FR2968946A1 - PROCESS FOR COLORING KERATIN FIBERS FROM RESORCINOL DERIVATIVES, SULPHATE SALTS, OXIDIZING AGENTS AND ALKALINIZING AGENT - Google Patents

Abstract

The subject of the invention is a method for dyeing keratin fibers, in particular hair, using i) at least one resorcinol derivative, ii) at least one particular sulfate salt, iii) at least one oxidizing agent and iv) at least one an alkalinizing agent. Another subject of the invention is a cosmetic composition for the coloration of keratinous fibers comprising ingredients i) to iv) as defined above. Another object of the invention is a multi-compartment device comprising ingredients i), ii), iii) and iv). This dyeing process makes it possible to obtain better chromatic coloring, which is intense and stubborn and without the use of oxidation bases, such as para-phenylenediamines and para-aminophenols.

Description

The subject of the invention is a method for dyeing keratinous fibers, in particular hair, using i) at least one keratinous fiber coloring process, for example: a resorcinol derivative, ii) at least one sulphate salt, iii) at least one oxidizing agent and iv) at least one basifying agent. This coloring process makes it possible to obtain better chromatic coloring, which is intense and stubborn and without the use of oxidation bases, such as para-phenylenediamines and para-aminophenols.

It is known to obtain so-called "permanent" stains with dyeing compositions containing oxidation dye precursors, generally called oxidation bases, such as ortho or para-phenylenediamines, ortho or para-aminophenols and compounds. heterocyclic. These oxidation bases are colorless or weakly colored compounds which, when combined with oxidizing products, give rise to colored compounds by a process of oxidative condensation. It is also known that the shades obtained can be varied by combining these oxidation bases with couplers or color modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds such as indolic compounds for stability to light and shampoo. This oxidation dyeing process consists in applying bases or a mixture of bases and couplers to the keratinous fibers with hydrogen peroxide (H2O2 or hydrogen peroxide) as an oxidizing agent, to be allowed to diffuse, then to rinse the fibers. The resulting colorations are permanent, strong, and resistant to external agents, including light, weather, washing, perspiration and friction. The derivatives of 5,6-dihydroxyindoles are also capable of generating, by "auto-oxidation", dark shades, but the resulting colorations are not always satisfactory, particularly in terms of chromaticity, power or remanence. To reach dark shades, the presence of oxidation base paraphenylenediamines is almost indispensable. There is a real need to search for new means of staining keratinous fibers allowing access to homogeneous, powerful and / or chromatic colorings with dark shades ideally without aromatic amine such as para-phenylenediamines and para-aminophenols, which would be light-stable, weather-resistant, stubborn to washings and transpiration, and sufficiently stable in the presence of oxidizing agents such as hydrogen peroxide so as to obtain a simultaneous lightening of the fiber with the advantages described above. There is also a need to provide coloring systems that make it possible to obtain dark, powerful and persistent coloring that does not use chemical oxidizing agents, but "auto-oxidizable" systems that can oxidize with the oxygen from the air.

This object is achieved by the present invention which relates to a process for dyeing keratinous fibers comprising the application to the keratinous fibers of: i) at least one resorcinol derivative of formula (I), and also its acid salts or organic or inorganic base, and its solvates such as hydrates: R3 (I) formula (I) in which R 'to R4, identical or different, represent a hydrogen atom, halogen; or a group chosen from: - (C, -C, o) optionally substituted alkyl, in particular optionally substituted with at least one hydroxyl radical; (C1-C10) alkoxy; carboxyl-C (O) -OH or carboxylate -C (O) -O-, W; with W representing a cationic counterion such as an alkali or alkaline earth metal, or an ammonium, -C (O) -O-R5 or -OC (O) -R5, with R5 representing a group (C, - C, o) alkyl, especially -C (O) -O-R5; amido -C (O) -NR6R7 or -NR6-C (O) -R7 with R6 and R7, identical or different, representing a hydrogen atom or a group (C, -C, o) alkyl, particularly -C (0) -N H2; (C1-C10) alkylcarbonyl; hydroxy; and ^ amino -NR8R9, with R8 and R9, identical or different, representing a hydrogen atom or a (C, -C, o) alkyl group, particularly -NH2; ii) at least one alkali metal, alkaline-earth metal or ammonium, (C 1 -C 6) alkylammonium or tri (C 1 -C 6) alkylammonium sulfate; iii) at least one oxidizing agent, preferably chemical; and iv) at least one basifying agent; it being understood that: ingredients i) to iv) may be applied to the fibers either together or separately; the pH of the composition comprising the ingredient or ingredients iv) is basic i.e greater than 7; preferably between 7.5 and 12; and when the compound (s) of formula (I) represent resorcinol i.e. R2, R3 and R4 represent a hydrogen atom, then the process does not use para-phenylenediamine. Another subject of the invention is a cosmetic composition for dyeing keratin fibers, comprising: i) at least one resorcinol derivative of formula (I), as defined above; ii) at least one sulfate salt; iii) at least one oxidizing agent, preferably chemical; and iv) at least one basifying agent; it being understood that: the pH of the composition is basic i.e greater than 7; preferably between 7.5 and 12; and when the compound or compounds of formula (I) represent resorcinol i.e. R2, R3 and R4 represent a hydrogen atom, then the composition does not contain para-phenylenediamine.

Another object of the invention relates to a multi-compartment device comprising ingredients i) to iv) as defined above.

The composition and the dyeing method of the invention have the advantage of coloring human keratinous fibers, with results of powerful coloring, chromatic, resistant to washes, perspiration, sebum and light and more durable without alteration said fibers. In addition, the colorations obtained from the process give homogeneous colors from the root to the tip of a fiber (low color selectivity). The shades obtained after staining with the composition or the process of the invention are very intense, in particular at a temperature greater than room temperature, preferably at a temperature of between 45 and 80.degree. In addition, the colorations obtained with the composition or the process of the invention are compatible with conventional oxidation conditions for lightening the hair. The hue is durable over time and does not turn even after several shampoos. The colorations are particularly stubborn with shampoos.

