FR2952817A1 - Composition, useful for dyeing keratin fibers, preferably human keratin fibers such as hair, comprises one or more dye precursors comprising indole derivatives and liquid organic compounds in a medium - Google Patents

Abstract

Composition (A) comprises: (i) one or more dye precursors comprising indole derivatives (I); and (ii) one or more liquid organic compounds having a Hansen solubility parameter (delta H) of = 15 (MPa) 1>>2>at 25[deg] C in a medium. Composition (A) comprises: (i) one or more dye precursors comprising indole derivatives of formula (I); and (ii) one or more liquid organic compounds having a Hansen solubility parameter (delta H) of = 15 (MPa) 1/2>at 25[deg] C in a medium. R1-R4 : 1-4C alkyl or 1-4C alkoxy (both optionally substituted), H, halo or OH; R : 2-6C acyl group or 1-4C alkyl carboxy (both optionally substituted), group derived from a polyol, PO 3MM1a group or SO 3M 2group; M : H or an ion derived from an alkali metal or alkaline earth metal, an ammonium ion or an ion from an organic amine; M1a : M or 1-4C trialkyl ammonio-1-4C alkyl; M 2undefined Z : 2-6C acyl group or 1-10C alkyl (both optionally substituted) or H; and W1 : 1-4C alkoxy, 2-4C acyl or 1-10C alkyl (all optionally substituted), H, halo, OH, optionally salified carboxy, -SCH 3or -SO 2CH 3. Independent claims are included for: (1) dyeing keratin fibers, preferably human keratin fibers such as hair, comprising application, on the fibers, of (A) for a sufficient time to obtain the desired color; and (2) device having many compartments or kit, comprising either one compartment containing (A), optionally a compartment, which at least contains a composition comprising one or more oxidizing agents, and optionally another compartment comprising a basic post treatment composition having a pH of 7.1-13, or two compartments to be generated by mixing (A). [Image].

Description

B09-2784FR GD / GL OA09483 A company known as L'OREAL A composition containing at least one indole-derived staining precursor and at least one liquid organic compound. Invention of: Boris LALLEMAN Alain LAGRANGE Composition containing at least one dye precursor derived from The present invention relates to a composition for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, comprising, in a medium suitable for dyeing, at least one dye precursor. particular indole and at least one particular liquid organic compound. The invention also relates to a use of said composition for dyeing keratinous fibers.

The invention also relates to dyeing processes using such components and a multi-compartment device comprising them. The present invention relates to the field of dyeing keratinous fibers and more particularly to hair dyeing.

The first type of coloration is the so-called permanent or oxidation coloration, which uses dyeing compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho- or para-phenylenediamines, ortho- or para-phenylenediamines, or para-aminophenols and heterocyclic compounds. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, can give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-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 oxidation dyeing process is generally carried out under conditions of alkaline pH by applying to the keratin fibers, oxidation bases or a mixture of oxidation bases and couplers in the presence of an oxidizing agent, such as than hydrogen peroxide (or "hydrogen peroxide"), which is added at the time of use. The resulting colorations are generally powerful and have good toughness, especially with shampoos. However, these conditions of implementation are not without consequences on the properties of the treated fibers. Indeed, in the long run, the keratinous fibers are more or less degraded and tend to become rough, dull, brittle and difficult to comb, which is particularly accentuated in the case of repeated staining. The second type of staining is so-called semipermanent staining or direct staining, which uses dyes capable of providing more or less marked modification to the natural coloring of the hair. The method conventionally used in direct dyeing consists in applying to the keratin fibers direct dyes which are colored and dyestuff molecules having an affinity for the fibers, to be allowed to pause in order to allow the colored molecules to penetrate by diffusion inside the dye fibers. the fiber, then rinsing the fibers. In order to perform these stains, it is known for example to use nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane direct dyes.

