WO2010133803A1

WO2010133803A1 - Dyeing composition comprising a secondary para-phenylenediamine oxidation base and a specific surfactant

Info

Publication number: WO2010133803A1
Application number: PCT/FR2010/050964
Authority: WO
Inventors: Jean-Baptiste Saunier
Original assignee: L'oreal
Priority date: 2009-05-19
Filing date: 2010-05-19
Publication date: 2010-11-25

Abstract

The invention relates to a composition for coloring keratin fibers, comprising, in a suitable dyeing medium: - one or more oxidation bases selected from the compound of formula (I) and the acid addition salts thereof; - one or more surfactants selected from the ones carrying at least one cationic charge, carboxylic ether acids or a salt thereof, and monoglycerol or polyglycerol nonionic surfactants and polyoxyethylene sorbitan esters. The invention also relates to a dyeing method in which said composition is used and in which the aforementioned dyeing composition is applied to the fibers with or without an oxidizing agent. The invention further relates to devices including a plurality of compartments.

Description

TINCTORIAL COMPOSITION COMPRISING A PARA-PHENYLENE DIAMINE SECONDARY OXIDATION BASE AND A PARTICULAR SURFACTANT

The subject of the invention is a dyeing composition comprising at least one particular secondary para-phenylenediamine oxidation base and at least one particular surfactant. The invention also relates to a process for dyeing keratinous fibers, in particular human fibers such as the hair, using this composition, as well as devices with several appropriate compartments. It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, generally known as oxidation bases, such as ortho or para-phenylenediamines, ortho 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 than indolic compounds. The variety of molecules involved in oxidation bases and couplers, allows to obtain a rich palette of colors.

The so-called "permanent" coloration obtained with these oxidation dyes must also meet a certain number of requirements. Thus, it must be harmless from the toxicological point of view, it must make it possible to obtain shades in the desired intensity and to have good resistance to external agents such as light, bad weather, washing, permanent undulations, sweating and friction.

The dyes must also make it possible to cover the white hair, and finally be the least selective possible, that is to say, to obtain the lowest possible color differences throughout the same keratin fiber, which is in general differently sensitized (ie damaged) between its point and its root.

It is already known to use oxidation bases of the para-phenylene diamine secondary type of formula (I) below for dyeing keratinous fibers, especially the hair. In particular, such a base is disclosed in EP1580184 and EP0055386. This base has the drawbacks of leading to insufficiently intense or chromatic and / or too selective staining. The object of the present invention is to obtain a composition for hair dyeing which has improved dyeing properties in terms of intensity or chromaticity, and / or selectivity and / or resistance to external agents.

This object is achieved with the present invention which relates to a coloring composition of keratinous fibers comprising, in an appropriate dyeing medium,

one or more oxidation bases selected from the compound of formula (I) or its addition salts with an acid,

and one or more surfactants chosen from those bearing at least one cationic charge, from carboxylic ether acids or one of their salts, or from mono- or polyglycerolated nonionic surfactants and polyoxyethylenated sorbitan esters.

The invention also relates to a dyeing process using this composition.

It also relates to a multi-compartment device comprising in one of them, the dye composition according to the invention without oxidant, and in another, a composition comprising one or more oxidizing agents.

According to another variant of the invention, the device comprises a first compartment containing the compound of formula (I) or its salts with an acid and optionally one or more different oxidation bases of the compound of formula (I) or its salts and optionally one or more couplers; a second compartment containing a composition comprising one or more surfactants as defined above and optionally a third compartment containing a composition comprising one or more oxidizing agents.

The composition of the present invention makes it possible in particular to obtain a keratinous fiber coloring composition which is suitable for use in oxidation dyeing and makes it possible to obtain a coloring with varied shades, intense or chromatic, aesthetic, not very selective and resistant. well to the various aggressions that can undergo the hair such as the shampoos, the sweat and the permanent deformations and the light.

It should be noted that in what follows, and unless otherwise indicated, the boundaries of a domain of values are included in this area. The compound of formula (I) may be in the form of addition salts chosen especially from acid addition salts such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates. The compound of formula (I) or its salts are generally present each in an amount of between 0.001 to 10% by weight relative to the total weight of the dye composition, preferably between 0.005 and 6% by weight.

The dye composition of the invention may optionally comprise one or more additional oxidation bases conventionally used for dyeing keratinous fibers, different from the compound of formula (I) or its salts.

By way of example, these additional oxidation bases are chosen from the different para-phenylenediamines of the compound of formula (I) and of its addition salts, bisphenylalkylenediamines, para-aminophenols, bis-para-amines and aminophenols, ortho-aminophenols, heterocyclic bases. Among the para-phenylenediamines, there may be mentioned by way of example, para-phenylenediamine, para-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl para phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N, N-dimethyl-para-phenylenediamine, N, N-diethyl-para-phenylenediamine, N, N-dipropyl para phenylenediamine, 4-amino N, N-diethyl-3-methylaniline, N, N-bis- (β-hydroxyethyl) para-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino 2- methyl aniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N- (β-hydroxypropyl) para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N, N-dimethyl-3-methyl-para-phenylenediamine, N, N- (ethyl, β-hydroxyethyl) para-phenylenediamine, N- (β, γ-dihydroxypropyl) para-phenylenediamine, N- (4'-aminophenyl) para-phenylenediamine, N-phenyl para-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2-β-acetylaminoethyloxy para-phenylenediamine, N- (β-methoxyethyl) para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl para-phenylenediamine, 2-β-hydroxyethylamino-5-amino-toluene, 3-hydroxy-1- (4 ') aminophenyl) pyrrolidine and their addition salts with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 2-isopropyl para-phenylenediamine, 2-β-hydroxyethyl para-phenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N, N-bis- (β-hydroxyethyl) para-phenylenediamine, 2-chloro para- phenylenediamine, 2-β-acetylaminoethyloxy para-phenylenediamine, and their addition salts with an acid are particularly preferred.