Unless otherwise indicated in the present invention, it is understood that: the "aryl" radical represents a mono or polycyclic carbon group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl; preferably the aryl group is a phenyl; the "aryl" radical or the aryl part of a radical may be substituted by at least one substituent borne by a carbon atom, chosen from: a C 1 -C 16, preferably C 1 -C 8, alkyl radical, optionally substituted; by one or more radicals chosen from hydroxyl, C 1 -C 2 alkoxy, (C 2 -C 4) (poly) -hydroxyalkoxy, acylamino, amino radicals substituted by two identical or different C 1 -C 4 alkyl radicals, optionally at least one hydroxyl group or both radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered, preferably 5 or 6-membered, optionally substituted saturated or unsaturated heterocycle optionally comprising another heteroatom identical or different from nitrogen; a halogen atom such as chlorine, fluorine or bromine; a hydroxy group; a (C 1 -C 2) alkoxy radical; a (C 1 -C 2) alkylthio radical; a (poly) -hydroxy (C2-C4) alkoxy radical; an amino radical; a 5- or 6-membered heterocycloalkyl radical such as cyclohexyl; a 5- or 6-membered optionally cationic heteroaryl radical, preferentially imidazolium, and optionally substituted with a (C 1 -C 4) alkyl radical, preferably methyl; an amino radical substituted with one or two identical or different (C 1 -C 6) alkyl radicals, optionally substituted with at least: i) a hydroxyl group; ii) an amino group optionally substituted with one or two optionally substituted C1-C3 alkyl radicals, said alkyl radicals being able to form, with the nitrogen atom to which they are attached, a 5- to 7-membered heterocycle, optionally saturated or unsaturated; substituted optionally comprising at least one other heteroatom different or different from nitrogen; -N (R) -C (O) -R 'in which the radical R is a hydrogen atom, a (C 1 -C 4) alkyl radical optionally bearing at least one hydroxyl group and the radical R' is a (C 1 -C 2) alkyl radical; - R2N-C (O) - wherein the radicals R, identical or different, represent a hydrogen atom, a (C 1 -C 4) alkyl radical optionally bearing at least one hydroxyl group; R'-S (O) 2 -N (R) - in which the radical R represents a hydrogen atom, a C 1 -C 4 alkyl radical optionally bearing at least one hydroxyl group and the radical R 'represents a (C 1 -C 4) alkyl radical, a phenyl radical; - R2N-S (O) 2- in which the radicals R, identical or not, represent a hydrogen atom, a (C 1 -C 4) alkyl radical optionally bearing at least one hydroxyl group; a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not); a cyano group; a polyhaloalkyl group comprising from 1 to 6 carbon atoms and from 1 to 6 halogen atoms, which are identical or different, the polyhaloalkyl group is, for example, trifluoromethyl; an "alkyl" radical is a saturated C 1 -C 16 saturated hydrocarbon radical, linear or branched, preferably C 1 -C 8 such as methyl or ethyl; the expression "optionally substituted" ascribed to the alkyl radical, that is to say that said alkyl radical may be substituted with one or more radicals chosen from the groups i) hydroxy, ii) (C 1 -C 4) alkoxy, iii) acylamino, iv) amino optionally substituted with one or two radicals (C 1 -C 6) alkyl, which are identical or different, said alkyl radicals being able to form, with the nitrogen atom carrying them, a heterocycle comprising from 5 to 7 ring members, possibly comprising another different heteroatom or not nitrogen; v) or a quaternary ammonium group -N + R'R "R" ', M-for which R', R ", R" ', which may be identical or different, represent a hydrogen atom, or a group (C, -C6) ), or -N + R'R "R" 'forms a heteroaryl such as imidazolium optionally substituted by a (C 1 -C 6) alkyl group, and M- represents the counterion of the organic acid, mineral or the corresponding halide; preferably when the alkyl radical is optionally substituted, it is substituted by at least one hydroxyl group, especially hydroxymethyl; an "alkoxy" radical is an alkyl-oxy or alkyl-O- radical for which the alkyl radical is a linear or branched C1-C16, preferably C1-C8, hydrocarbon radical; an "alkylthio" radical is an alkyl-S- radical for which the alkyl radical is a hydrocarbon radical, linear or branched, C1-C16, preferably C1-C8; the boundaries delimiting the range of a range of values lie within this range of values; and - the expression "at least" means "one or more". i) derivative of resorcinol of formula (I): A particular embodiment of the invention relates to resorcinol derivatives or their mixtures of formula (I) in which: R 'which represents: a hydrogen atom; a halogen atom, preferably a chlorine atom; a linear or branched (C 1 -C 4) alkyl group; a hydroxy group; a (C 1 -C 4) alkylcarbonyl group, preferentially methylcarbonyl; a carboxyl or carboxylate group as defined above; an amido radical such as -C (O) -NH 2; or an amino radical such as NH 2; and / or - R3 which represents: a hydrogen atom; a (C 1 -C 4) alkyl group optionally substituted by a hydroxy group; a carboxyl group; a (C 1 -C 4) alkylcarbonyl group, preferentially methylcarbonyl; a hydroxy group; an amido group such as -C (O) -NH 2; an amino group such as -NH 2; or a (C 1 -C 4) alkoxy group, preferably a methoxy radical. and / or - R2 or R4 independently of one another represent: a hydrogen atom; a halogen atom, preferably a chlorine atom; a linear or branched (C 1 -C 8) alkyl group, preferably C 1 -C 4; a (C 1 -C 4) alkoxy group, preferentially a methoxy radical; a carboxyl group; an alkyl carboxylate group such as -C (O) -O-R5 with R5 representing a (C1-C4) alkyl group; a (C 1 -C 4) alkylcarbonyl group, preferentially methylcarbonyl; a hydroxy group; or an amino group such as -NH 2.

According to one particular embodiment of the invention, the resorcinol derivatives of formula (I) in which: R 4 represents a hydrogen atom; and - R 'represents: a hydrogen atom; or a linear or branched (C 1 -C 4) alkyl group; and / or - R3 represents: a hydrogen atom; a linear or branched (C 1 -C 4) alkyl group; a hydroxy group; or a (C 1 -C 4) alkoxy group, preferably a methoxy radical; and / or - R2 represents: a hydrogen atom; a halogen, preferably a chlorine atom; a linear or branched (C 1 -C 4) alkyl group; a (C1-C4) alkoxy group; a carboxyl group; or a hydroxy group.

