WO2012059409A1

WO2012059409A1 - Foam dyeing composition comprising at least one specific amphoteric terpolymer

Info

Publication number: WO2012059409A1
Application number: PCT/EP2011/068929
Authority: WO
Inventors: Caroline Goget; Gautier Deconinck; Richard Sabourin; Daisuke Misu
Original assignee: L'oreal
Priority date: 2010-11-02
Filing date: 2011-10-28
Publication date: 2012-05-10
Also published as: FR2966730A1; FR2966730B1

Abstract

A subject-matter of the present invention is a composition for dyeing human keratinous fibres, such as the hair, in the foam form, comprising: (a) at least one amphoteric polymer obtained from - at least one monomer chosen from acrylic acid and methacrylic acid, - at least one monomer chosen from acrylamide and one of its derivatives, - at least one monomer chosen from monomers comprising one or more quaternary ammonium groups; (b) at least one basifying agent; (c) at least one surface-active agent chosen from amphoteric surfactants and anionic surfactants; (d) at least one oxidizing agent; (e) at least one oxidation dye precursor. The present invention also relates to a method for the treatment of human keratinous fibres starting from this composition in the foam form and to aerosol or non-aerosol devices which make it possible to generate this foam.

Description

FOAM DYEING COMPOSITION COMPRISING AT LEAST ONE SPECIFIC AMPHOTERIC TERPOLYMER

The subject-matter of the present invention is a method for dyeing the hair in the foam form starting with a composition comprising oxidation dye precursors, and a composition in the foam form.

Mention may be made, among methods for dyeing human keratinous fibres, such as the hair, of oxidation or permanent dyeing. More particularly, this dyeing method uses one or more oxidation dyes and usually one or more oxidation bases, optionally in combination with one or more couplers.

In general, oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or ara-aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds which, in combination with oxidizing products, make it possible to access coloured entities.

The shades obtained with these oxidation bases are very often varied by combining them with one or more couplers, the latter being chosen in particular from aromatic mefa-diamines, mefa-aminophenols, mefa-diphenols and certain

heterocyclic compounds, such as indole compounds.

The variety of molecules deployed as oxidation bases and couplers makes it possible to obtain a rich palette of colours.

Permanent dyeing methods thus consist in employing, with the dyeing composition, an aqueous composition comprising at least one oxidizing agent, such as hydrogen peroxide, under alkaline pH conditions in the great majority of cases. The basifying agent conventionally used is aqueous ammonia or other basifying agents, such as alkanolamines.

The dyeing compositions can be provided in various forms, such as lotions, gels, emulsions, creams or foams. Dying foams are pleasant to use but they often exhibit a poor hold over time. For example, rapid disappearance of the foam after application or non-uniform application along the fibres may be observed.

There exists a continuous real need to develop oxidation dye combinations in the foam form which are easy to prepare and to apply and which remain sufficiently stable over time while retaining successful dyeing properties.

This aim and others are achieved by the present invention, a subject-matter of which is thus a composition for dyeing human keratinous fibres, such as the hair, in the foam form comprising:

a) at least one amphoteric polymer obtained from

- at least one monomer chosen from acrylic acid or methacrylic acid,

- at least one monomer chosen from acrylamide or one of its derivatives, - at least one monomer chosen from monomers comprising one or more quaternary ammonium groups;

b) at least one basifying agent

c) at least one surfactant chosen from amphoteric surfactants and anionic surfactants;

d) at least one oxidizing agent;

e) at least one oxidation dye.

It also relates to a method for dyeing human keratinous fibres starting from this composition.

A subject-matter of the invention is likewise a two-compartment device comprising, in one, a composition including one or more amphoteric and/or anionic surfactants, one or more oxidation dye precursors, one or more basifying agents and one or more amphoteric polymers obtained from at least one monomer chosen from acrylic acid or methacrylic acid, from at least one monomer chosen from acrylamide or one of its derivatives and from at least one monomer chosen from monomers comprising one or more quaternary ammonium groups, in a second, a composition including one or more oxidizing agents and, in a third, a container provided with an element which makes possible the delivery, in the form of a foam, of the composition of the invention resulting from the mixing of the two preceding compositions.