This results in colorations which may be particularly chromatic which are, however, temporary or semi-permanent because of the nature of the bonds between the direct dyes and the keratinous fiber. These interactions make the desorption of dyes from the surface and / or the core of the fiber easily. The colorations generally have a low dyeing power and poor resistance to washing or perspiration. It is already known to use indole derivatives for hair coloring. In particular, the document EP 843994 describes a hair dyeing composition comprising the combination of indoxyacetate and ispropanol. However, this combination under these conditions has insufficient color intensity and / or chromaticity. Thus, there is a real need to provide dyeing compositions which do not have all of the disadvantages mentioned above, that is to say which lead to improved colorations in terms of intensity and / or chromaticity. while leading to good results of tenacity and respect for the fiber. The subject of the present invention is therefore a composition for dyeing keratinous fibers, in particular human keratin fibers such as the hair, comprising, in a cosmetically acceptable medium: (i) one or more indole-derived staining precursors of formula (I): (I) wherein: R1, R2, R3 and R4 represent, independently of one another, a hydrogen atom; a halogen atom; a hydroxyl group; a linear or branched, optionally substituted C1-C4 alkyl group; a linear or branched, optionally substituted C1-C4 alkoxy group; R represents a radical derived from a polyol; a C2-C6 acyl group, linear or branched, optionally substituted; a group PO3MM '; a group SO3M2; a linear or branched, optionally substituted alkyl (C1-C4) carboxy group; with M denoting a hydrogen atom or an ion derived from an alkali or alkaline earth metal, an ammonium ion or an ion derived from an organic amine and M 'having the same possible meanings as M and may also designate a trialkyl (C1-C4) ammonioalkyl (C1-C4) group; Z represents a hydrogen atom; a C2-C6 acyl group, linear or branched, optionally substituted; a linear or branched, optionally substituted C1-C10 alkyl group; W represents a hydrogen atom; a halogen atom; a hydroxyl group; a linear or branched, optionally substituted C1-C4 alkoxy group; a C2-C4 acyl group, linear or branched, optionally substituted; a linear or branched, optionally substituted C1-C10 alkyl group; a salified carboxy group or not; a group ûSCH3; a group - SO2CH3; and (ii) one or more liquid organic compounds having a Hansen solubility parameter value bH of less than or equal to 15 (MPa) 12 at 25 ° C. The dyeing composition according to the invention makes it possible to lead to powerful, chromatic and resistant colorings, in particular to shampoos and to ultraviolet and visible radiation. In addition, the dyeing composition according to the invention has the advantage of leading to little selective coloring, that is to say homogeneous staining along the same fiber, which is generally differently sensitized (ie damaged) between its tip and its root. The present invention also relates to the use of the dye composition as described above for dyeing keratinous fibers, in particular human keratinous fibers such as the hair. Another subject of the present application relates to a process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, which consists in applying the dyeing composition as described above for a time sufficient to obtain the coloration. desired, optionally followed by rinsing and washing the keratinous fibers. The present invention also relates to a multi-compartment device comprising the composition according to the invention.

Other features, aspects, objects and advantages of the present invention will become more apparent upon reading the description and the examples which follow. By the term "substituted" is meant substituted by a linear or branched C1-C4 alkyl group, preferably methyl or ethyl; a hydroxyl group; a linear C1-C4 alkoxy group, preferably methoxy, or branched; a halogen atom, preferably chlorine or bromine; a carboxyl group. In the case where R1, R2, R3, R4, R'1, R'2, R'3 and R'4 and / or Z comprise at least one substituted linear or branched alkyl group, it is clear that the substitution by a or more linear or branched alkyl groups has no chemical meaning. According to one embodiment, R1, R2, R3 and R4 represent, independently of one another, a hydrogen atom; a halogen atom, preferably a chlorine, bromine or iodine atom; a linear C1-C4 alkoxy group, preferably methoxy. Preferably, R 1 and / or R 2 and / or R 3 and / or R 4 represent a hydrogen atom or a halogen atom. In the first variant, one or more substituents R1 to R4 represent a halogen atom, preferably a chlorine, bromine or iodine atom, the other substituents R1 to R4 being a hydrogen atom. More particularly, one of the substituents R 1 to R 4 represents a halogen atom, preferably a chlorine, bromine or iodine atom, the other substituents R 1 to R 4 being a hydrogen atom. In the second variant, R1, R2, R3 and R4 all represent a hydrogen atom. This second variant is particularly preferred. According to one embodiment, Z represents a hydrogen atom, a linear C 2 -C 4 acyl group, preferably acetyl -COCH 3, or a linear C 1 -C 4 alkyl group, preferably methyl. Preferably, Z represents a hydrogen atom or an acetyl group -COCH3. Even more preferentially, Z represents a hydrogen atom.

According to one embodiment, R represents a radical derived from a polyol. In a first variant, R represents a radical derived from a polyol of formula (II): embedded image in which: n denotes 0 or 1; - R5 represents a hydroxyl group or a ketone function; R6 represents a hydroxyl group, a group -CH2OH, a group -CH2O00CH2CO2H; R7 represents a hydrogen atom or a hydroxyl group; - R8 represents a hydrogen atom or a hydroxyl group. In a second variant, R represents a radical derived from a polyol of formula (III): embedded image in which - n 'denotes 0 or 1; - R'5 represents a hydroxyl group or a ketone function; O ~ CO n5 - R'6 represents a hydroxyl group or a group - CH2OH; - R'7 represents a hydrogen atom or a hydroxyl group.

Preferably, R represents an optionally substituted linear or branched C2-C6 acyl group; a group - S03M2 with M denoting a hydrogen atom or an ion derived from an alkali or alkaline earth metal, an ammonium ion or an ion derived from an organic amine; a radical derived from a polyol of formula (II) or (III).

Even more preferably, R represents a linear or branched, optionally substituted C2-C4 acyl group. More particularly, R represents an acetyl group -COCH3. According to one embodiment, W represents a hydrogen atom or a group -SCH3.