More particularly, the resorcinol derivatives of formula (I) according to the invention are chosen from the following compounds: compounds Structure Name Resorcinol; Benzene-1,3-diol or 3- HO OH hydroxyphenol 2 HO OH 2-Methyl-benzene-1,3-diol 3 OH OH 2,5-Dimethyl-benzene-1,3-diol 4 HO OH 2,4 4-Chloro-benzene-1,3-diol OH-OH-5-Methyl-benzene-1,3-diol 7-OH-4-Methyl-benzene-1,3-diol OH 5-Methoxy-benzene-1,3-diol HOOMOM 4-Methoxy-benzene-1,3-diol OH 1,2-Benzene-1,2,4-triol OH-1,3-benzene 5-triol 12 HO OH 4-butyl-benzene-1,3-diol 13 HO OH 4-hexyl-benzene-1,3-diol 14 HO O 2,4-Dihydroxy-benzoic acid methyl ester OH HO OH 2,4 1,3-Dihydroxy-6-methyl-benzoic acid 1,3-dihydroxy-6-methyl-benzoic acid 1,3-diol-benzene-1,3-diol Methyl 2,4-dihydroxy-3,6-dimethylbenzoate OH OH 5-Hydroxymethyl-benzene-1,3-diol 21 OH OH 1- (2,6-Dihydroxy-phenyl) -ethanone 22 HO OH 4-ethyl-benzene-1,3-diol 23 HO O OH OH 3,5-Dihydroxy-benzoic acid 24 HO O 1- (2,4-Dihydroxy-phenyl) -ethanone OH 25 HO OH 1 - (3 , 5-Dihydroxy-phenyl) -ethanone 2,6-Dihydroxy-benzoic acid OH 27 O NH 2 3,5-Dihydroxybenzamide HO 2,6-Dihydroxy-benzamide NH 2 29 NH NH 4 amino-benzene-1,3-diol OH 2 NH 2 OH-amino-benzene-1,3-diol HO NH 2 OH 5-amino-benzene-1,3-diol 3-Dihydroxy-3-methyl-phenyl) -ethanone HO 3- (2,3,4-Trihydroxy-phenyl) -ethanone 3,4,5-Trihydroxy-benzamide OH HO OH OH 2,3,4-Trihydroxy-benzoic acid OH 2,4-Trihydroxybenzoic acid OH HOOH 4-pentylbenzene-1,3-diol 37 And / or their organic or mineral base salts and / or their solvates. Preferentially, the resorcinol derivatives of formula (I) are chosen from compounds 1 to 11 as defined in the preceding table.

According to the invention, the resorcinols derivative (s) are synthetic, natural, or found in natural extracts. For example, mention may be made of resorcinols obtained from gum-resin extract of the galbanum, sagapenum or ferula galbaniflua sap type.

According to one embodiment, the resorcinol derivative (s) of formula (I) are present in the composition without the presence of an oxidation agent or coupler. According to another embodiment of the oxidation dyes are present with possibly couplers, it being understood that the oxidation base is different from para-phenylenediamine. In this latter variant, the resorcinol derivative (s) of formula (I) are at a total concentration which is at least 10 times greater than the concentration of other oxidation dye precursors, such as the bases that may be present in a mixture.

Preferably, the resorcinol derivative (s) are in the composition or in the process according to the invention at a concentration of between 10 -4 and 10 -1 mol per 100 g (%) of the composition containing the resorcinol derivative (s). or the extract or extracts comprising them, especially between 10-4 to 5.10-2 mol% and preferably between 0.01 to 0.025 mol%. ii) sulfate salt: Sulfates are salts derived from sulfuric acid H2SO4 whose sulphate ion is SO42- (See "Sulfites, Thiosulfates, and Dithionites" in Ullmann's Encyclopedia of Industrial Chemistry, 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim - http://onlinelibrary.wiley.com/doi/10.1002/14356007.a25_477/pdf). The pH of the sulphates according to the invention is neutral or slightly acidic (pH between 7 and 6.6).

According to another preferred embodiment of the invention the sulphates are sulphates of formula M2SO3 or M'SO3 or hydrogen sulphate of formula MHSO3 with M representing an alkali metal such as Na, K or (di) (C, -C6) ( alkyl) ammonium or tri (C 1 -C 6) alkylammonium such as NH 4 + The sulphates of the invention are in particular salts of alkali or alkaline earth metals or of ammonium, (di) (C 1 -C 6) alkylammonium or tri (C 1 -C 6) alkylammonium; preferentially, the cationic counterion of the sulphate is chosen from sodium and potassium, and ammonium. Preferably, the sulphate salts according to the invention are chosen from: a) potassium disulfate [16731-55-8]: K2S205; b) sodium disulfate [7681-57-4]: Na2S2O5; c) ammonium sulfate [10196-04-0]: (NH4) 2SO3; d) sodium sulfate [7757-83-7]: Na2SO3; and e) sodium hydrogen sulfate [7631-90-5]: NaHSO3.

According to a preferred embodiment of the invention, the sulphate salt or salts used in the composition or process of the invention represent from 0.001% to 10% by weight approximately of the total weight of the composition (s) containing this or these salts of sulphates and even more preferably from 0.05% to 0.1% by weight approximately. According to a more preferred embodiment of the invention, the sulphate salt or salts used in the composition or in the process of the invention represent between 0.25 and 10 mol. %, especially between 0.5 and 10 mol. %; between 2 and 10 mol. %; and 0.5 and 10 mol. %. iii) oxidizing agent:

In the context of the present invention, the process of the invention can be carried out in the absence of a chemical oxidizing agent, that is to say by letting the oxygen of the air act. According to another dyeing process of the invention, said method uses a chemical oxidation agent.

By chemical oxidizing agent is meant: a) ozone; b) alkali metal persalts or quaternary ammonium persalt such as perborates, persulfates, percarbonates, peroxodiphosphates, Oxone® particularly the oxidant is selected from sodium perborate, sodium persulfate, persulfate potassium, ammonium persulfate, sodium percarbonate, potassium percarbonate; c) aliphatic organic C1-C6 and C6-C20 aromatic peracids and their percarboxylate forms, such as performic acid, peracetic acid, perbenzoic acid derivatives, trifluoroacetic acid, peroxyphthalic acid, peroxymaleic acid, peroxypropionic acid especially the oxidant is peracetic acid; d) organic peroxides, such as dioxirane, C1-C6 alkyl peroxides, benzoyl peroxide, peroxo (C 1 -C 6) alkyl carboxylates, bis (tri) (C 1 -C 6) peroxides alkylsilyl such as bis (trimethylsilyl) peroxide, C 1 -C 6 alkyl peroxydicarbonates, sodium nonanoyloxybenzene sulfonate as described in WO1995000625 and US4412934 e) oxidizing anions such as nitrites, nitrates, hypochlorites, hypobromites, hypoiodites, chlorites, bromites, iodites, chlorates, bromates, iodates, periodates, the particular oxidant is selected from hypochlorite or alkali metal periodate such as sodium hypochlorite or potassium periodate. sodium; f) N-oxy stable radicals (NO.), such as the radical 2,2,6,6-tetra (C 1 -C 6) alkylpiperidino-oxy, 2,2,6,6-tetra (C 1 -C 6) alkylmorpholino-oxy salts of Frémy nitrosodisulfonates, N-oxide morpholine; the oxidant is especially selected from the 2,2,6,6-tetramethylpiperidinyloxy radical; and (g) hypervalent iodine derivatives, such as iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid derivatives, periodinanes, alkyls and benzoylhypoiodites More preferentially the oxidant is chosen from iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid, Dess-Martin periodinane h) the following organic compounds: N-halosuccinimides, the trichloroisocyanuric acid, N-hydroxyphthalimide, alkyl nitrites The possible supports of these oxidants a) to h) can be selected from silica, alumina, coal, charged or neutral polymers i) hydrogen peroxide or hydrogen peroxide or hydrogen peroxide generator systems, such as: (1) urea peroxide; i-2) polymeric complexes that can release hydrogen peroxide such as polyvinylpyrrolidone / H2O2 in particular being in the form of powders and other polymer complexes described in US 5,008,093; US 3,376,110; US 5,183,901; i-3) oxidases producing hydrogen peroxide in the presence of a suitable substrate (for example glucose in the case of glucose oxidase or uric acid with uricase); i-4) metal peroxides generating hydrogen peroxide in water such as calcium peroxide, magnesium peroxide; i-v) perborates; or i-vi) percarbonates.