Another subject-matter of the invention is a device for dyeing keratinous fibres comprising the composition of the invention and a foam dispenser for delivering the composition in the form of a foam.

The composition of the invention is provided in the form of a foam which is particularly pleasant to apply. It exhibits a light and airy texture which makes them particularly pleasant to use. The qualities of the foam are sufficiently persistent over time to make it possible to apply the dyeing product in a homogeneous fashion devoid of run-off. The composition of the invention makes it possible to retain particularly impressive dyeing properties, such as the power of the colour, the resistance to external agents (shampoos, perspiration, light) and the selectivity.

Other characteristics and advantages of the invention will become more clearly apparent in the light of the description and examples which follow.

In that which follows and unless otherwise indicated, the limits of a range of values are included within this range. The term "at least one" associated with an ingredient of the composition means "one or more".

The human keratinous fibres treated by the method according to the invention are preferably the hair.

The composition of the invention comprises at least one amphoteric polymer obtained from -at least one monomer chosen from acrylic acid or methacrylic acid,

-at least one monomer chosen from acrylamide or one of its derivatives,

-at least one monomer chosen from monomers comprising one or more quaternary ammonium groups.

The acrylamide derivatives are preferably chosen from methacrylamide,

N-octylacrylamide, N-(tert-butyl)acrylamide and Ν,Ν-dimethylacrylamide. More preferably still, the monomer chosen from acrylamide or one of its derivatives is acrylamide.

The monomer chosen from acrylic acid and methacrylic acid is preferably acrylic acid.

The monomer chosen from monomers comprising one or more quaternary ammonium groups is preferably chosen from diallyldialkylammonium salts and in particular from diallyldimethylammonium salts. More preferably still, this monomer is diallyldimethylammonium chloride.

Mention may be made, as an example of amphoteric polymer according to the invention, of acrylic acid/diallyldimethylammonium chloride/acrylamide terpolymers.

Mention may more particularly be made of the acrylic

acid/diallyldimethylammonium chloride/acrylamide (35/30/35) terpolymer sold under the name Merquat 3330; the acrylic acid/diallyldimethylammonium

chloride/acrylamide (66/16/18) terpolymer sold under the name Merquat 3333 and the acrylic acid/diallyldimethylammonium chloride/acrylamide (22.5/26.5/51) terpolymer sold under the name Merquat Plus 3331.

According to the present invention, the amphoteric polymer or polymers (a) are present in the composition in a quantity ranging from 0.01 to 3% by weight, with respect to the total weight of the composition.

The composition comprises at least one basifying agent. This agent may be chosen from mineral or organic or hybrid basifying agents, or mixtures thereof.

The mineral basifying agent(s) are preferably chosen from aqueous ammonia, alkali metal carbonates or bicarbonates such as sodium or potassium carbonates and sodium or potassium bicarbonates, sodium hydroxide or potassium hydroxide, or mixtures thereof.

The organic basifying agent(s) are preferably chosen from organic amines with a pK at 25°C of less than 12, preferably less than 10 and even more advantageously less than 6. It should be noted that it is the pK corresponding to the function of highest basicity.

Mention may be made, as hybrid compounds, of the salts of the

abovementioned amines with acids, such as carbonic acid or hydrochloric acid. The organic basifying agent(s) are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds of formula (I) below:

Rx Rz

W N

Ry ^X R. _(I)

in which W is a C C₆ alkylene residue optionally substituted with a hydroxyl group or a C C₆ alkyl radical; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom or a C C₆ alkyl, C C₆ hydroxyalkyl or C C₆ aminoalkyl radical.