Preferably, W represents a hydrogen atom. According to a particularly advantageous embodiment of the invention, the indole derived dye precursor (s) of formula (I) are chosen from the following compounds: HOCH. VS; Indoxyl bD-glucoside Ho '~ -o H (Indican) -r_ HO OH Indoxyl-3-O- (6'-O-malonyl- (3-D-O-ribohexo-3-ulopyranoside) whereI I (Isatan A) ooo ## STR2 ## Indoxyl-5-ketogluconate H Indoxyl-3-O- (3-D-ribohex-3-H-OH-N-olopyranoside (Isatan B) ## STR5 ## HO 3-acetoxy indole N-methyl-indoxyl acetate / o 1,3-diacetoxyindole oo 0 Disodium salt 3-indoxyl-phosphate 0 OP / Na-Na 'N 3 -indoxyl choline phosphate 3 ON Propanoic acid of 2- (5-bromo-4-bromo-3-chloroindoxyl) N (5-bromo-4-chloro-3-indolyl) -bD-Br. Cl ~ ribofuranoside N 6-bromo acetate - Indoxyl Br O o N 5-Bromo- indoxyl acetate Br O ~~ ON 5-Bromo- indoxyl diacetate Br OO ~ N-4-chloro-indoxyl-1,3-diacetate 0 \ / Acetate 5 -chloro-indoxyl CI OON 6-chloro-3-indoyl acetate CI o NOO 7-chloroindoxyl-1,3-diacetate and 6-chloro-3-indoxyl-1,3-diacetate o / o 0 Br O,, 5-bromo-4-chloro indolyl acetate N and 5-bromo-4-chloroindoxyl diacetate Bru, / 0 ~ / ~ N -acetyl-5-bromo-6-chloro-N-hydroxyindole 1H-Indol-H 3-ole N 1 OPO3H2 3-dihydrogenphosphate of 5-bromo-N-4-chloro-1H- Indol-3-ol Br OP03H2 5- and N-bromo-6-chloro-1H-Indol-3-ole bromo-6-ol dihydrogen phosphate Ester of 6-chloro-1H-Indol-3-ole OPO3H2 dihydrogen phosphate ester HN dihydrogen phosphate ester 4-chloro-1H-Indol-3-ole 1 OP03H2 1 1H-FN-6-fluoro-Indol-3-ole 1H-dihydrogenphosphate ester 1N 0P03H2 6-N-iodo-1H-Indole dihydrogen phosphate ester 1N 0P03H2 0P03H2 1-methyl-1H-Indol-3-01 MeOH S-dihydrogen phosphate ester / Potassium salt 3-indoxylsulfate // K. K + 0-0 Potassium salt of 5-bromo-6-Br. I-O Hydrochloro-3-indolyl sulfate hydrate ° OI ~ OS03- tyrindoxyl sulphate SCH3 Br N Potassium salt of 5-bromo-4- o-cIsket K 'chloro-3-indolylsulfate Bru / o ° N Preferably, the compound of formula (I) is chosen from the following compounds: Indican, potassium 3-indoxysulfate, Isatan A, Isatan B, 3-acetoxyindole, 3-indoxyl disodium phosphate, tyrindoxyl sulfate and 6-bromoindoxyl acetate. Even more preferably, the compound of formula (I) is 3-acetoxyindole.

The indole-derived staining precursor (s) of formula (I) may be present in a content ranging from 0.01 to 20% by weight, preferably in a content ranging from 0.05 to 15% by weight, and even more preferably in a content ranging from 0.1 to 10% by weight, relative to the total weight of the dyeing composition according to the invention.

As indicated above, the dyeing composition according to the invention further comprises one or more liquid organic compounds which have a Hansen solubility parameter value bH of less than or equal to 15 (MPa) 1/2 at 25 ° C. For the purposes of the present invention, the term "organic liquid compound" is intended to mean an organic compound which is liquid at ambient temperature at 25.degree. The liquid organic compound or compounds having a Hansen solubility parameter value bH of less than or equal to 15 (MPa) 1/2 at 25 ° C. are for example described in the reference work "Hansen solubility parameters A user's handbook", Charles M. Hansen, CRC Press, 2000, pages 167 to 185 as well as in the book "Handbook of solubility parameters and other cohesion parameters" CRC, Press, pages 95 to 121 and pages 177 to 185. As a reminder, the organic compounds have a global solubility parameter 8 according to Hansen, which is defined in the article "Solubility parameters values" by Eric A. Grulke of the book "Polymer Handbook", 3rd edition, Chapter VII, pages 519-559 by the relation: (5d2 + Sp2 + Sh2) 1/2 in which: - 5d characterizes the LONDON dispersion forces resulting from the formation of dipoles induced during molecular impacts, that is to say the non-polar interactions, - 8p characterizes the interaction forces of DEBYE between permanent dipoles, - 6h characterizes the interaction forces of the hydrogen bonding type.

Thus, the Hansen solubility parameter bH accounts for the solubility associated with the formation of hydrogen bonds in liquid organic compounds. According to one embodiment, the liquid organic compound (s) have a Hansen solubility parameter value bH ranging from 6 (MPa) 1/2 to 14 (MPa) 1/2 at 25 ° C, and preferably ranging from 4 (MPa) 1/2 to 10 (MPa) 1/2 at 25 ° C. Preferably, the liquid organic compound (s) comprise a molecular weight of less than 500 g / mol, and even more preferentially less than 250 g / mol.