Among the bis-phenylalkylenediamines, N, N'-bis- (β-hydroxyethyl) N, N'-bis (4'-aminophenyl) -1,3-diamino propanol, N, may be mentioned by way of example. , N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- ( β-hydroxyethyl) N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis (ethyl) N, N ' -bis- (4'-amino, 3'-methylphenyl) ethylenediamine, 1,8-bis (2,5-diamino phenoxy) -3,6-dioxaoctane, and their addition salts with an acid. Examples of para-aminophenols include para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluoro phenol, 4-amino-3-hydroxymethylphenol, 4- amino 2-methyl phenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (β-hydroxyethylaminomethyl) phenol, 4- amino 2-fluoro phenol, 1-hydroxy-4-methylamino-benzene, 2-2'-methylenebis-4-amino phenol and their addition salts with an acid.

Among the ortho-aminophenols, there may be mentioned by way of example, 2-amino phenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-amino phenol, and their addition salts with an acid.

Among the heterocyclic bases that may be mentioned by way of example are pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Among the pyridine derivatives, mention may be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, 2- (4-methoxyphenyl) amino 3-amino pyridine, 2,3-diamino-6-methoxy pyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxy pyridine, 3,4-diamino pyridine, and their addition salts with an acid.

Among the pyrimidine derivatives, mention may be made of the compounds described, for example, in DE 2359399; JP 88-169571; JP 05-63124; EP 0770375 or patent application WO 96/15765 such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy 2,5,6-triaminopyrimidine, 2-hydroxy 4,5,6-triaminopyrimidine, , 4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine, and pyrazolopyrimidine derivatives such as those mentioned in patent application FR-A-2750048 and among which mention may be made of pyrazolo [1, 5-a] -pyrimidine-3,7-diamine; 2,5-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine; pyrazolo [1,5-a] pyrimidine-3,5-diamine; 2,7-dimethyl pyrazolo [1,5-a] pyrimidine-3,5-diamine; 3-amino pyrazolo [1,5-a] pyrimidin-7-ol; 3-amino pyrazolo [1,5-a] pyrimidin-5-ol; 2- (3-amino pyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol, 2- (7-amino pyrazolo [1,5-a] pyrimidin-3-ylamino) - ethanol, 2 - [(3-amino-pyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxyethyl) amino] ethanol, 2 - [(7-amino-pyrazolo [ 1,5-a] pyrimidin-3-yl) - (2-hydroxyethyl) amino] ethanol, 5,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, the 2,6-dimethyl pyrazolo [1,5-a] pyrimidine-3,7-diamine, 2,5-N, 7-N-tetramethyl pyrazolo [1,5-a] pyrimidine-3,7 -diamine, 3-amino-5-methyl-7-imidazolylpropylamino pyrazolo [1,5-a] pyrimidine and their addition salts with an acid and their tautomeric forms, when tautomeric equilibrium exists. Among the pyrazole derivatives, mention may be made of the compounds described in the DE patents

3843892, DE 4133957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749 and DE 195 43 988 such as 4,5-diamino-1-methyl pyrazole, 4,5-diamino 1- (β-hydroxyethyl) pyrazole, 3,4-diamino pyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4,5-diamino-1,3-dimethyl pyrazole, 4,5-diamino 3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazino-pyrazole, 1-benzyl-4,5-diamino-3-methyl-pyrazole, 4,5-diamino-3-tert-butyl-1-methyl pyrazole, 4,5-diamino-1-tert-butyl-3-methyl pyrazole, 4,5-diamino 1- (β-hydroxyethyl) 3-methyl pyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole, 4,5-diamino-1-ethyl-3-hydroxymethyl pyrazole, 4, 5-diamino-3-hydroxymethyl-1-methyl pyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropyl pyrazole, 4,5-diamino-3-methyl-1-isopropyl pyrazole, 4-amino-5- (2'-aminoethyl) ) amino 1,3-dimethyl pyrazole, 3,4,5-triamino pyrazole, 1-methyl 3,4,5-triamino pyrazole, 3,5-diamino-1-methyl-4-methylamino pyrazole, 3,5-diamino-4- (β-hydroxyethyl) amino 1-methyl pyrazole, and their addition salts with an acid. There may also be mentioned diaminopyrazolinones described in the patent application

FR2886137 and in particular 2,3-diamino-6,7-dihydro-1H, 5H-pyrazol-1-one and its salts.

In general, the addition salts of the oxidation bases and couplers that can be used in the context of the invention are chosen especially from the addition salts with an acid such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates and addition salts with a base such as sodium hydroxide, potassium hydroxide, ammonia, amines or alkanolamines.

When the composition comprises one or more additional oxidation bases, that (s) represents (s) more particularly from 0.0005 to 12% by weight relative to the total weight of the dyeing composition, preferably from 0.005 to 8 % in weight.

The dye composition according to the invention may also optionally comprise one or more couplers conventionally used for dyeing keratinous fibers. Among these couplers, there may be mentioned meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalenic couplers, heterocyclic couplers and their addition salts.

