes that can be used according to the invention, mention may be made of the following compounds: - Basic Green 1 - Basic Violet 3 - Basic Violet 14 - Basic Blue 7 - Basic Blue 2 Among the indoamine dyes that may be used according to the invention, mention may be made of the following compounds: 2- (3-hydroxyethlyamino-5- [bis- (13-4'-hydroxyethyl) amino] anilino-1,4-benzoquinone -2 - (3-hydroxyethylamino-5- (2'-methoxy-4'-amino) anilino-1,4-benzoquinone-3-N (2'-chloro-4'-hydroxy) phenyl-acetylamino-6-methoxy-1 4-Benzoquinone imine-3-N (3'-Chloro-4'-methylamino) -phenyl-ureido-6-methyl-1,4-benzoquinone imine-3- [4'-N- (ethyl, carbamylmethyl) -amino ] -phenyl-ureido-6-methyl-1,4-benzoquinone imine. Among the dyes of the tetraazapentamethine type that can be used according to the invention, mention may be made of the following compounds appearing in the table below, An being defined as above: ## STR1 ## ## STR2 ## I NN, ~ N,, N \ NN X N + ^ N ~~ N ~ N \ N ^ N N + ~ N% N ~ N ~ NnN / OH OH X + ~ INXNN% N ~ N. NN N-IV X represents an anion preferably selected from chloride, iodide, methyl sulfate, ethyl sulfate, acetate and perchlorate. Among the polychromophoric dyes, mention may be made more particularly of azo and / or azomethine (hydrazonic) di- or trichromophoric dyes, symmetrical or not, comprising on the one hand at least one aromatic heterocycle comprising 5 or 6 ring members, optionally fused, comprising at least one quaternized nitrogen atom engaged in said heterocycle and optionally at least one other heteroatom (such as nitrogen, sulfur, oxygen), and on the other hand, at least one phenyl or naphthyl group, optionally substituted, optionally bearing at least one OR group with R representing a hydrogen atom, an optionally substituted C1-C6 alkyl radical, an optionally substituted phenyl ring, or at least one N (R ') 2 group with R 'identical or not, representing a hydrogen atom, an optionally substituted alkyl radical C1-C6, an optionally substituted phenyl ring; the radicals R 'which can form, with the nitrogen atom to which they are bonded, a saturated 5- or 6-membered heterocycle, or else one and / or both radicals R' may each form with the carbon atom of the aromatic ring placed in ortho of the nitrogen atom, a 5- or 6-membered saturated heterocycle. As aromatic cationic heterocycle, there may be mentioned, preferably, 5- or 6-membered rings comprising 1 to 3 nitrogen atoms, preferably 1 or 2 nitrogen atoms, one being quaternized; said heterocycle being optionally further fused to a benzene ring. It should also be noted that the heterocycle may optionally comprise another heteroatom different from nitrogen, such as sulfur or oxygen. Embedded image If the heterocycles or phenyl or naphthyl groups are substituted, they are substituted, for example, with one or more C 1 -alkyl radicals. -C8 optionally substituted with a hydroxyl group, C1-C2 alkoxy, C2-C4 hydroxyalkoxy, acetylamino, amino substituted with one or two C1-C4 alkyl radicals, optionally carrying at least one hydroxyl group or both radicals which may form with the nitrogen atom to which they are attached, a 5- or 6-membered heterocycle, optionally comprising another heteroatom identical or different from nitrogen; a halogen atom; a hydroxyl group; a C1-C2 alkoxy radical; a C2-C4 hydroxyalkoxy radical; an amino radical; an amino radical substituted with one or two identical or different C 1 -C 4 alkyl radicals optionally bearing at least one hydroxyl group. These polychromophores are connected to one another by means of at least one linking arm optionally comprising at least one quaternized nitrogen atom, which may or may not be engaged in a saturated or unsaturated, optionally aromatic heterocycle. Preferably, the linker is a linear, branched or cyclic C1-C20 alkyl chain, optionally interrupted by at least one heteroatom (such as nitrogen, oxygen) and / or by at least one group comprising (CO, SO2), optionally interrupted by at least one heterocyclic ring which may or may not be condensed with a phenyl ring and comprising at least one quaternized nitrogen atom engaged in said ring and optionally at least one other heteroatom (such as oxygen, nitrogen or sulfur), optionally interrupted by at least one unsubstituted or substituted phenyl or naphthyl group, optionally at least one quaternary ammonium group substituted by two optionally substituted C1-C15 alkyl groups; the linking arm does not comprise a nitro, nitroso or peroxo group. The link between the linker and each chromophore is generally by means of a heteroatom which substitutes the phenyl or naphthyl ring or by means of the quaternized nitrogen atom of the cationic heterocycle.