Among the liquid organic compounds having a Hansen solubility parameter bH value of less than or equal to 15 (MPa) 1/2 at 25 ° C, mention may be made of propylene glycol derivatives, phenyl alcohols such as benzyl alcohol, alkylenecarbonates, lactones, in particular lactones of formula (IV): in which: n is 1, 2 or 3; R 'represents a hydrogen atom; a linear or branched C1-C8 alkyl radical; a hydroxyalkyl radical, linear or branched C1-C4. According to an advantageous embodiment, the liquid organic compound (s) having a Hansen solubility parameter value bH of less than or equal to 15 (MPa) 1/2 at 25 ° C. are chosen from the following compounds: Denomination bH Benzyl alcohol 13.7 Dipropylene glycol methyl ether 11.2 Tripropylene glycol methyl ether 10.4 propylene glycol n-butyl ether (PnB) 9.2 propylene glycol n-propyl ether 9.2 (PnP) Dipropylene glycol 8 monomethyl ether acetate 3-phenyl-1 propanol 12.1 2-phenyl-1-propanol 12.9 Ethylene glycol 2-ethyl hexyl ether 5.1 1-octanol 11.9 1-decanol 10 Tridecyl alcohol 9 y-Butyrolactone 7.4 Propylene Carbonate 4.1 Preferably the liquid organic compound (s) having a Hansen solubility parameter value 6H of less than or equal to 15 (MPa) -2 at 25 ° C are chosen from alcohols, ethers, acids and / or a mixture of these compounds. According to one embodiment, the organo compound (s) Liquid esters having a Hansen solubility parameter value 6H of less than or equal to 15 (MPa) -2 at 25 ° C are selected from alcohols.

In particular, the alcohol or alcohols that can be used as liquid organic compounds having a Hansen solubility parameter 6 h as described above can be chosen from benzyl alcohol, 3-phenyl-1-propanol and 2-phenyl. -1-ethanol, 1-decanol and / or a mixture of these compounds.

According to one embodiment, the liquid organic compound (s) having a value of the Hansen solubility parameter 6 h of less than or equal to 15 (MPa) -2 at 25 ° C. are chosen from ethers, in particular the ethers which can be used as that liquid organic compounds having a Hansen solubility parameter 6 h as described above can be propylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol propyl ether, etc. According to one embodiment, the the liquid organic compounds having a Hansen solubility parameter value bH of less than or equal to 15 (MPa) 1/2 at 25 ° C. are chosen from among the acids, as examples of acids according to the present invention, In particular, the liquid organic compound (s) having a solubility parameter value of 6 h Hansen less than or equal to 15 (MPa) 1/2 at 25 °. C are selected from benzyl alcohol and / or propylene carbonate. The liquid organic compound (s) having a Hansen solubility parameter bH less than or equal to 15 (MPa) 1/2 at 25 ° C. can be present in the dyeing composition according to the invention in a content ranging from 0.5% at 50% by weight, preferably in a content ranging from 1% to 30% by weight, and more preferably in a content ranging from 5% to 20% by weight, relative to the total weight of the dyeing composition.

Preferably, the dyeing composition according to the invention comprises 3-acetoxyindole and one or more liquid organic compounds having a Hansen solubility parameter value bH of less than or equal to 15 (MPa) 1/2 at 25 ° C. The medium that is suitable for the coloration, also called staining medium, is a cosmetic medium generally constituted by water or by a mixture of water and at least one organic solvent, preferably different from the liquid organic compounds as described above. . As a different organic solvent for liquid organic compounds having a Hansen solubility parameter value 6 h of less than or equal to 15 (MPa) 1/2 at 25 ° C., linear or branched alkanols, for example, C1-C4, such as ethanol and isopropanol; glycerol; glycols such as propylene glycol, dipropylene glycol, the like and mixtures thereof.

This or these solvents may be present in proportions ranging preferably from 1 to 40% by weight relative to the total weight of the dye composition, and even more preferably from 5 to 30% by weight approximately.

The pH of the composition according to the invention generally varies from 1 to 12, and preferably is less than 7, and even more preferably varies from 1 to 5. It can be adjusted to the desired value by means of acidifying agents. or alkalizing agents usually used in the field.

Among the acidifying agents, mention may be made, by way of 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.