By way of example of a coupler, there may be mentioned 2-methyl-5-aminophenol, 5-N- (β-hydroxyethyl) amino-2-methylphenol, 6-chloro-2-methyl-5-aminophenol, 3 amino phenol, 2,4-dichloro-3-aminophenol, 5-amino-4-chloro-o-cresol, 1,3-dihydroxy benzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1- (β-hydroxyethyloxy) benzene, 2-amino-4- (β-hydroxyethylamino) 1-methoxybenzene, 1,3-diamino benzene, 1,3-bis (2,4-diaminophenoxy) propane, 3-ureido aniline, 3-ureido 1-dimethylamino benzene, sesamol, 1-β 3-hydroxyethylamino-3,4-methylenedioxybenzene, α-naphthol, 2-methyl-1-naphthol, 1,5-dihydroxy naphthalene, 2,7-naphthalenediol, 1-acetoxy-2-methylnaphthalene, 6- hydroxy indole, 4-hydroxyindole, 4-hydroxy N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxybenzomorpholine 3,5-diamino-2,6-dimethoxypyridine, 2,6 dihydroxy-3-4-dimethylpyridine, 3-amino-2-methylamino-6-methoxypyridine, 1-N- (β-hydroxyethyl) amino-3,4-methylene dioxybenzene, 2,6-bis- ( β-hydroxyethylamino) toluene, 3-methyl-1-phenyl-5-pyrazolone and their addition salts with an acid.

In the composition of the present invention, the coupler (s), if present, generally represent an amount of between 0.001% and 10% by weight relative to the total weight of the dyeing composition, preferably between 0.005% and 6% by weight. weight. The dye composition in accordance with the invention may also contain one or more direct dyes that may be chosen in particular from nitro dyes of the benzene series, azo direct dyes and methine direct dyes. These direct dyes may be nonionic, anionic or cationic in nature.

In the composition of the present invention, the direct dye (s), if present, generally represent an amount of between 0.001% and 20% by weight relative to the total weight of the dyeing composition, preferably between 0.01% and 10% by weight.

As indicated above, the dye composition according to the invention may comprise one or more surfactants carrying at least one cationic charge. More particularly, these surfactants are chosen from compounds comprising at least one cationic charge and at least one C ₁₂ -C 30 alkyl or alkenyl chain optionally bearing at least one ester or amide function.

Thus the surfactants used in the composition according to the invention may comprise a cationic charge and no anionic charge, or comprise both a cationic charge and an anionic charge. In the latter case, the surfactants are amphoteric or zwitterionic species.

As examples of suitable cationic surfactants, mention may be made of: (i) the quaternary ammonium salts of formula (II) below:

in which

X ^' is an anion chosen for example from the group of halides (chloride, bromide or iodide) or alkyl (C ₂ -C ₆ ) sulphates, more particularly methylsulphate, phosphates, alkyl-or-alkylarylsulfonates, anions derived from an organic acid such as acetate or lactate, and

(1) the radicals R 1 to R ₃ , which may be identical or different, represent an aliphatic radical, linear or branched, in dC ₄ , or an aryl or alkylaryl radical, the alkyl radical optionally carrying an alkoxy, alkylamide, R _{4 group;} denotes an alkyl radical, linear or branched, Ci ₆ -C ₃ O, preferably Ci ₄ - C ₂₂ ; or

(2) the radicals R 1 and R ₂ , which are identical or different, represent an aliphatic radical, linear or branched, in dC ₄ , or a radical such as aryl or alkylaryl, the alkyl radical optionally carrying an alkoxy, alkylamide or hydroxyalkyl group; in dC ₄ ;

R ₃ and R ₄ , which may be identical or different, denote a linear or branched C ₁ -C ₃₀ alkyl or alkenyl radical, said radical optionally comprising at least one ester or amide function;

Advantageously, the cationic surfactant according to the above-mentioned option (1) is a salt (for example chloride) of behenyltrimethylammonium, and according to option (2) a salt (for example chloride) of stearamidopropyl dimethyl (myristylacetate) ammonium marketed under the denomination "CERAPHYL 70" by the company VAN DYK.

(ii) the quaternary ammonium salts of the imidazolinium of formula (III) below:

in which

R ₅ represents an alkenyl or a C ₂ -C ₃₀ alkyl radical,

R ₆ represents a hydrogen atom, a C ₁ -C ₄ alkyl radical or an alkenyl or C ₂ -C ₃₀ alkyl radical,

R ₇ represents a C ₁ -C ₄ alkyl radical, R ₈ represents a hydrogen atom, a C ₁ -C ₄ alkyl radical,

X is an anion X especially selected from the group of halides, phosphates, acetates, lactates, alkylsulfates, alkyl-or-alkylarylsulfonates.

Preferably, R ₅ and R ₆ denote a mixture of alkenyl or alkyl radicals containing from 12 to 21 carbon atoms, for example fatty acid derivatives of tallow, R ₇ denotes methyl and R ₃ denotes hydrogen. Such a product is, for example, Quaternium-27 (CTFA 1997) or Quaternium-83 (CTFA 1997) sold under the names "REWOQUAT" W 75, W90, W75PG, W75HPG by the company WITCO; (iii) quaternary diammonium salts of formula (IV):

2X

(IV) in which

R ₉ denotes a C 12 -C 30 alkyl or alkenyl radical,

R _10, Rn, R _12, R ₁ 3 and R _14, identical or different are selected from hydrogen or an alkyl radical in C ₄ and X is an anion chosen in particular from the group of halides, acetates, phosphates, nitrates and methylsulfates.

Such diammonium quaternary salts include in particular propane dichloride diammonium.