Examples of such amines that may be mentioned include 1 ,3-diaminopropane, 1 ,3-diamino-2-propanol, spermine and spermidine.

The term "alkanolamine" means an organic amine comprising a primary, secondary or tertiary amine function, and one or more linear or branched C C₈ alkyl groups bearing one or more hydroxyl radicals.

Alkanolamines such as mono-, di- or tri- alkanolamines comprising from one to three identical or different C C₄ hydroxyalkyl radicals are in particular suitable for performing the invention.

Among compounds of this type, mention may be made of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N- dimethylaminoethanolamine, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2- amino-2-methyl-1 ,3-propanediol, 3-amino-1 ,2-propanediol, 3-dimethylamino-1 ,2- propanediol and tris(hydroxymethyl)amino methane.

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

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

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

Such basic amino acids are preferably chosen from those corresponding to formula (II) below: i osen from:

-(CH₂)₃NH₂

-(CH₂)₂NH₂ -(CH₂)₂NHCONH₂

-(CH₂)₂NH C— NH₂

N^H

The compounds corresponding to formula (II) are histidine, lysine, arginine, ornithine and citrulline.

The organic amine may also be chosen from organic amines of heterocyclic type. Besides histidine that has already been mentioned in the amino acids, mention may be made in particular of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.

The organic amine may also be chosen from amino acid dipeptides. As amino acid dipeptides that may be used in the present invention, mention may be made especially of carnosine, anserine and baleine.

The organic amine is chosen from compounds comprising a guanidine function.

As amines of this type that may be used in the present invention, besides arginine, which has already been mentioned as an amino acid, mention may be made especially of creatine, creatinine, 1 , 1-dimethylguanidine, 1 , 1-diethylguanidine, glycocyamine, metformin, agmatine, N-amidinoalanine, 3-guanidinopropionic acid, 4- guanidinobutyric acid and 2-([amino(imino)methyl]amino)ethane-1-sulphonic acid.

Mention may be made in particular of the use of guanidine carbonate or monoethanolamine hydrochloride as hybrid compounds.

The composition of the invention preferably contains one or more

alkanolamines and/or one or more basic amino acids, more advantageously one or more alkanolamines. More preferentially still, the organic amine is

monoethanolamine.

According to a specific embodiment, the composition of the invention comprises, as basifying agent, at least one alkanolamine.

Preferably, the alkanolamine is monoethanolamine.

In an alternative form of the invention, the composition of the invention comprises, as basifying agent, one or more alkanolamines, preferably

monoethanolamine and aqueous ammonia. In this alternative form, the alkanolamine or alkanolamines are present in a predominant amount with respect to the aqueous ammonia.

Advantageously, the composition according to the invention exhibits a content of basifying agent(s) ranging from 0.01 to 30% by weight, preferably from 0.1 to 20% by weight and better still from 1 to 10% by weight, with respect to the weight of the said composition.

The composition according to the invention also comprises at least one oxidizing agent.

The oxidizing agents are, for example, chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, or peroxygenated salts, such as, for example, persulphates, perborates, peracids and their precursors and percarbonates of alkali metals or alkaline earth metals. Advantageously, the oxidizing agent is hydrogen peroxide.

The content of oxidizing agent(s) more particularly represents from 0.1 to 20% by weight and preferably from 0.5 to 10% by weight, with respect to the weight of the composition.

As indicated above, the composition according to the invention comprises one or more oxidation dye precursors.

Use may be made, as oxidation dye precursors, of oxidation bases and couplers.

By way of example, the oxidation bases are chosen from para- phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho- aminophenols, heterocyclic bases and their addition salts.