Among the alkalinizing agents that may be mentioned, by way of example, are ammonia, alkaline carbonates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium or potassium hydroxides and following formula (V): wherein R is a propylene residue optionally substituted by a hydroxyl group or a C 1 -C 6 alkyl radical; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom, a C1-C6 alkyl radical or a C1-C6 hydroxyalkyl radical. The cosmetic composition may furthermore comprise one or more additional direct dyes, different from the dye precursors derived from indoles (i) of nonionic, cationic or anionic nature, and preferably cationic or nonionic, or their combinations. Generally, these direct dyes are chosen from nitrobenzene dyes, azo, azomethine, methine, anthraquinone, naphthoquinone, benzoquinone, phenotiazine indigo, xanthene, phenanthridine, phthalocyanine dyes, those derived from triarylmethane, natural dyes other than dye precursors. indole derivatives (i), alone or in mixtures. Preferably, the additional direct dyes are chosen from curcumin, orcein, chlorophylline, sorghum, laccaic acid, lawsone, haematin, hematoxylin, brasiline, brasiline, isatin, purpurine, alizarin or mixtures thereof. When they are present, the additional direct dye or dyes preferably represent 0.01 to 20% by weight, and even more preferably 0.05 to 10% by weight relative to the total weight of the composition. When it is intended for the oxidation dyeing, the cosmetic composition in accordance with the invention further comprises at least one oxidation base chosen from the oxidation bases conventionally used for the oxidation dyeing and of which one mention may especially be made of para-phenylenediamines, bis-phenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and their addition salts with an acid or with an alkaline agent. When used, the oxidation base (s) preferably represent from 0.005 to 15% by weight, and even more preferably from 0.01 to 10% by weight, relative to the total weight of the composition. When it is intended for the oxidation dyeing, the composition according to the invention may also comprise at least one coupler so as to modify or enrich in glints the shades obtained by using the direct dyes and the dye base (s). 'oxidation. The couplers that may be used may be chosen from the couplers conventionally used in oxidation dyeing, among which may be mentioned in particular meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers and their addition salts with an acid or with an alkaline agent. When present, the coupler or couplers preferably represent from 0.001 to 15% by weight, and even more preferably from 0.05 to 10% by weight relative to the total weight of the composition.

In general, the addition salts with an acid that can be used in the context of the compositions of the invention (oxidation bases and couplers) are chosen especially from hydrochlorides, hydrobromides, sulphates, citrates and succinates. , tartrates, tosylates, benzenesulfonates, lactates and acetates. The addition salts with an alkaline agent that can be used in the context of the compositions of the invention (oxidation bases and couplers) are chosen in particular from the addition salts with the alkaline or alkaline-earth metals, with ammonia, with organic amines including alkanolamines and compounds of formula (V). The cosmetic composition according to the invention may also comprise one or more cosmetic adjuvants. The cosmetic adjuvant (s), which are conventionally used in cosmetic compositions, in particular for dyeing human keratin fibers, may be chosen from anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof; anionic, nonionic, cationic or amphoteric surfactants; pigments; mineral thickeners; antioxidants; penetrants; sequestering agents; perfumes ; buffers; dispersants; conditioning agents such as, for example, cations, cationic or amphoteric polymers, chitosans, volatile or non-volatile silicones, modified or unmodified; film-forming agents; ceramides; preservatives; stabilizing agents; opacifying agents. Of course, one skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition according to the invention are not, or not substantially, impaired by the addition or additions considered. The adjuvants above are generally present in an amount for each of them between 0 and 20% by weight relative to the total weight of the composition.

In a preferred variant of the invention, the compositions according to the invention contain one or more thickening polymers. For the purposes of the present invention, the term "thickening polymer" is intended to mean any polymer whose presence in the composition makes it possible to increase the viscosity by at least 100 cp at the temperature of 25 ° C. and at a shear rate of 1%. this viscosity can be determined by a Rheometer or a cone / plane viscometer. In a preferred variant of the invention, the compositions according to the invention comprise one or more surfactants. This or these surfactants may be nonionic, anionic, cationic or amphoteric. The composition according to the invention may be in various forms, such as in the form of liquids, shampoos, creams, gels, or in any other suitable form.

In particular, the dyeing composition according to the invention is in the form of a gel. The composition comprising the compounds of formula (I) may be anhydrous. For the purposes of the present invention, the term "anhydrous composition" means a composition containing less than 5% by weight of water, preferably less than 2% and even more preferably less than 1% relative to the total weight of the composition. The dyeing composition according to the invention may further comprise one or more oxidizing agents chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, and enzymes such as peroxidases and two- or four-electron oxidoreductases. The use of hydrogen peroxide is particularly preferred.

Another subject of the invention consists of a process for dyeing keratinous fibers, in particular human keratinous fibers such as the hair, which consists in applying to said fibers the dyeing composition according to the invention for a time sufficient to obtain the desired coloring, then possibly rinsing and washing the fibers. According to a first variant, a composition as defined is applied to said fibers, dry or wet, for a sufficient time, after which it is rinsed. It is washed optionally with shampoo, then rinsed again and dried or allowed to dry the resulting fibers. According to a second variant of the process, a composition as defined is applied to said fibers, dry or wet, without final rinsing. The first variant can be used for any type of composition, whether or not these comprise an oxidizing agent and / or an additional direct dye different from those of the invention and / or an oxidation base possibly associated with a coupler.

The second variant is particularly suitable for compositions which do not comprise oxidation dye (oxidation base and optionally coupler) or an oxidizing agent. In the case of the first variant of the method, the application time is usually sufficient to develop the desired coloration and / or lightening (s). In these two variants, it is possible to add a heating step and / or a post- or pre-treatment step carried out using a basic composition having a pH ranging from 7.1 to 13 and preferably ranging from 8 to 12 optionally containing one or more oxidizing agents. Treatment with a basic composition having a pH of from 7.1 to 13 is most preferred. In this basic composition can be used all the alkalinizing agents described above and in particular ammonia, alkanolamines, carbonates or alkali hydroxides. As an indication, the duration of application of the various compositions is about 1 to 60 minutes and more particularly about 5 to 45 minutes.