(iv) quaternary ammonium salts containing at least one ester function of formula (V) below:

(G _r H _2r O) _z O

R ₁₇ - C - (OC _n H _2n) _y N - (C H _2p O) _χ - R ₁₆ X

^R15 (V) in which:

• R ₅ is selected from alkyl, -C ₆ hydroxyalkyl, -C ₆ dihydroxyalkyl, C ₂ -C _6; • R ₁ 6 is selected from the radical R ₁₉ -CO-, an alkyl radical or R ₂ o alkenyl

C ₁ -C ₂₂ linear or branched, a hydrogen atom,

R ₁₈ is chosen from the radical R ₂₁ -CO-, a radical R ₂₂ alkyl or alkenyl C ₁ -C ₆ linear or branched, a hydrogen atom,

R ₁₇ , R ₁₉ and R ₂₁ , which are identical or different, are chosen from linear or branched C ₁₂ -C ₂₂ alkyl or alkenyl radicals;

• n, p and r, identical or different, are integers ranging from 2 to 6;

• y is an integer from 1 to 10;

• x and z, identical or different, are integers from 0 to 10;

• X ^' is a simple or complex anion, organic or inorganic. Ammonium salts of formula (V) in which:

R ₁₅ denotes a methyl or ethyl radical,

X and y are equal to 1;

Z is 0 or 1;

• n, p and r are equal to 2; R ₁₆ is selected from R ₁₉ -CO-, methyl, ethyl, C ₁₄ -C ₂₂ alkyl or alkenyl - hydrogen;

R ₁₇ , R ₁₉ and R ₂₁ , which are identical or different, are chosen from linear or branched, saturated or unsaturated C ₇ -C ₂₁ alkyl or alkenyl radicals;

R ₁₈ is chosen from the radical R ₂₁ -CO-, the hydrogen atom. Such compounds are for example marketed under the names

DEHYQUART by COGNIS, STEPANQUAT by STEPAN, NOXAMIUM by CECA, REWOQUAT WE 18 by REWO-WITCO. According to a particularly advantageous embodiment of the invention, the composition comprises, as cationic surfactant (s), one or more cationic surfactants of formula (II), and preferably one or more cationic surfactants of formula (II) corresponding to option (1). As examples of amphoteric (s) or zwitterionic (s) surfactant (s), mention may be made of compounds derived from secondary or tertiary aliphatic amines, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 and preferably from 10 to 24 carbon atoms and containing at least one anionic group such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. There may be mentioned in particular (C ₈ _ ₂ o) alkylbetaines, sulphobetaines, (C ₈

₂ o) amido (C _6-8) alkyl betaines or (C ₈ _ ₂ o) amido (C ₆ _ ₈₎ sulphobetaines.

Among the amine derivatives include the products sold under the name Miranol ^®, as described in US patents 2,528,378 and US 2,781,354 and classified in the CTFA dictionary, ^3rd edition, 1982, under the names Amphocarboxy-glycinate and Amphocarboxypropionate of respective structures (a) and (b):

R _a -CONHCH ₂ CH ₂ -N (R _b ) (R _c ) (CH ₂ COO ^- ) (a) in which:

R ₃ represents an alkyl group derived from an R ₃ -COOH acid present in the hydrolysed coconut oil, a heptyl, nonyl or undecyl group, R _b represents a beta-hydroxyethyl group, and

R _c represents a carboxymethyl group; and

R _a '-CONHCH ₂ CH ₂ -N (B) (B') (b) in which: B represents -CH ₂ CH ₂ OX ',

B 'represents - (CH ₂ ) _Z -Y \ with z = 1 or 2,

X 'represents the group -CH ₂ CH ₂ -COOH or a hydrogen atom, Y' represents -COOH or the group -CH ₂ -CHOH-SO ₃ H,

R ₃ 'represents an alkyl group of a R _a ' -COOH acid present in coconut oil or in hydrolysed linseed oil, an alkyl group, in particular Ci ₇ and its iso form, a C _{7 group} unsaturated.

These compounds are classified in the CTFA dictionary, ^5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate caprylamphodiacetate disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate disodium capryloamphodipropionate, disodium lauroamphodipropionic acid, cocoamphodipropionic acid. Examples include the cocoamphodiacetate sold by Rhodia under the trade name Miranol ^® C2M concentrate.

Preferably, the surfactant (s) carrying at least one cationic charge are chosen from behenyltrimethylammonium chloride, behenyltrimethylammonium methosulfate and methylalkylamidoethylimidazolinium methosulfate (QUATERNIUM).

87), cetyl trimethyl ammonium chloride, and a mixture of cocamido propyl betaine and cetyl betaine (MIRASPEC TAM 40 / M - RHODIA), or mixtures thereof.

Preferably, the surfactant (s) carrying at least one cationic filler of the invention are cationic. As indicated above, the dyeing composition according to the invention may also comprise one or more carboxylic ether acids or one of its salts.

The carboxylic ether acids or their salts are chosen from polyoxyalkylenated alkyl- or alkenyl- (C ₆ -C ₂₄ ) ether carboxylic acids and their salts, polyoxyalkylenated (C ₆ -C ₂₄ ) aryl ether aryl ether carboxylic acids and their salts; polyoxyalkylenated alkyl (C ₆ -C ₂₄ ) alkyl amido ether acids and their salts, in particular those containing from 2 to 50 alkylene oxide groups, in particular ethylene, such as the compounds proposed by KAO under the names AKYPO.

Mixtures of these surfactants can also be used.

The salts are in particular chosen from alkali metal salts, especially sodium salts, ammonium salts, amine salts, aminoalcohol salts such as triethanolamine or monoethanolamine and magnesium salts.

The surfactants of the polyoxyalkylenated ether carboxylic acid type are, in particular, those which have the following formula (N '): R ₁ - (OC ₂ H ₄ ) n - OCH ₂ COOA in which:

R 1 represents a radical or a mixture of linear or branched C ₈ -C ₂₂ alkyl or alkenyl radicals, a (C ₈ -C ₉ ) alkyl phenyl radical, a radical R ₂ CONH-CH ₂ -CH ₂ - with R ₂ denoting a linear or branched Cn-C ₂ - _I alkyl or alkenyl radical, and n is an integer or decimal number (average value) which can vary from 2 to 24 and preferably from 2 to 10,

A denotes H, ammonium, Na, K, Li, Mg or a monoethanolamine or triethanolamine residue. It is also possible to use mixtures of compounds of formula (N '), in particular mixtures in which the groups R- | are different.