In particular, the chemical oxidizing agent (s) are chosen from (i) hydrogen peroxide or hydrogen peroxide generating systems. More particularly H2O2.

According to a preferred embodiment of the invention, the method uses one or more hydrogen peroxide generator systems selected from among i) urea peroxide, i-2) complexes polymers capable of releasing hydrogen peroxide selected from polyvinylpyrrolidone / H 2 O 2; i-3) oxidases; i-v) perborates and i-vi) percarbonates.

More preferentially, the composition according to the invention comprises hydrogen peroxide. Furthermore, the composition (s) comprising hydrogen peroxide or the hydrogen peroxide generator (s) may also contain various adjuvants conventionally used in hair dyeing compositions and as defined below in accordance with US Pat. point entitled "cosmetic composition".

According to one particular embodiment of the invention, the hydrogen peroxide or hydrogen peroxide generator system (s) used is (are) preferably from 0.001% to 12% by weight. expressed as hydrogen peroxide relative to the total weight of the composition or compositions containing them. More particularly, the concentration of hydrogen peroxide at 20 volumes is between 0.01 to 0.15 mol per 100 g (%) of composition of the composition containing peroxide; preferably between 10.4 and 5.10-1 mol% and in particular between 0.0125 and 0.25 mol%. iv) alkalizing agent

The basifying agent present in the composition according to the invention or used in the dyeing process according to the invention as the fourth ingredient iv) is an agent for increasing the pH of the composition (s) in which it is found and which is different from the sulphate salts as defined above. The basifying agent is a Bronsted, Lowry or Lewis base. It can be mineral or organic. In particular, said agent is chosen from i) (bi) carbonates, ii) ammonia, iii) alkanolamines such as mono-, di- and triethanolamines and their derivatives iv) oxyethylenated and / or oxypropylenated ethylenediamines, v) inorganic or organic hydroxides, vi) alkali metal silicates such as sodium metasilicates, vii) basic amino acids such as arginine, lysine, ornithine, citruline and hystidine, and viii) the compounds of formula (II) below: ## STR2 ## wherein W is divalent (C 1 -C 10) alkylene group optionally interrupted by at least one heteroaromatome such as O , S, NRe, and / or said alkylene group is optionally substituted by at least one hydroxy group or a (C 1 -C 4) alkyl radical; Ra, Rb, Rd, Rd and Re, identical or different, represent a hydrogen atom, (C 1 -C 4) alkyl or hydroxyC 1 -C 4 alkyl, preferably a propylene group. The inorganic or organic hydroxides, particularly the inorganic or organic hydroxides, are preferably selected from a) the hydroxides of an alkali metal, b) the hydroxides of an alkaline earth metal, such as hydroxides of sodium or of potassium, c) hydroxides of a transition metal, such as the hydroxides of metals of groups III, IV, V and VI, d) hydroxides of lanthanides or actinides, quaternary ammonium hydroxides and guanidinium hydroxide. The hydroxide may be formed in situ such as, for example, guanidine hydroxide by reaction of calcium hydroxide and guanidine carbonate.

By (bi) carbonates i) is understood to mean: a) alkali metal carbonates (Met2 +, CO32-), alkaline earth metal (Met2 +, CO32-) ammonium ((R "4N +) 2, CO32-) or phosphonium ((R "4P +) 2, CO32- with Met 'representing an alkaline earth metal and Met representing an alkali metal, and R", which may be identical or different, represent a hydrogen atom, a group ( C, -C6) optionally substituted alkyl such as hydroxyethyl), and b) bicarbonates, also called hydrogenocarbonates, of the following formulas: - R '+, HCO3 with R' representing a hydrogen atom, an alkali metal, an ammonium group R "4N + - or phosphonium R" 4P + - where R ", identical or different, represent a hydrogen atom, an optionally substituted (C 1 -C 6) alkyl group such as hydroxyethyl and when R 'represents a hydrogen atom the hydrogencarbonate is then called dihydrogen carbonate (CO2, H2O); and - Met'2 + (HCO3) 2 with Met 'representing an alkaline earth metal. More particularly, the basifying agent is chosen from alkali metal or alkaline earth metal (bi) carbonates; preferentially alkali metal (bi) carbonates. There may be mentioned carbonates or hydrogenocarbonates of Na, K, Mg, Ca and mixtures thereof, and in particular Na hydrogen carbonate. These hydrogencarbonates can come from natural water, for example spring water from the Vichy basin, from La Roche Posay, Badoit water (see patent for example document FR 2 814 943). Particularly mention may be made of sodium carbonate [497-19-8] = Na2CO3, sodium hydrogencarbonate or sodium bicarbonate [144-55-8] = NaHCO3, and sodium dihydrogen carbonate = Na (HCO3) 2.

According to a particularly advantageous embodiment, the alkalinizing agent or agents iv) are chosen from among i) bicarbonates, particularly alkali or ammonium, ii) ammonia, iii) alkanolamines such as ethanolamine or 2 -amino-2-methyl-1-propanol, more preferably ammonia.

The alkalinizing agent (s) as defined above preferably represent from 10 -3 to 2.5 × 10 -1 mol per 100 g (%) of the composition containing said alkalinizing agents. Particularly from 0.05 to 0.5 mol%, preferably from 0.1 to 0.25 g% by weight of the composition.

v) optionally one or more mordant (s). The composition according to the invention may also contain a mordant or etching agent conventionally used in the textile industry and cosmetically acceptable preferentially in the form of metal salts such as iron, aluminum, titanium and calcium salts. Manganese, Copper, Zinc, Strontium. By way of example, the mordant may be iron sulfate, iron gluconate, iron chloride, iron acetate, manganese gluconate, copper sulfate, iron gluconate, copper, copper chloride, copper acetate , zinc gluconate, calcium chloride, magnesium chloride, potassium titanyl oxalate, strontium acetate. Preferably the mordant used is iron sulfate. In particular, the mordants are present in the composition in proportions of between 0.001% and 10% relative to the total weight of the composition containing them.