Furthermore, the temperature at which the process according to the invention is carried out is generally between room temperature (15 to 25 ° C.) and 210 ° C. and more particularly between 20 and 80 ° C.

The post-treatment or pre-treatment composition by applying a basic composition to the keratin fibers may also be applied under heat. Another object of the invention is a multi-compartment device.

A first version is a device comprising at least one compartment containing a composition comprising one or more staining precursors of formula (I) as described above and a compartment comprising one or more liquid organic compounds having a lower solubility parameter value bH or equal to 15 (MPa) 1/2 at 25 ° C. A second device corresponds to the first device as described above further comprising one or more other compartments, at least one of which contains a composition comprising one or more oxidizing agents.

A third device comprises at least one compartment containing a composition comprising one or more staining precursors of formula (I) as described above and one or more liquid organic compounds having a solubility parameter value bH of less than or equal to 15 ( MPa) 1/2 at 25 ° C and a compartment containing a composition comprising one or more oxidizing agents. All these devices may further comprise an additional compartment containing a basic post-treatment composition having a pH ranging from 7.1 to 13. Thus, the invention relates to a multi-compartment device or "kit", comprising either a compartment containing a dyeing composition as defined above, and optionally a compartment at least one of which contains a composition comprising one or more oxidizing agents, and optionally another compartment comprising a basic post-treatment composition having a pH of 7, 1 to 13, two compartments for generating by mixing a dyeing composition as defined above. All these devices can be equipped with means for delivering the desired mixture onto the hair, such as the devices described in patent FR 2586913. The following examples are intended to illustrate the invention without limiting its scope. .

Examples of dyeing compositions: Example 1 The following coloring composition A was prepared from the following ingredients in the following proportions indicated in% in grams of active material except for the dyes. Composition A 3-acetoxyindole 0.0034 mole Isopropanol 12.5g Propylene carbonate g Benzyl alcohol 2.5 g Ethanol 5 g Hydroxyethyl cellulose [2] 2g (molecular weight: 720 000) pH agent qsp pH = 2.7 Perfume qs Water qs 100g 10x'13-acetoxyindole [2] Natrosol 250 MR marketed by the company Aqualon The composition (A) is applied to strands of natural hair at 90% white (BN) and to locks of hair at 90% white permed. After 45 minutes of exposure at 40 ° C., the locks are dewatered and then again treated for 15 minutes at room temperature with an aqueous composition comprising 10% by weight of ammonia containing 20% of ammonia in water. The locks are then washed with a standard shampoo, rinsed and then dried. This results in an intense blue color that is stubborn to shampoos. It can also be seen that the medium of the composition A makes it possible to confer satisfactory colors on the locks of hair.

Example 2

The following coloring compositions B and C are prepared from the following ingredients in the following proportions indicated in grams of active material except for the dyes. Composition B Composition C 3-acetoxyindole 0.0034 mole 0.0034 mole Isopropanol 5g - Benzyl alcohol - 5 g Ethanol 15g 15g pH agent pH = 2.7 pH = 2.7 Water Qsp = 100 g Qsp = 100 g The The procedure of dyeing with compositions B and C is identical to that of example 1. It is observed that composition B leads to a coloration having a low intensity while composition C leads to a coloration having a sustained intensity.

EXAMPLE 3 The following coloring compositions D, E, F and G are prepared from the following ingredients in the following proportions indicated in grams of active material except for the dyes. Composition Composition Composition Composition DEFG 3-acetoxyindole 0.0034 0 , 0034 0.0034 0.0034 [1] mole mole mole mole Ethanol 15g 15g 15g 15g Alcohol 5g 1g - - benzyl 3-phenyl-1- - 0.5g - - propanol 2-phenyl-1- - 1g - - ethanol Acid 0.5g 0.5g - - benzoic Decanol - - 5g - Propylene - - - 6g glycol butyl ether Lauryl sulfate - - 2g - sodium Hydroxyethyl 2g 2g 2g 2g cellulose [2] (molecular weight: 720,000) Agent pH qsp qsp qsp qsp pH = 2.7 pH = 2.7 pH = 2.7 pH = 2.7 Perfume qs qs qs qs Water qs 100g qs 100g qs 100g qs 100g [1] 3-acetoxy indole marketed [2] Natrosol 250MR marketed by the company Aqualon The compositions D, E, F and G are applied to strands of 5 natural hair with 90% white (BN) and on locks of hair at 90% white permeded (BP). After 30 minutes of exposure at 40 ° C., the locks are dewatered and then again treated for 15 minutes at room temperature with a composition obtained by mixing weight for weight with an aqueous solution containing 10% by weight of ammonia and an aqueous solution containing 6%. by weight of hydrogen peroxide. The locks are then washed with a standard shampoo, rinsed and then dried. A powerful coloring is then obtained which is resistant to shampoos and ultraviolet radiation.