More particularly, the radical R 1 is an alkyl group comprising from 8 to 18 carbon atoms and the aryl group preferably denotes phenyl.

The polyoxyalkylenated ether carboxylic acids or their salts are preferably chosen from those of formula (N ') in which R 1 denotes a radical or a mixture of alkyl (C 12 -C ₁₄ ), cocoyl, oleyl radicals; a nonylphenyl or octylphenyl radical A denotes a hydrogen or sodium atom, and n ranges from 2 to 20 and preferably 2 to 10.

More preferably still, compounds of formula (N ') in which R 1 denotes an alkyl radical (C ₁ -C ₄ ), A denotes a hydrogen or sodium atom, and n varies from 2 to 10.

Among the commercial products, it is preferable to use the products sold by CHEM Y under the names:

AKYPO® NP 70 (R = nonylphenyl, n = 7, A = H) AKYPO® NP 40 (R = nonylphenyl, n = 4, A = H) AKYPO® OP 40 (R = octylphenyl, n = 4, A = H )

AKYPO® OP 80 (R = octylphenyl, n = 8, A = H) AKYPO® OP 190 (R = octylphenyl, n = 19, A = H) AKYPO® RLM 38 (R = C ₁₂ -C ₁₄ alkyl), n = 3.8, A = H) AKYPO® RLM 38 NV (R = C ₁₂ -C ₁₄ alkyl, n = 4, A = Na) AKYPO® RLM 45 (R = C ₁₂ -C ₁₄ alkyl) , n = 4.5, A = H)

AKYPO® RLM 45 NV (R = C ₁₂ -C ₁₄ alkyl, n = 4.5, A = Na) AKYPO® RLM 100 (R = C ₁₂ -C ₁₄ alkyl), n = 10, A = H AKYPO® RLM 100 NV (R = C ₁₂ -C ₁₄ alkyl, n = 10, A = Na) AKYPO® RLM 130 (R = C ₁₂ -C ₁₄ alkyl, n = 13, A = H) AKYPO® RLM 160 NV (R = alkyl (C ₁₂ -C ₁₄ ), n = 16, A = Na) or by SANDOZ under the names: SANDOPAN DTC-Acid (R = alkyl (C _{1 3} ), n = 6, A = H) SANDOPAN DTC (R = alkyl (C _{1 3} ), n = 6, A = Na) SANDOPAN LS 24 (R = alkyl (C ₁₂ -C ₁₄ ), n = 12, A = Na) SANDOPAN JA 36 (R = alkyl (C 1 -C 3), n = 18, A = H), and more particularly, the products sold under the following names: AKYPO® RLM 45 AKYPO® RLM 100 AKYPO® RLM 38. The composition according to the invention may also comprise one or more nonionic surfactants chosen from mono- or polyglycerolated nonionic surfactants and polyoxyethylenated sorbitan esters.

In particular, the mono- or polyglycerolated nonionic surfactants are chosen from the group formed by mono- or polyglycerolated fatty alcohols. The term "fatty alcohol" denotes more particularly aliphatic alcohols comprising a saturated alkyl chain or an alkenyl chain comprising at least one (-C = C-) and preferably 1 to 3 unsaturations, these chains being linear or branched and comprising 8 to 40 carbon atoms, more preferably 10 to 30 carbon atoms carbon. The alkyl or alkenyl chain may optionally be substituted by an additional hydroxy group. More precisely, the fatty alcohols are preferably of formula R-OH, with R denoting a linear or branched alkyl or alkenyl radical, optionally substituted with a hydroxyl group and containing from 8 to 40 carbon atoms, more preferably from 10 to 30 carbon atoms. carbon.

According to an advantageous embodiment of the invention, the surfactant (s) not corresponding to the following formula (IM '):

in which: R represents an alkyl or alkenyl radical comprising 1 to 3 unsaturations (-C = C-), linear or branched, comprising from 8 to 40 carbon atoms and preferably from 10 to 30 carbon atoms; m represents a number (average value) ranging from 1 to 30, preferably from 1 to 15 and even more preferably from 1.5 to 10. Preferably, the mono- or polyglycerolated fatty alcohols of formula (IM ') are chosen from fatty alcohols -C ₂ -C ₂₄ comprising from 1 to 10 moles of glycerol, more particularly from oleyl alcohol containing 2 mol of glycerol, oleyl 4 mol of glycerol alcohol, lauryl alcohol 1 5 moles of glycerol.

The polyoxyethylenated sorbitan ester (s) of the invention are polyoxyethylenated esters of fatty alcohols and sorbitol anhydride. Preferably these esters are monoesters. These esters more particularly comprise a number of moles of ethylene oxide less than or equal to 30, preferably between 2 and 30, more preferably between 2 and 10, better still between 2 and 6. Preferably they have the following structure (IV)

w, x, y, z respectively denoting a number between 0 and 20 and such that w + x + y + z is less than or equal to 30, preferably between 2 and 30, more preferably between 2 and 10, better between 2 and 6 (average values). R denotes a linear or branched alkyl or alkenyl radical containing from 8 to 30 carbon atoms and optionally substituted by a hydroxyl radical. According to an even more preferred embodiment of the invention, the polyoxyethylenated sorbitan ester (s) are such that the number of moles of ethylene oxide varies from 2 to 5 (inclusive).