The dye may comprise identical or different chromophores. By way of examples of such dyes, reference may especially be made to the patent applications EP 1637566, EP 1619221, EP 1634926, EP 1619220, EP 1672033, EP 1671954, EP 1671955, EP 1679312, EP 1671951, EP167952, EP167971, WO 06/063866, WO 06/063867, WO 06/063868, WO 06/063869, EP 1408919, EP 1377264, EP 1377262, EP 1377261, EP 1377263, EP 1399425, EP 1399117, EP 1416909, EP 1399116, EP 1671560.

It is also possible to use the cationic direct dyes mentioned in applications EP 1006153, which describes dyes comprising two anthraquinone chromophores connected by means of a cationic linker; EP 1433472, EP 1433474, EP 1433471 and EP 1433473 which describe identical or different dichromophoric dyes, connected by a cationic or non-cationic linking arm, as well as EP 6291333 which describes in particular dyes comprising three chromophores, one of them being an anthraquinone chromophore to which are connected two azo-type chromophores or diazacarbocyanine or one of its isomers.

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, brazilin, braziline, haematein, hematoxylin. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna. When present, the direct dye or dyes advantageously represent an amount greater than 0.005 to 10% by weight of the total weight of the inverse emulsion (A), and preferably an amount greater than 0.005 to 5% in weight. According to a third embodiment of the invention, the emulsions (A) and (B) do not comprise a direct dye, an oxidation dye precursor (bases and couplers) or, if present, their total content does not exceed 0.005% by weight relative to the weight of each emulsion. In this embodiment, the agent according to the invention is advantageously used for the bleaching of keratinous fibers.

In this embodiment, the inverse emulsion (A) may advantageously comprise one or more solid or pasty adjuvants, and preferably pulverulent. The adjuvants may then be chosen from the salts different from the ammonium salts, the natural or synthetic thickeners other than those previously defined, the optionally modified starch, the glass beads, the silica, the nylon, the alumina, the titanium dioxide, zeolites, poly (methyl methacrylate) (PMMA), chitosan, maltodextrin, cyclodextrin, mono- or disaccharides such as glucose, sucrose, sorbitol or fructose, zinc oxide , zirconium, silicates, talc, calcium borosilicates, polyethylene, polytetrafluoroethylene (PTFE), cellulose and its derivatives, superabsorbent compounds, magnesium or calcium carbonates, polyacrylamide, porous hydroxyapatite sawdust, fucus powder, cross-linked polyvinylpyrrolidone, calcium alginate, activated carbon, polyvinylidene / acrylonitrile particles, especially those marketed or the general name of "Expancel®" by AKZO NOBEL under the particular references "Expancel® WE" or "DE" Expancels, and their mixtures.

In general, the emulsions (A) and (B) constitute a cosmetically acceptable medium optionally comprising one or more organic solvents. As organic solvent, there may be mentioned for example linear or branched C2-C4 alkanols, such as ethanol and isopropanol; glycerol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, dipropylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

Such organic solvents may be present in proportions preferably of between 1 and 40% by weight relative to the total weight of each composition in which they are contained, and more preferably between 5 and 30% by weight.

The emulsions (A) and / or (B) according to the present invention may also comprise one or more adjuvants, chosen from those conventionally used in compositions for dyeing and / or bleaching keratinous fibers such as conditioning polymers, in particular cationic, organic thickeners different from the oil thickeners defined above, with in particular anionic, cationic and nonionic polymeric associative thickeners, surfactants of HLB less than 8, antioxidants; penetrants; sequestering agents; perfumes ; dispersants; film-forming agents; ceramides; preservatives; opacifying agents. The direct emulsion (B) may also comprise the thickeners as described above for the inverse emulsion (A), as well as anionic, cationic, amphoteric and nonionic surfactants, such as those described above. for the inverse emulsion (A). The adjuvants above can be generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of each composition. The present invention also relates to a method for dyeing and / or bleaching keratinous fibers, comprising applying to said fibers the agent as described above. According to the invention, the agent applied to the keratinous fibers results from the mixing of the emulsions (A) and (B), this mixture being produced either before application to the keratin fibers (extemporaneous preparation) or directly to the keratinous fibers (successive application the fibers of emulsions (A) and (B) without intermediate rinsing Thus, according to a first variant of the process according to the invention, the emulsions (A) are applied to the keratinous fibers, dry or wet, successively and without intermediate rinsing. and then (B) According to a second variant of the process according to the invention, a composition obtained by extemporaneous mixing before application of the emulsions (A) and (B) is applied to the dry or moist keratinous fibers. In this case, then the time between the mixing of the emulsions (A) and (B) and the application of the mixture to the hair does not exceed preferably 30 minutes, preferably 10 minutes, so that e preferred 5 minutes Regardless of the variant used, the weight ratio of the amount of the inverse emulsion (A) used to the amount of the direct emulsion (B) used may vary from 0.2 to 3 and from preferably from 0.3 to 1.