According to another particular embodiment of the invention neither the dyeing method, nor the composition of the invention implements or contains etching agent. Water: According to one embodiment of the invention, water is preferably included in the process of the invention. It may come from the wetting of the keratinous fibers and / or the composition or compositions comprising compounds i) to iv) as defined above or from one or more other compositions. Preferably the water comes from at least one composition comprising at least one compound selected from i) to iv) as defined above. cosmetic compositions:

The cosmetic compositions according to the invention are cosmetically acceptable i.e. they comprise a coloring support which generally contains water or a mixture of water and one or more organic solvents or a mixture of organic solvents. By organic solvent is meant an organic substance capable of dissolving or dispersing another substance without chemically modifying it.

Organic Solvents: As an organic solvent, there may be mentioned, for example, C1-C4 lower alkanols, such as ethanol and isopropanol; polyols and polyol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether and monomethyl ether, hexylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol. The organic solvents are present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

Adjuvants: The composition (s) of the dyeing process according to the invention may also contain various adjuvants conventionally used in hair dyeing compositions, such as anionic, cationic, nonionic, amphoteric surfactants, zwitterionic or their mixtures, anionic, cationic, nonionic, amphoteric or zwitterionic polymers or their mixtures, mineral or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidant agents, penetrating agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as, for example, volatile or non-volatile silicones, modified or unmodified, film-forming agents, ceramides, preserving agents , opacifying agents. Said adjuvants are preferably chosen from surfactants such as anionic, nonionic surfactants or mixtures thereof and inorganic or organic thickeners. The above adjuvants are generally present in an amount for each of them ranging from 0.01 to 40% by weight based on the weight of the composition, preferably from 0.1 to 20% by weight based on the weight of the composition. of the composition. Of course, those skilled in the art will take care to choose this or these optional additional compounds in such a way that the advantageous properties intrinsically attached to the composition or to the composition (s) useful in the coloring process according to the invention are not not, or not substantially, impaired by the addition or additions envisaged.

The additional dyes: the process employing the ingredients i) to iv) as defined previously or the cosmetic composition according to the invention comprising the ingredients i) to iv) as defined previously can further implement or understand one or several additional direct dyes. These direct dyes are, for example, chosen from those conventionally used in direct dyeing, and among which may be mentioned all the aromatic and / or nonaromatic dyes of current use such as neutral, benzene neutral, acidic or cationic direct dyes, direct dyes neutral azo, acidic or cationic, natural direct dyes other than orthodiphenols, direct quinone dyes and in particular neutral, acidic or cationic anthraquinone dyes, azine, triarylmethane, indoamine, methines, styryls, porphyrins, metalloporphyrins, direct dyes, phthalocyanines, methine cyanines, and fluorescent dyes. All these additional dyes are different from orthodiphenol derivatives according to the invention. Among the natural direct dyes that may be mentioned are lawsone, juglone, indigo, isatin, curcumin, spinulosin, apigenidine, orceins. It is also possible to use the extracts or decoctions containing these natural dyes, and in particular poultices or extracts made from henna. The additional direct dye (s) used in the composition (s) preferably represent from 0.001% to 10% by weight approximately of the total weight of the composition (s) containing them and even more preferentially from 0.05% to 5% by weight approximately. . The compositions of the process using the ingredients i) to iv) as defined above or the cosmetic composition according to the invention comprising the ingredients i) to iv) as defined above can also implement or comprise one or more bases of oxidation and / or one or more couplers conventionally used for dyeing keratinous fibers. Among the oxidation bases that may be mentioned are para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, bis-para-aminophenols, ortho-aminophenols, heterocyclic bases and their addition salts. Among these couplers, mention may notably be made of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts. The oxidation base (s) present in the composition (s) are in general present each in an amount of between 0.001% and 10% by weight relative to the total weight of the corresponding composition (s).

When the oxidation bases, in particular aromatic amines such as para-phenylenediamines and / or para-aminophenols, are present in the composition of the invention or used in the process of the invention, they are in such quantities that the ratio between the amount of resorcinol derivatives of formula (I) as defined above / the amount of oxidation base is at least greater than 5; preferably, greater than 10, more preferably greater than 20. According to a preferred embodiment of the invention, the dyeing method and the composition according to the invention do not comprise para-phenylenediamines and / or para-aminophenols.

The cosmetic composition (s) of the invention may be in various galenical forms, such as a powder, a lotion, a mousse, a cream, a gel or in any other form suitable for dyeing keratinous fibers. They can also be packaged in a pump bottle without propellant or under pressure in an aerosol bottle in the presence of a propellant and form a foam. pH of the composition (s) The pH of the composition (s) containing iv) the alkalinizing agent (s) is greater than 7 and preferably between 8 and 12. Particularly between 8 and 10.

If the composition or compositions do not contain an alkalinizing agent, the pH of the composition (s) containing the oxidizing agent such as hydrogen peroxide or the hydrogen peroxide generating system is preferably less than 7, more particularly between 1 and 5. Preferably, the composition or compositions containing the resorcinol derivative (s) of formula (I) as defined previously and not containing basifying agent are at a pH of less than 7 and preferably of between 3 and 6.5. According to one particular embodiment of the invention, the compositions containing the sulfate salt (s) containing or without alkalinizing agent are at a pH greater than 7 and preferably between 8 and 12. The pH of these compositions may be adjusted to the value desired by means of acidifying or alkalizing agents usually used in dyeing keratinous fibers as defined in "iv) alkalinizing agent" previously or else using conventional buffer systems. Among the acidifying agents of the compositions, mention may be made especially of those selected from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H 2 SO 4, iv) alkyl sulphonic acids: Alk-S (0) 2OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S (O) 2OH such as benzene sulfonic acid and toluene sulfonic acid; (vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid, x) alkoxysulfinic acids: Alk-OS (O) OH such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3PO4; xiii) acetic acid CH30OOH; xiv) triflic acid CF3SO3H and xv) tetrafluoroboric acid HBF4.

Staining process in one or more steps According to a particular embodiment of the invention, the staining process is carried out, in one or more steps, by application to the keratinous fibers of one or more cosmetic compositions containing, taken together or separately in the said composition or compositions, the following ingredients: i) at least one resorcinol derivative of formula (I) as defined above; ii) at least one sulfate salt; iii) at least one oxidizing agent, preferably chemical; and iv) at least one basifying agent; it being understood that: the pH of the composition comprising the ingredient (s) iv) is basic i.e greater than 7; preferably between 7.5 and 12; and when the compound (s) of formula (I) represent resorcinol i.e. R ', R2, R3 and R4 represent a hydrogen atom, then the process does not use para-phenylenediamine; and - at least one of said compositions is aqueous. The pause time between the stages of application of the compositions comprising the ingredient or ingredients i), ii), iii) and / or iv) is set between 3 and 120 minutes, preferably between 10 and 60 minutes and more particularly between 15 and 45 minutes.