By way of example of polyoxyethylenated sorbitan esters of the invention, there may be mentioned sorbitan monolaurate oxyethylenated at 40E or polysorbate 21, sorbitan mono-stearate oxyethylenated at 40E or polysorbate 61, the mono-oleate of oxyethylenated sorbitan at 5OE or polysorbate 81. These sorbitan esters are for example sold by the company Uniquema under the name Tween 21, Tween 61 or Tween 81.

The composition according to the invention has a content of surfactant (s) as described above ranging from 0.01 to 20% by weight relative to the weight of the dye composition, and preferably from 0.05 to 10% by weight.

It should be noted that in the particular case of surfactants of the type of carboxylic acid (s), their content may vary from 0.01 to 30% by weight relative to the weight of the dyeing composition, and preferably from 0.1 to 15% by weight. The medium which is suitable for dyeing, also known as a dyeing medium, generally comprises water or a mixture of water and one or more solvents such as, for example, lower alkanols in dC ₄ , such as ethanol and isopropanol, polyols such as propylene glycol, dipropylene glycol or glycerol, and polyol ethers such as dipropylene glycol monomethyl ether. The solvent or solvents are generally present in proportions which can be between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 3 and 30% by weight approximately.

The dyeing composition in accordance with the invention may also contain various adjuvants conventionally used in compositions for dyeing hair, such as anionic, nonionic surfactants, or mixtures thereof, anionic, cationic, nonionic, amphoteric and zwitterionic polymers. or mixtures thereof, inorganic or organic thickeners, and in particular anionic, cationic, nonionic and amphoteric polymeric associative thickeners, antioxidants, 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.

The adjuvants above are generally present in an amount for each of them between 0.01 and 20% by weight relative to the weight of the composition. Of course, one skilled in the art will take care to choose this or these optional additional compounds such that the advantageous properties intrinsically attached to the oxidation dyeing composition according to the invention are not, or not substantially impaired by the addition or additions envisaged. The pH of the dye composition according to the invention is generally between 3 and 12 approximately, and preferably between 5 and 1 1 approximately. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used for dyeing keratin fibers or else using conventional buffer systems. 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, for example, ammonia, alkali carbonates, alkali silicates and metasilicates, alkanolamines such as mono-, di- and triethanolamines and their derivatives, sodium hydroxides, potassium or magnesium, the alkaline salts of pyrrolidine carboxylate and the compounds of formula (VI) below:

N W N

^{Rc Rd} (Vl) in which W is a propylene residue optionally substituted by a hydroxyl group or an alkyl radical in dC ₄ ; R _3, R b, R _c and R _d, identical or different, represent a hydrogen atom, an alkyl radical or C ₄ -C ₄ hydroxyalkyl. The composition according to the invention may comprise one or more oxidizing agents. The oxidizing agents conventionally used for the oxidation dyeing of keratin fibers are, for example, hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates, peracids and oxidase enzymes. among which there may be mentioned peroxidases, 2-electron oxidoreductases such as uricases and 4-electron oxygenases such as laccases. Hydrogen peroxide is particularly preferred. The dye composition according to the invention may be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratinous fibers, and especially human hair. It can result from mixing at the time of use of several compositions. In a first particular variant it results from the mixture of at least two compositions, one comprising one or more oxidation bases selected from compounds of formula (I) or their addition salts with an acid, optionally one or more different additional oxidation bases of the compound of formula (I) or of its salts, and optionally one or more couplers, a second composition comprising the surfactant (s) as described above and optionally a third composition comprising one or more oxidizing agents such as previously described In a second particular variant it results from the mixture of two compositions, one comprising one or more oxidation bases chosen from the compound of formula (I) or its addition salts with an acid, the surfactant (s) as described previously, optionally one or more additional oxidation bases different from the compound of formula (I) or its salts, and optionally one or more couplers, another composition comprising one or more oxidizing agents as described above.

The composition of the invention is therefore applied to the hair for dyeing keratinous fibers either as such or in the presence of one or more oxidizing agents, for dyeing keratinous fibers.

The process of the present invention is a process in which the composition according to the present invention as defined above, either alone or in the presence of one or more oxidizing agents, is applied to the fibers.

The color may be revealed at acidic, neutral or alkaline pH In addition, the oxidizing agent (s), if present, may be added to the composition of the invention just at the time of use or may be work from an oxidizing composition containing (s), applied simultaneously or sequentially to the composition of the invention.

According to a particular and preferred embodiment of the invention, the composition according to the present invention free of oxidizing agent (s) is mixed, preferably at the time of use, with a composition comprising, in a medium suitable for dyeing, one or more oxidizing agents. The mixture obtained is then applied to the keratinous fibers.

The oxidizing agents are those indicated above. Whether with or without oxidizing agents, the pause time of the composition (s) varies from approximately 3 to 50 minutes, preferably from 5 to approximately 30 minutes.

The temperature during the application is conventionally between room temperature (between 15 and 25 ° C.) and 80 ^° C., preferably between room temperature and 60 ^° C.

At the end of this pause time, the keratinous fibers are rinsed with water, optionally washed with shampoo, rinsed with water again and then dried.

The oxidizing composition may also contain various adjuvants conventionally used in compositions for dyeing hair and as defined above.

The pH of the oxidizing composition containing the oxidizing agent is such that, after mixing with the dyeing composition, the pH of the resulting composition applied to the keratinous fibers preferably varies between 3 and 12 approximately, and even more preferably between 5 and 1. 1. It can be adjusted to the desired value by means of acidifying or alkalizing agents usually used in dyeing keratinous fibers and as defined above. The ready-to-use composition with or without an oxidizing agent, which is finally applied to the keratinous fibers may be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for carrying out dyeing keratinous fibers, and in particular human hair. The invention also relates to a multi-compartment device or "kit" of dyeing in which a first compartment contains the dye composition of the present invention defined above without any oxidizing agent and a second compartment contains a composition comprising one or more several oxidizing agents.