In addition, regardless of the variant used, the mixture present on the fibers (resulting either from the extemporaneous mixing of the emulsions (A) and (B) or from the successive application thereof) is left in place for a period of time. in general, of the order of 1 minute to 1 hour, preferably 5 minutes to 30 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. At the end of the treatment, the keratin fibers are optionally rinsed with water, optionally washed with a shampoo followed by rinsing with water, before being dried or allowed to dry. Finally, the invention also relates to a multi-compartment device or "kit" for staining and / or bleaching, comprising a first compartment containing an inverse emulsion (A) and a second compartment containing a direct emulsion (B ), the emulsions (A) and (B) being as described above. This device may also comprise one or more compositions for washing and / or conditioning the keratinous fibers, intended to be applied before and / or after the coloring and / or discoloration treatment according to the invention. This device may advantageously be equipped with a means for delivering the desired mixture onto the hair, such as the devices described in the patent FR2586913. The following examples serve to illustrate the invention without being limiting in nature. EXAMPLE The following inverse oxidation dye (A) emulsion was prepared (in the table below, the amounts are expressed in% by weight): Reverse emulsion comprising color precursors Cl (% by weight) Vaseline 51.5 Octyl dodecanol 9 Modified Hectorite distearyl dimethyl ammonium 1.3 Propylene carbonate 0.45 Oleic alcohol 10 EO (i) 4.3 Propylene glycol 2 Ethanol 3 Hexylene glycol 1 Dipropylene glycol 1 Monoethanolamine 4 POE / POP / POE (Poloxamer 184) (2) 13 Ascorbic acid 0.25 Paraphenylenediamine 0.03 Resorcinol 0.04 1-hydroxy-3-aminobenzene 0.002 1-beta-hydroxyethyloxy-2,4-diamino-benzene 0.0003 dihydrochloride N, N-bis (2-hydroxyethyl) -p-0.006 phenylendiamine sulphate, 1 H2O water Qs 100 (1) HLB = 12.4 (2) HLB = 15 Direct oxidizing emulsion (% by weight) C2 Paraffin oil 20 Cylylenearyl alcohol C16 / C18 (30/70) 8 Ceylstearyl alcohol 33 EO 3 Disodium Tin hexahydroxide 0.04 Oxygenated rapeseed acid amides (4O E) 1.5 Vitamin E 0.1 Glycerin 1 Hydrogen peroxide 6 Sodium stannate, 6 H2O 0.04 Diethylene triamine pentacetic acid 0.015 Tetrasodium pyrophosphate, 10 H2O 0.03 Phosphoric acid Qsp pH = 3 Demineralized water Qs 100 At the time of use, mix a part by weight of the direct emulsion C1 with one part by weight of the inverse emulsion C2.

The mixture is then applied to 90% natural white hair strands. After 30 minutes of resting at room temperature (23 ° C), the hair is rinsed, washed with a standard shampoo and dried. We then obtain a very light blond golden ash color.5

Claims (18)