The keratinous fibers may or may not be previously moistened. More particularly, in the process of the invention the chemical oxidizing agent (s) such as hydrogen peroxide (iii) are: - either in admixture with ingredients i), ii) and iv) - or applied separately after application of a cosmetic composition comprising ingredients i), ii) and iv); or else - be applied together with ingredient ii) after application of a cosmetic composition comprising ingredients i) and iv). A particular embodiment of the invention relates to staining methods in one or two steps.

According to one particular embodiment of the invention, the process for dyeing keratinous fibers is carried out in a single step by the application to the keratinous fibers of the cosmetic composition according to the invention, preferably aqueous, comprising: i) at least one derivative of resorcinol of formula (I), as defined above; ii) at least one sulfate salt as defined above; iii) at least one oxidizing agent, preferably chemical, as defined above; and iv) at least one basifying agent; it being understood that: the pH of the composition is basic i.e greater than 7; preferably between 7.5 and 12; and when the compound (s) of formula (I) represent resorcinol i.e. R ', R2, R3 and R4 represent a hydrogen atom, then the composition does not contain para-phenylenediamine. The pause time after application is generally set between 5 minutes and 24 hours, particularly between 10 and 120 minutes and more particularly between 15 and 60 minutes in particular between 15 and 45 minutes.

According to another particular embodiment of the invention, the method for dyeing keratin fibers is in two steps. In a first variant, the two-step process comprises, in the first step, the application to said fibers of a cosmetic composition comprising the ingredients i), ii), iv) as defined above, then in a second step a cosmetic composition comprising the ingredient iii) at least one chemical oxidizing agent as defined above is applied to said fibers, it being understood that at least one of the two cosmetic compositions is aqueous.

In a second variant of two-step keratinous fiber staining process, comprises in the first step the application to said fibers of a composition comprising ingredients i) and iv), as defined previously, then in a second step a second cosmetic composition comprising the ingredients ii) and iii) as defined above is applied to said fibers, it being understood that preferably at least one of the two compositions is aqueous.

An advantageous aspect relates to the dyeing process as described previously preceded by one or more etching steps by using prior treatment of the keratinous fibers with at least one mordant as defined above (see "v) optionally one or more mordant (s) "). The mordant or mordants are in particular in a cosmetic composition and are applied at least 5 minutes before the implementation of the dyeing process comprising the ingredients i) to iv) as defined above. Especially the mordant used is iron sulfate.

Another advantageous aspect relates to the dyeing process as described above followed by post-treatment steps such as shampooing with conventional shampoo, rinsing for example with water and / or drying. keratinous fibers by heat treatment as defined below.

Preferably, the dyeing process according to the invention is carried out in one step by applying to the keratin fibers the composition according to the invention comprising the ingredients i) to iv) as defined above followed by post-treatment rinsing steps. example with water, shampooing with a classic shampoo and / or the drying of keratinous fibers. Whatever the mode of application, the application temperature is generally between room temperature (15 to 25 ° C) and 150 ° C and particularly between 15 and 85 ° C, and preferably between 20 and 60 ° C. Thus, it is advantageous, after application of the composition according to the invention, to subject the hair to a heat treatment by heating at a temperature of between 30 and 60 ° C. In practice, this operation can be carried out by means of a hairdressing helmet, a hair dryer, an infrared dispenser and other conventional heating devices. Both heating and smoothing of the hair can be used as a heating iron at a temperature of between 60 and 220 ° C and preferably between 120 and 200 ° C. A particular embodiment of the invention relates to a dyeing process which is carried out at room temperature (25 ° C). In all the particular modes and variants of the processes described above, the compositions mentioned are ready-to-use compositions which may result from the extemporaneous mixing of two or more compositions, and in particular of compositions present in dyeing kits.

Device or "kit" for dyeing: Another object of the invention is a multi-compartment device or "kit" of dyeing. Advantageously, this kit comprises from 2 to 5 compartments containing from 2 to 5 compositions in which are distributed the ingredients i) at least one resorcinol derivative of formula (I), as defined above, ii) at least one salt of sulfate as defined above, iii) at least one chemical oxidizing agent such as hydrogen peroxide and iv) at least one basifying agent as defined above. According to a first variant, the kit comprises five compartments, the first four compartments respectively comprising powder ingredients i), ii), iii) and iv) as defined above and the fifth compartment containing an aqueous composition such as water. In this case, the compound (s) iii) are precursors of hydrogen peroxide. Or the kit comprises four compartments, the first three compartments respectively comprising powder ingredients i), ii), and iv) as defined above and the fourth compartment containing an aqueous composition such as water. Another variant relates to a kit with four compartments, at least one of which contains an aqueous composition, and comprising an ingredient i) to iv) as defined above. Another preferred embodiment relates to a device comprising three compartments: (a) a first compartment contains a composition containing: i) at least one resorcinol derivative of formula (I) as defined above; and (b) a second compartment contains a composition comprising: ii) at least one sulfate salt as defined above; iii) at least one chemical oxidizing agent such as hydrogen peroxide; (c) a third compartment contains iv) at least one basifying agent as defined above. In this other embodiment, at least one of the three compositions is preferably aqueous and the resorcinol derivative (s) of formula (I) may be in the form of a powder. One can also have a kit with three compartments, the first a) containing a composition comprising i) at least one resorcinol derivative of formula (I) and ii) at least one sulfate salt as defined above, the second b) containing a composition comprising iii) at least one chemical oxidizing agent such as hydrogen peroxide and the third c) containing a composition comprising iv) at least one basifying agent as defined above. In this other kit at least one of the compositions is preferably aqueous. This composition preferably contains hydrogen peroxide. According to a particular embodiment of the invention, the kit comprises two compartments: a first compartment comprising a composition containing i) at least one resorcinol derivative of formula (I) as defined above, ii) at least one sulfate salt such as defined above, iii) at least one chemical oxidizing agent such as hydrogen peroxide and a second compartment containing iv) at least one basifying agent as defined above.

Among the kits with two compartments are also possible the kits which contain in a first compartment a composition comprising the compounds i), ii) and iv) as defined above and in a second compartment a composition comprising the compound iii) at least one agent chemical oxidant such as hydrogen peroxide as defined above.

According to a variant, the device according to the invention further comprises an additional composition (c) comprising one or more treating agents.

The compositions of the device according to the invention are packaged in separate compartments, possibly accompanied by appropriate, identical or different application means, such as brushes, brushes or sponges.

The device mentioned above can also be equipped with a means for delivering the desired mixture onto the hair, for example such as the devices described in the patent FR 2,586,913.