A second device is constituted by a first compartment containing a composition comprising one or more oxidation bases selected from the compound of formula (I) or its addition salts with an acid, optionally one or more additional oxidation bases other than compound of formula (I) or its salts and optionally one or more couplers and a second compartment containing a composition comprising the surfactant or surfactants as previously described. A third device may optionally comprise the two compartments of the second device plus a third compartment containing a composition comprising one or more oxidizing agents.

These devices may be equipped with means for delivering the desired product onto the hair, such as the devices described in patent FR-2 586 913. The following examples serve to illustrate the invention without, however, being limiting in nature. .

Example 1

We have the following composition: the quantities extracted in ramme:

MA: expressed as active ingredient Mode of application

The composition was diluted extemporaneously with 1.5 times its weight in hydrogen peroxide at 20 volumes.

The mixture was applied to 90% white natural gray hair at the rate of 10 g per 1 g of hair for 30 minutes.

The hair was then rinsed, washed with standard shampoo and dried.

Results

The hair color was evaluated visually.

Example 2

The following composition is prepared (the quantities expressed in grams unless otherwise stated:

MA: expressed as active ingredient Mode of application

The mixture was applied to 90% white natural gray hair at the rate of 10 g per 1 g of hair for 30 minutes at room temperature.

The hair was then rinsed, washed with standard shampoo and dried.

Results

The hair color was evaluated visually.

Example 3

MA: expressed as active ingredient

Mode of application

The composition was diluted extemporaneously with 1.5 times its weight in hydrogen peroxide at 25 volumes and whose pH is 3.

The mixture thus produced was applied to natural gray hair at 90% white, at the rate of 10 g per 1 g of hair for 30 minutes.

The hair was then rinsed, washed with standard shampoo and dried.

Results

Capillary staining was evaluated visually.

Reflection height

Composition 1 Golden Brown Chestnut

Example 4

Mode of application

The composition was diluted extemporaneously with 1.5 times its weight in hydrogen peroxide at 20 volumes and whose pH is 3.

The hair was then rinsed, washed with standard shampoo and dried.

Result

The hair color was evaluated visually.

Claims

1. Coloring composition of keratinous fibers comprising, in a medium suitable for dyeing keratinous fibers: one or more oxidation bases chosen from the compound of formula (I) or its addition salts with an acid,

and

one or more surfactants chosen from those bearing at least one cationic charge, from carboxylic ether acids or one of their salts, or from mono- or polyglycerolated nonionic surfactants and polyoxyethylenated sorbitan esters.

2. Composition according to the preceding claim, characterized in that the content of compound of formula (I) is between 0.001 to 10% by weight relative to the total weight of the dye composition.

3. Composition according to any one of the preceding claims, characterized in that the surfactant (s) carrying at least one cationic charge are chosen from: (i) the quaternary ammonium salts of formula (II) below:

in which

X ^' is an anion chosen for example from the group of halides (chloride, bromide or iodide) or alkyl (C ₂ -C ₆ ) sulphates, more particularly methyl sulphate, phosphates, alkyl or alkylarylsulphonates, anions derived from acid organic compound such as acetate or lactate, and

(1) the radicals R 1 to R 3, which may be identical or different, represent a linear or branched aliphatic radical, in d ₄ , or an aryl or alkylaryl radical, the alkyl radical optionally carrying an alkoxy, alkylamide group, R ₄ denotes an alkyl radical, linear or branched, Ci ₆ -C ₃₀ , preferably Ci ₄ -

(2) the radicals R 1 and R ₂ , which are identical or different, represent an aliphatic radical, linear or branched, in dC ₄ , or a radical that aryl or alkylaryl, the the alkyl radical optionally carrying a C ₁ -C ₄ alkoxy, alkylamide or hydroxyalkyl group;

R ₃ and R ₄ , identical or different, denote a linear or branched C ₁₂ -C 30 alkyl or alkenyl radical, said radical optionally comprising at least one ester or amide function; (ii) the quaternary ammonium salts of the imidazolinium of formula (III) below:

in which

R ₅ represents an alkenyl or C 12 -C 30 alkyl radical,

R ₆ represents a hydrogen atom, a C 1 -C ₄ alkyl radical or an alkenyl or C 12 -C 30 alkyl radical,

X is an anion X especially selected from the group of halides, phosphates, acetates, lactates, alkylsulfates, alkyl-or-alkylarylsulfonates. (iii) quaternary diammonium salts of formula (IV):

in which

R ₉ denotes a C 12 -C 30 alkyl or alkenyl radical,

R _10, Rn, R _2, R ₁ 3 and R _14, identical or different are selected from hydrogen or an alkyl radical -C _4, and

X is an anion chosen especially from the group of halides, acetates, phosphates, nitrates and methylsulphates;

(C _n H _2n O) _z

R ₁₇ - C - (OC _n H _2n) _y N - (C _p H _2p O) _x - R ₁₆

R "(V) in which:

• R ₅ is selected from alkyl, dC ₆ hydroxyalkyl dC ₆ dihydroxyalkyl, C ₂ -C _6;

Ri ₆ is chosen from the radical R ₁₉ -CO-, a radical R ₂ o alkyl or alkenyl Ci-C ₂₂ linear or branched, a hydrogen atom, Ris is chosen from the radical R ₂₁ -CO-, a radical R ₂₂ alkyl or alkenyl in linear or branched CrC ₆ , a hydrogen atom,

R ₁₇ , R ₁₉ and R ₂₁ , which are identical or different, are chosen from linear or branched C ₁₂ -C ₂₂ alkyl or alkenyl radicals; • n, p and r, identical or different, are integers ranging from 2 to 6;

• y is an integer from 1 to 10;

• x and z, identical or different, are integers from 0 to 10;

• X ^' is a simple or complex anion, organic or inorganic.