REVENDICATIONS1. Coloring and / or bleaching agent for keratinous fibers, comprising: a water-in-oil inverse emulsion (A) comprising -30 to 70% by weight relative to the weight of the emulsion (A) of one or more oils containing no carboxylic acid function, - water, - one or more surfactants with an HLB value of 8 or more, - one or more basifying agents, - an oil-in-water emulsion ( B) comprising: - water, - one or more oils containing no carboxylic acid function, - one or more oxidizing agents, the total amount of said oils contained in the mixture of emulsions (A) and (B) representing at least less than 20% by weight relative to the total weight of said mixture. 2. Agent according to claim 1, characterized in that the basifying agent is chosen from ammonia, alkali carbonates, alkanolamines and their derivatives, hydroxides of sodium or potassium, and compounds of formula (I) the following: wherein W is a C1-C6 alkylene radical optionally substituted by a hydroxyl group or a C1-C6 alkyl radical; Rx, Ry, Rz and Rt, identical or different, represent a hydrogen atom, a C1-C6 alkyl or C1-C6 hydroxyalkyl, C1-C6 aminoalkyl radical; and is preferably selected from alkanolamines. 3. Agent according to any one of the preceding claims, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, preferably persulfates, perborates and percarbonates of alkali or alkaline earth metals, oxidation-reduction enzymes, preferably laccases, peroxidases and 2-electron oxidoreductases, optionally in the presence of their respective donor or cofactor; and is preferably hydrogen peroxide. 4. Agent according to any one of the preceding claims, characterized in that the inverse emulsion (A) comprises one or more oil thickening agents. 5. Agent according to the preceding claim, characterized in that the thickener present in the inverse emulsion (A) is an organophilic clay selected from montmorrilonite, bentonite, hectorite, attapulgite, sepiolite, and their mixtures, possibly modified. 6. Agent according to any one of claims 4 and 5, characterized in that the concentration of thickener in the inverse emulsion (A) is between 0.1 and 10% by weight relative to the total weight of the inverse emulsion (A), preferably ranging from 0.5 to 7% by weight, and more preferably ranging from 1 to 5% by weight. 7. Agent according to any one of the preceding claims, characterized in that the surfactant having an HLB value greater than or equal to 8 is anionic or nonionic, preferably nonionic. 8. Agent according to any one of the preceding claims, characterized in that the surfactant having an HLB value greater than or equal to 8 present in the inverse emulsion (A) is chosen from oxyalkylenated nonionic surfactants belonging preferably to following families: - oxyethylenated alkylphenols, - EO / PO condensates, - oxyethylenated vegetable oils, - oxyethylenated fatty alcohols, - polyethylene glycol fatty acid esters, - polyoxyethylenated fatty acid and sorbitol esters. 9. Agent according to any one of the preceding claims, characterized in that the concentration of surfactant having an HLB value greater than or equal to 8 present in the inverse emulsion (A) is between 1 and 20% by weight, of preferably between 1 and 15% by weight, and more preferably from 2 to 10% by weight, relative to the total weight of the inverse emulsion (A). 10. Agent according to any one of the preceding claims, characterized in that the oil or oils containing no carboxylic acid function are chosen from hydrocarbons, non-silicone oils of animal, vegetable, mineral or synthetic origin, fatty alcohols, esters of fatty acids and / or fatty alcohols, silicones and mixtures thereof; preferably from liquid petroleum jelly, polydecenes, esters of fatty acids and / or of liquid fatty alcohols, liquid fatty alcohols, and mixtures thereof; and more preferably from vaseline oil, polydecenes, liquid fatty alcohols and mixtures thereof. 11. Agent according to any one of the preceding claims, characterized in that the emulsion (B) contains from 5 to 50% by weight, preferably from 10 to 30% by weight relative to the total weight of the emulsion ( B) one or more oils not containing a carboxylic acid function, 12. Agent according to any one of the preceding claims, characterized in that the total amount of oil (s) not containing a carboxylic acid function in the mixture of emulsions (A) and (B) is at least 25% by weight. weight, and preferably at least 30% by weight, relative to the total weight of the mixture of these two emulsions. 13. Agent according to any one of the preceding claims, characterized in that the inverse emulsion (A) further comprises one or more oxidation dyes chosen from oxidation bases, optionally combined with one or more several couplers. 14. Agent according to any one of the preceding claims, characterized in that the inverse emulsion (A) further comprises one or more direct dyes. 15. Agent according to any one of claims 1 to 12, characterized in that the emulsions (A) and (B) comprise a total content of direct dye or oxidation dye precursor (bases and couplers) not exceeding 0.005% by weight relative to the weight of each emulsion. 16. A method for dyeing and / or bleaching keratin fibers, comprising applying to said fibers, dry or wet, successively and without intermediate rinsing, emulsions (A) and (B) as defined in any one of preceding claims. 17. A method for dyeing and / or bleaching keratinous fibers, comprising applying to said fibers, dry or wet, a composition obtained by extemporaneous mixing of the emulsions (A) and (B) as defined in one of the following: any of claims 1 to 15. 18. Multi-compartment device or "kit" for staining and / or bleaching, comprising a first compartment containing an inverse emulsion (A) and a second compartment containing a direct emulsion (B), the emulsions (A) and (B) being as defined in any one of claims 1 to 15.