EXAMPLES OF COLORING EXAMPLE 1 The following 4 compositions were prepared: Coloring compositions (A) (B) (C) (D) HO ® OH (1) Benzene-1,3-0,025 mol diol or resorcinol HO® OH 2- Methyl-0.025 mol (2) benzene-1,3-diol HO (3) 5-Methyl-0.025 mol benzene-1,3-diol HO OH OH (4) Benzene-1,3,5-0,025 mol ® triol sodium sulphate 0.125 mol 0.125 mol 0.125 mol 0.125 mol hydrogen peroxide 0.125 mol 0.125 mol 0.125 mol 0.125 mol ammonia 20% vol NH3 10 mL 10 mL 10 mL 10 mL demineralized water qs 100 g 100 g 100 g 100 g of each composition (A) to (D) obtained is applied to strands of 0.5 g of gray hair with 90% of whites. After 60 minutes of exposure at 45 ° C., the locks are rinsed, washed with a standard shampoo and then dried.

Color results:

After treatment with the compositions of the invention, the locks are colored in a powerful, chromatic manner, even in the absence of para-phenylenediamines. Stains are very stubborn to washing and light.

Compositions Colors after treatment on 90% natural white wick (A) Dark green (B) Dark blue-green (C) Dark Bordeaux (D) Dark beige According to the same protocol and by applying the compositions identical to (A) to (D) ) but containing no sulphate, the locks were very little colored (very light blond color).

Claims (16)