4. Composition according to the preceding claim, characterized in that the surfactant or surfactants carrying at least one cationic charge are chosen from cationic surfactants of formula (II), and preferably one or more cationic surfactants of formula (II) corresponding to option (1).

5. Composition according to the preceding claim, characterized in that the surfactant or surfactants carrying at least one cationic charge are chosen from amphoteric or zwitterionic surfactants, mention may be made of: derivatives of secondary or tertiary aliphatic amines, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms and comprising at least one anionic group such as, for example, a carboxylate, sulphonate, sulphate, phosphate or phosphonate group, alkylbetaines, sulphobetaines, alkylamidoalkyls (C ₆ -C ₈ ) betaines, alkylamidoalkyl (C ₆ -C ₈ ) sulfobetaines.

6. Composition according to any one of the preceding claims, characterized in that the carboxylic acid or acids are chosen from polyoxyalkylenated alkyl- or alkenyl- (C ₆ -C ₂₄ ) ether carboxylic acids, alkyl (C ₆ - C ₂₄ ) polyoxyalkylenated carboxylic aryl ether and their salts, polyoxyalkylenated (C ₆ -C ₂₄ ) alkylamido carboxylic acids and their salts, and mixtures thereof.

7. Composition according to any one of the preceding claims, characterized in that the carboxylic acid or acids correspond to the following formula (N '): R ₁ - (OC ₂ H ₄ ) - - OCH ₂ COOA in which:

R ₁ represents a radical or a mixture of linear or branched C ₈ -C ₂₂ alkyl or alkenyl radicals, a (C ₈ -C ₉ ) alkyl phenyl radical, a radical R ₂ CONH-CH ₂ -CH ₂ - with R ₂ denoting a linear or branched C ₁₁ -C ₂₁ alkyl or alkenyl radical, n is an integer or decimal number ranging from 2 to 24 A denotes H, ammonium, Na, K, Li, Mg or a monoethanolamine or triethanolamine residue.

8. Composition according to the preceding claim, characterized in that the carboxylic acid ether or acids correspond to the formula (N ') in which R ₁ denotes a radical or a mixture of alkyl (C ₁₂ -C ₁₄ ), cocoyl, oleyl radicals. ; a nonylphenyl or octylphenyl radical; A denotes a hydrogen or sodium atom; n varies from 2 to 20.

9. Composition according to any one of the preceding claims, characterized in that the mono- or polyglycerolated nonionic surfactant or surfactants correspond to the

in which :

R represents an alkyl or alkenyl radical comprising 1 to 3 unsaturations (-C = C-), linear or branched, comprising from 8 to 40 carbon atoms; m represents a number ranging from 1 to 30.

10. Composition according to Claim 3, characterized in that the mono- or poly-glycerolated fatty alcohols of formula (IM ') are chosen from C ₁₂ -C ₂₄ fatty alcohols comprising from 1 to 10 moles of glycerol, more particularly from oleic alcohol containing 2 moles of glycerol, oleic alcohol containing 4 moles of glycerol and lauryl alcohol containing 1.5 moles of glycerol.

11. Composition according to any one of the preceding claims, characterized in that the polyoxyethylenated sorbitan esters have the structure (IV)

w, x, y, z respectively denoting a number between 0 and 20 and such that w + x + y + z is less than or equal to 30, preferably between 2 and 30,

R denotes a linear or branched alkyl or alkenyl radical containing from 8 to 30 carbon atoms and optionally substituted by a hydroxyl radical.

12. Composition according to any one of the preceding claims, characterized in that the sorbitan ester or esters comprise a number of moles of ethylene oxide of between 2 and 10, better still between 2 and 6 (average values).

13. Composition according to any one of the preceding claims, characterized in that the polyoxyethylenated sorbitan ester or esters are chosen from sorbitan monolaurate oxyethylenated at 40E, sorbitan mono-stearate oxyethylenated at 40E, mono-oleate. of oxyethylenated sorbitan at 5OE.

14. Composition according to any one of the preceding claims, characterized in that the content of surfactant (s) is from 0.01 to 20% by weight relative to the weight of the dye composition, and preferably from 0.05 to 10% by weight.

15. Composition according to any one of the preceding claims, characterized in that it comprises one or more couplers.

16. Composition according to any one of the preceding claims, characterized in that it contains one or more different additional oxidation bases of the compound of formula (I) or its salts, in particular chosen from ortho- or para-phenylenediamines. , double bases, ortho- or para-aminophenols, and heterocyclic bases, as well as the addition salts of these compounds with an acid.

17. Composition according to any one of the preceding claims, characterized in that it contains one or more oxidizing agents, in particular chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts. peracids and oxidase enzymes and preferably hydrogen peroxide.

18. A process for dyeing keratin fibers, characterized in that a composition as defined in any one of claims 1 to 16 is applied to the keratin fibers without an oxidizing agent.

19. A process for dyeing keratinous fibers, characterized in that a composition as defined in any one of claims 1 to 16 is applied to the keratinous fibers in the presence of one or more oxidizing agents.

20. A multi-compartment device in which a first compartment contains a dye composition as defined in any one of claims 1 to 16 and a second compartment containing a composition comprising one or more oxidizing agents.

21. A multi-compartment device in which a first compartment comprises one or more oxidation bases chosen from the compound of formula (I) or one of its salts with an acid according to claim 1 and optionally one or more bases of different oxidation of the compound of formula (I) or its salts and optionally one or more couplers; a second compartment contains a composition comprising one or more surfactants as described in any one of claims 1 and 3 to 13, and optionally a third compartment containing a composition comprising one or more oxidizing agents.