Example 4

The following H, I, J and K coloring compositions are prepared from the following ingredients in the following proportions in grams of active material in the following table except for the dyes. Composition Composition Composition Composition HIJK 3-acetoxyindole 0.0034 0.0034 0.0034 0.0034 [1] mole mole mole mole Curcumin 0.5g 0.5g 0.5g 0.5g Orcein 0.3g 0.3g 0, 3g 0.3g Chlorophylline 0.15g 0.15g 0.15g 0.15g Sorghum 0.02g 0.02g 0.02g 0.02g Lactic Acid 0, Olg 0, Olg 0, Olg 0, Olg Ethanol 15g 16g 15g 10g Alcohol 5g 1g - - benzyl 3-phenyl-1- - 0.5g - - propanol 2-phenyl-1- - 1g - - ethanol Acid 0.5g 0.5g - - benzoic Decanol - - 5 g - Propylene - - - 6g glycol butyl ether Lauryl sulphate - - 2g - sodium Hydroxyethyl 2g 2g 2g 2g cellulose ~ 21 (molecular weight: 720 000) pH agent qsp qsp qsp pH = 2.7 pH = 2.7 pH = 2.7 pH = 2.7 Perfume qs qs qs qs Water qs 100g qs 100g qs 100g qs 100g [1] 3-acetoxyindole marketed [2] NATROSOL 250 MR sold by Aqualon.

The compositions H, I, J and K are applied to locks of natural hair 90% white (BN) and strands of hair 90% white permed (BP). After 30 minutes of exposure at 40 ° C., the locks are dewatered and then again treated for 15 minutes at room temperature with a composition obtained by mixing weight for weight with an aqueous solution containing 10% by weight of ammonia and an aqueous solution containing 6%. of hydrogen peroxide. The locks are then washed with a standard shampoo, rinsed and then dried. The result is strong brown colourations that are resistant to shampoo and ultraviolet radiation.

Claims (18)