REVENDICATIONS1. A process for dyeing keratinous fibers comprising the application to the keratinous fibers of: i) at least one resorcinol derivative of formula (I), as well as its salts of organic or inorganic acid or base, and its solvates such as the hydrates: R3 (I) formula (I) in which R 'to R4, identical or different, represent a hydrogen atom, halogen; or a group chosen from: - (C, -C, o) optionally substituted alkyl; (C1-C10) alkoxy; carboxyl-C (O) -OH or carboxylate -C (O) -O-, W; with W representing a cationic counterion such as an alkali or alkaline earth metal, or an ammonium, -C (O) -O-R5 or -OC (O) -R5, with R5 representing a group (C, - C, o) alkyl, especially -C (O) -O-R5; amido -C (O) -NR6R7 or -NR6-C (O) -R7 with R6 and R7, identical or different, representing a hydrogen atom or a group (C, -C, o) alkyl, particularly -C (0) -N H2; (C1-C10) alkylcarbonyl; hydroxy; and ^ amino -NR8R9, with R8 and R9, identical or different, representing a hydrogen atom or a (C, -C, o) alkyl group, particularly -NH2; ii) at least one alkali metal, alkaline-earth metal or ammonium, (C 1 -C 6) alkylammonium or tri (C 1 -C 6) alkylammonium sulfate; iii) at least one chemical oxidizing agent; and iv) at least one basifying agent; It being understood that: ingredients i) to iv) may be applied to the fibers either together or separately; the pH of the composition comprising the ingredient or ingredients iv) is basic i.e greater than 7; Preferably between 7.5 and 12; and when the compound (s) of formula (I) represent resorcinol i.e. R ', R2, R3 and R4 represent a hydrogen atom, then the process does not use para-phenylenediamine. 2. Staining process according to the preceding claim wherein the resorcinol derivative (s) of formula (I) are such that R 'represents: a hydrogen atom; a halogen atom, preferably a chlorine atom; a linear or branched (C 1 -C 4) alkyl group; a hydroxy group; a (C 1 -C 4) alkylcarbonyl group, preferentially methylcarbonyl; a carboxyl or carboxylate group as defined above; an amido radical such as -C (O) -NH 2; or an amino radical such as NH 2. 3. Staining process according to the preceding claim wherein the resorcinol derivative (s) of formula (I) are such that R 'represents: a hydrogen atom; or a linear or branched (C 1 -C 4) alkyl group. 4. A method of dyeing according to any one of the preceding claims wherein the resorcinol derivative (s) of formula (I) are such that R3 represents: a hydrogen atom; a (C 1 -C 4) alkyl group optionally substituted by a hydroxy group; a carboxyl group; a (C 1 -C 4) alkylcarbonyl group, preferentially methylcarbonyl; a hydroxy group; an amido group such as -C (O) -NH 2; an amino group such as -NH 2; or a (C 1 -C 4) alkoxy group, preferably a methoxy radical. 5. Staining process according to the preceding claim wherein the resorcinol derivative (s) of formula (I) are such that R3 represents: a hydrogen atom; a linear or branched (C 1 -C 4) alkyl group; a hydroxy group; or a (C 1 -C 4) alkoxy group, preferably a methoxy radical. 6. The method of dyeing according to any one of the preceding claims wherein the resorcinol derivative (s) of formula (I), are such that R2 or R4, identical or different, represent: a hydrogen atom; a halogen atom, preferably a chlorine atom; a linear or branched (C 1 -C 8) alkyl group, preferably C 1 -C 4; a (C 1 -C 4) alkoxy group, preferentially a methoxy radical; a carboxyl group; an alkyl carboxylate group such as -C (O) -O-R5 with R5 representing a (C1-C4) alkyl group; a (C 1 -C 4) alkylcarbonyl group, preferentially methylcarbonyl; a hydroxy group; or an amino group such as -NH 2. 7. The method of dyeing according to the preceding claim wherein the resorcinol derivative (s) of formula (I) are such that: R2 represents: a hydrogen atom; a halogen, preferably a chlorine atom; a linear or branched (C 1 -C 4) alkyl group; a (C 1 -C 4) alkoxy group; a carboxyl group; or a hydroxy group; and - R4 represents a hydrogen atom. 8. The method of dyeing according to any one of the preceding claims wherein the resorcinol derivative (s) of formula (I) are chosen from the following compounds: compounds Structure Name HO OH Resorcinol; Benzene-1,3-diol or 3-hydroxyphenol 2 HO 2-Methyl-benzene-1,3-diol 3 HO 2-OH 2,5-Dimethyl-benzene-1,3-diol 4 HO O 2,4-d Acid 4-Chloro-benzene-1,3-diol OH 5-Methyl-benzene-1,3-diol 7 OH OH 4-Methyl-benzene-1,3-diol 5-Methoxy-benzene-1,3-diol HO 4-Methoxy-benzene-1,3-diol OH O-Benzene-1,2,4-triol OH 11 OH-Benzene-1 , 3,5-triol 12 HO OH 4-butyl-benzene-1,3-diol 13 HOC-OH 4-hexyl-benzene-1,3-diol HO O OH 2,4-Dihydroxy-benzoic acid methyl O-ester HO 2 2,4-Dimethylbenzene-1,3-diol 16-OH-2-chloro-benzene-1,3-diol 17-OH-1,2-benzene-benzene 18 HO 2,4-Dihydroxy acid Methyl 6-methyl-1-benzoic acid Methyl OH-2,4-Dihydroxy-3,6-dimethyl-benzoate OH 5-Hydroxymethyl-benzene-1,3-diol 21 OH OH OH (2) , 6-Dihydroxy-phenyl) -ethanone 22H-OH-4-ethyl-benzene-1,3-diol 23H-dihydroxy-3,5-dihydroxybenzoic acid phenyl) -ethanone OH 2 1- (3,5-Dihydroxy-phenyl) -ethanone 2,6-dihydroxybenzoic acid OH 27 O NH 2 3,5-Dihydroxybenzamide HO OH OH OH OH 6-Dihydroxybenzamide NH 2 NH 2 4-amino-benzene-1,3-diol OH 2-amino-benzene-1,3-diol HO 2 NH 2 OH 5-aminobenzene-1,3-diol O-diol 32 OH O 1- (2,4-Dihydroxy-3-methyl-phenyl) -OH ethanone 33 OH OH OH OH (2,3,4-Trihydroxy-phenyl) -ethanone 4,5-Trihydroxy-benzamide OH 2,3,4-Trihydroxy-benzoic acid OH 2,4,5-Trihydroxybenzoic acid OH 37 OH OH 4-pentyl-benzene-1 , 3-diol and / or their organic or inorganic base salts and / or their solvates. 9. A method of dyeing according to any one of the preceding claims wherein ii) the sulphate salt or salts are selected from sulfates of formula M2SO3 or M'SO3 or hydrogen sulfate of formula MHSO3 with M representing an alkali metal such as Na, K or (di) (C 1 -C 6) (alkyl) ammonium or tri (C 1 -C 6) alkylammonium such as NH 4 + and M 'representing an alkaline earth metal. The staining method according to any of the preceding claims wherein ii) the sulfate salt (s) are selected from: a) potassium disulfate [16731-55-8]: K2S205; b) sodium disulfate [7681-57-4]: Na2S2O5; c) ammonium sulfate [10196-04-0]: (NH4) 2SO3; d) sodium sulfate [7757-83-7]: Na2SO3; and e) sodium hydrogen sulfate [7631-90-5]: NaHSO3. 11. The method of dyeing according to the preceding claim wherein the chemical oxidizing agent (s) is (are) chosen from: a) ozone; b) alkali metal or quaternary ammonium persalt such as perborates, persulfates, percarbonates, peroxodiphosphates, Oxone®; c) C 6 -C 20 aliphatic organic aliphatic peracids and their percarboxylate forms, such as performic acid, peracetic acid, perbenzoic acid derivatives, trifluoroacetic acid, peroxyphthalic acid, peroxymaleic acid, peroxypropionic acid; d) organic peroxides, such as dioxirane, C1-C6 alkyl peroxides, benzoyl peroxide, peroxo (C 1 -C 6) alkyl carboxylates, bis (tri) (C 1 -C 6) peroxides alkylsilyl, C 1 -C 6 alkyl peroxydicarbonates, sodium nonanoyloxybenzene sulfonate; e) oxidizing anions such as nitrites, nitrates, hypochlorites, hypobromites, hypoiodites, chlorites, bromites, iodites, chlorates, bromates, iodates, periodates; f) stable radicals N-oxy (NO), 2,2,6,6-tetra (C 1 -C 6) alkylmorpholino-oxy salts of Fremy nitrosodisulfonates, N-oxide morpholine; (g) hypervalent iodine derivatives, such as iodotriacetate, iodosobenzene, iodobenzenetriacetate, iodoperbenzoic acid derivatives, periodinans, alkyls and benzoylhypoiodites; h) the following organic compounds: N-halosuccinimides, trichloroisocyanuric acid, N-hydroxyphthalimide, alkyl nitrites, the optional supports of these oxidants a) to h) may be chosen from silica, alumina, coal charged or neutral polymers; i) hydrogen peroxide or system (s) generator (s) of hydrogen peroxide; preferentially hydrogen peroxide. 12. Coloring process according to any one of the preceding claims wherein the alkalinizing agent or agents iv) are chosen from a) the (bi) carbonates, b) ammonia, c) alkanolamines d) oxyethylenated ethylene and / or oxypropylene e) inorganic or organic hydroxides, f) alkali metal silicates such as sodium metasilicates, g) basic amino acids and h) compounds of the following formula (II): RR a \, b NWN R ~ Rd (II) formula (II) wherein W is divalent (C 1 -C 0) alkylene group optionally interrupted by at least one heteroaromatic such as O, S, NRe, and / or said alkylene group is optionally substituted by at least one hydroxy group or a (C 1 -C 4) alkyl radical; Ra, Rb, Rd, Rd and Re, identical or different, represent a hydrogen atom, (C 1 -C 4) alkyl or hydroxy-C 1 -C 4 alkyl. 13. The method of dyeing according to any one of the preceding claims which does not employ para-phenylenediamines nor para-aminophenols. 14. The method of dyeing according to any one of the preceding claims which is carried out in a single step by the application to the keratinous fibers of the cosmetic composition, preferably aqueous, comprising: i) at least one resorcinol derivative of formula (I), as defined in any one of claims 1 to 8; ii) at least one alkali metal, alkaline-earth metal or ammonium, (di) (C 1 -C 6) alkylammonium or tri (C 1 -C 6) alkylammonium sulphate as defined in any one of claims 1, 9 or 10; iii) at least one chemical oxidizing agent as defined in claims 1 or 11; and iv) at least one basifying agent as defined in claims 1 or 12; it being understood that: the pH of the composition is basic i.e greater than 7; preferably between 7.5 and 12; and when the compound (s) of formula (I) represent resorcinol i.e. R ', R2, R3 and R4 represent a hydrogen atom, then the composition does not contain para-phenylenediamine. 15. Cosmetic composition, preferably aqueous, comprising: i) at least one resorcinol derivative of formula (I), as defined in any one of claims 1 to 8; ii) at least one alkali metal, alkaline-earth metal or ammonium, (di) (C 1 -C 6) alkylammonium or tri (C 1 -C 6) alkylammonium sulphate as defined in any one of claims 1, 9 or 10; iii) at least one chemical oxidizing agent as defined in claims 1 or 11; and iv) at least one basifying agent as defined in claims 1 or 12; it being understood that: the pH of the composition is basic i.e greater than 7; preferably between 7.5 and 12; and when the compound (s) of formula (I) represent resorcinol i.e. R ', R2, R3 and R4 represent a hydrogen atom, then the composition does not contain para-phenylenediamine. 16. A multi-compartment device comprising 2 to 5 compartments containing from 2 to 5 compositions in which ingredients i), ii), iii) and iv), as defined in any one of Claims 1 to 14, are distributed, said compositions being aqueous or powdery, with at least one of these compositions being aqueous.