REVENDICATIONS1. A dyeing composition for keratinous fibers, in particular human keratin fibers such as the hair, comprising, in a medium suitable for dyeing (i) one or more indole-derived dye precursors of formula (I): I) in which: R1, R2, R3 and R4 represent, independently of one another, a hydrogen atom; a halogen atom; a hydroxyl group; a linear or branched, optionally substituted C1-C4 alkyl group; a linear or branched, optionally substituted C1-C4 alkoxy group; R represents a radical derived from a polyol; a C2-C6 acyl group, linear or branched, optionally substituted; a group PO3MM '; a group S03M2; a linear or branched, optionally substituted alkyl (C1-C4) carboxy group; with M denoting a hydrogen atom or an ion derived from an alkali or alkaline earth metal, an ammonium ion or an ion derived from an organic amine and M 'having the same possible meanings as M and may also designate a trialkyl (C1-C4) ammonioalkyl (C1-C4) group; Z represents a hydrogen atom; a C2-C6 acyl group, linear or branched, optionally substituted; a linear or branched, optionally substituted C1-C10 alkyl group; W represents a hydrogen atom; a halogen atom; a hydroxyl group; a linear or branched C1-C4 alkoxy group, optionally substituted; a C2-C4 acyl group, linear or branched, optionally substituted; a linear or branched, optionally substituted C1-C10 alkyl group; a salified carboxy group or not; a group ûSCH3; a group - 5 SO2CH3; and (ii) one or more liquid organic compounds having a Hansen solubility parameter value 8H of less than or equal to 15 (MPa) 1/2 at 25 ° C. 2. Composition according to claim 1, characterized in that R1 and / or R2 and / or R3 and / or R4 represent a hydrogen atom or a halogen atom. 3. Composition according to claim 1 or 2, characterized in that Z represents a hydrogen atom. 4. Composition according to any one of claims 1 to 3, characterized in that R represents a radical derived from a polyol of formula (II): embedded image in which: n denotes 0 or 1; - R5 represents a hydroxyl group or a ketone function; - R6 represents a hydroxyl group, a group -CH2OH, a group -CH2000CH2CO2H; R7 represents a hydrogen atom or a hydroxyl group; - R8 represents a hydrogen atom or a hydroxyl group, or R represents a radical derived from a polyol of formula (III): ## STR2 ## in which - n 'denotes 0 or 1; - R'5 represents a hydroxyl group or a ketone function; - R'6 represents a hydroxyl group or a group - CH2OH; - R'7 represents a hydrogen atom or a hydroxyl group. 5.Composition according to any one of the preceding claims, characterized in that W represents a hydrogen atom or a group -SCH3, and preferably a hydrogen atom. 6. Composition according to any one of the preceding claims, characterized in that the precursor (s) of coloring of formula (I) are chosen from the following compounds: Hop H. ~ Indoxyl bD-glucoside ~~ 'In Indican H>, ,) o ~ - k 'F {HJ OH. . Wherein Indoxyl-3-O- (6'-O-malonyl- (3-D-o-ribohexo-3-ulopyranoside) oester (Isatan A) Indoxyl-5-ketogluconate H 0 HO aH ¢ 7H H co OH-3-O-O- (3-D-ribohexyl-3H-OH-1-uroxyranoside N, O); R (Isatan B) O HO 3-acetoxyindole / o / o N-methyl acetate; indoxyl O 1,3-diacetoxyindole OON o Disodium salt 3-indoxylphosphate OP // O Na * Na 'N 3 -indoxyl choline phosphate // N Propanoic acid of 2- (5-bromo-4-, o (3-chloro-3-indoxyl) N-o (5-bromo-4-chloro-3-indolyl) -bD-Clibofuranoside Br-6-bromoindoxyl Br-6-acetate N-acetate bromo- indoxyl Br O ~~ ON Br, / O, O 5-Bromo- indoxyl diacetate O CI O ~ O 4-chloro-indoxyl-1,3-diacetate N 5-chloro-indoxyl acetate CI NO-O 6-chloro-3-indoyl acetate O CI NO ~ O 7-chloroindoxyl-1,3-diacetate N and O 6-chloro-3-indoxyl-1,3-diacetate C) 1 CI-N-O 5-bromo-4-chloro indolyl acetate Br and OON 5-bromo 4-chloroindoxyl diacetate Br and 0 O-ON / N-acetyl-5-bromo-6-chloro-Br-O-hydroxyindole Cl N 3-dihydrogenphosphate 1H-Indol-H OPO3H2 3-ole N 1 3-dihydrogenphosphate of 5-bromo-N-4-chloro-1H-indol-3-ol Br OPO3H2 5- and 6-bromo-6-chloro-1H-Indol-3-ole di-dihydrogen phosphate ester Br 0P03H2 Dihydrogen phosphate ester c 6 1-chloro-1H-Indol-3-ole 0P03H2 Dihydrogen phosphate ester N 4-chloro-1H-Indol-3-ole N 1 OPO3H2 1 1H-F 6-fluoro-Indol-3-ole 1N dihydrogenphosphate ester 1N OP03H2 Ester of 6-iodo-1H-Indole dihydrogen phosphate 1N 0P03H2 1-OPO3H2 methyl-1H-Indol-3-ol dihydrogen phosphate ester 0 0 // Potassium salt 3-indoxyl sulfate N 0% o K. Salt potassium 5-bromo-6-CI 0 K + chloro-3-indolyl-sulfate hydrate O-10 ° N OS03-Tyrindoxyl sulphate Br A SCH3 N Potassium salt 5-bromo-4-bromo-chloro-3-indolylsulfate 0 wherein K 'δ / ° N 7.Composition according to any one of the preceding claims, characterized in that the compound (s) of formula (I) is or are selected from Indican, potassium 3-indoxysulfate, Isatan A, Isatan B, 3-acetoxyindole, 3-indoxyl disodium phosphate, tyrindoxyl sulfate and 6-bromoindoxyl acetate . 8.Composition according to any one of the preceding claims, characterized in that the liquid organic compound or compounds have a Hansen solubility parameter value 6h ranging from 6 (MPa) 1/2 to 14 (MPa) 1/2 to 25 ° C, and preferably ranging from 4 (MPa) 1/2 to 10 (MPa) 1/2 at 25 ° C. 9. Composition according to any one of the preceding claims, characterized in that the liquid organic compound (s) have a molecular weight of less than 500 g / mol, and even more preferentially less than 250 g / mol. 10. Composition according to any one of the preceding claims, characterized in that the liquid organic compound (s) are alcohols, preferably chosen from benzyl alcohol, 3-phenyl-1-propanol and 2-phenyl-1. -ethanol, 1-decanol and / or a mixture of these compounds. 11. Composition according to any one of the preceding claims, characterized in that the liquid organic compound (s) are acids, preferably acetic acid. 12. Composition according to any one of the preceding claims, characterized in that the liquid organic compound (s) are ethers, preferably chosen from propylene glycol butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether and / or propylene glycol propyl ether. 13. Composition according to any one of the preceding claims, characterized in that it further comprises one or more surfactants and / or a plurality of thickening agents. 14. Composition according to any one of the preceding claims, characterized in that it has a pH ranging from 1 to 12, preferably less than 7, and even more preferably from 1 to 5. 15. A process for dyeing keratinous fibers, in particular human keratinous fibers, such as the hair, characterized in that it comprises the application, on the fibers, of the dyeing composition as defined according to any one of the Claims 1 to 14 for a time sufficient to obtain the desired color. 16. The method of dyeing according to claim 15, characterized in that it further comprises a heating step and / or a step of post- or pre-treatment with a basic composition having a pH ranging from 7.1 to 13. and preferably from 8 to 12 optionally containing one or more oxidizing agents. 17. Use of the dye composition as defined in any one of claims 1 to 14 for dyeing keratinous fibers, in particular human keratin fibers such as hair. 18. Multi-compartment device or "kit", comprising either a compartment containing a dyeing composition as defined in any one of claims 1 to 14, and optionally a compartment of which at least one contains a composition comprising one or a plurality of oxidizing agents, and optionally another compartment comprising a basic post-treatment composition having a pH ranging from 7.1 to 13, or two compartments for generating by mixing a dyeing composition as defined according to any one of claims 1 at 13.