Mention may be made, among para-phenylenediamines, by way of example, of para-phenylenediamine, para-toluylenediamine, 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, Ν,Ν-diethyl-para-phenylenediamine, N,N-dipropyl-para- phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis^-hydroxyethyl)- para-phenylenediamine, 4-N,N-bis^-hydroxyethyl)amino-2-methylaniline, 4-N,N- bis^-hydroxyethyl)amino-2-chloroaniline, 2-^-hydroxyethyl)-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, Ν-(β- hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl, -hydroxyethyl)-para- phenylenediamine, N-^j-dihydroxypropyl)-para-phenylenediamine, N-(4'-amino- phenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-(β- hydroxyethyloxy)-para-phenylenediamine, 2-^-acetylaminoethyloxy)-para-phenylene- diamine, N-^-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2- thienyl-para-phenylenediamine, 2- -hydroxyethylamino)-5-aminotoluene, 3-hydroxy-

1- (4'-aminophenyl)pyrrolidine and their addition salts with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluylenediamine, 2-isopropyl-para-phenylenediamine, 2-( -hydroxyethyl)-para- phenylenediamine, 2-^-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-^-acetylaminoethyloxy)-para-phenylenediamine and their addition salts with an acid are particularly preferred.

Mention may be made, among bisphenylalkylenediamines, by way of example, of N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, N,N'-bis - hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine, N,N'-bis(4- aminophenyl)tetramethylenediamine, N,N'-bis -hydroxyethyl)-N,N'-bis(4-amino- phenyl)tetramethylenediamine, N,N'-bis(4-methylaminophenyl)tetra- methylenediamine, N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'- methylphenyl)ethylenediamine, 1 ,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctane and their addition salts.

Mention may be made, among para-aminophenols, by way of example, of para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3- chlorophenol, 4-amino-3-(hydroxymethyl)phenol, 4-amino-2-methylphenol, 4-amino-2- (hydroxymethyl)phenol, 4-amino-2-(methoxymethyl)phenol, 4-amino-2-(amino- methyl)phenol, 4-amino-2-[(β-hydroxyethyl)aminomethyl]phenol, 4-amino-2- fluorophenol and their addition salts with an acid.

Mention may be made, among ortho-aminophenols, by way of example, of 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-

2- aminophenol and their addition salts.

Mention may be made, among heterocyclic bases, by way of example, of pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.

Mention may be made, among pyridine derivatives, 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-aminopyridine, 3,4-diaminopyridine and their addition salts.

Other pyridine oxidation bases of use in the present invention are the 3- aminopyrazolo[1 ,5-a]pyridine oxidation bases or their addition salts described, for example, in patent application FR 2 801 308. Mention may be made, by way of example, of pyrazolo[1 ,5-a]pyridin-3-ylamine; 2-(acetylamino)pyrazolo[1 ,5-a]pyridin-3- ylamine; 2-(morpholin-4-yl)pyrazolo[1 ,5-a]pyridin-3-ylamine; 3-aminopyrazolo- [1 ,5-a]pyridine-2-carboxylic acid; 2-methoxypyrazolo[1 ,5-a]pyridin-3-ylamine; (3- aminopyrazolo[1 ,5-a]pyridin-7-yl)methanol; 2-(3-aminopyrazolo[1 ,5-a]pyridin-5- yl)ethanol; 2-(3-aminopyrazolo[1 ,5-a]pyridin-7-yl)ethanol; (3-aminopyrazolo[1 ,5- a]pyridin-2-yl)methanol; 3,6-diaminopyrazolo[1 ,5-a]pyridine; 3,4-diaminopyrazolo[1 ,5- a]pyridine; pyrazolo[1 ,5-a]pyridine-3,7-diamine; 7-(morpholin-4-yl)pyrazolo- [1 ,5-a]pyridin-3-ylamine; pyrazolo[1 ,5-a]pyridine-3,5-diamine; 5-(morpholin-4- yl)pyrazolo[1 ,5-a]pyridin-3-ylamine; 2-[(3-aminopyrazolo[1 ,5-a]pyridin-5-yl)(2-hydroxy- ethyl)amino]ethanol; 2-[(3-aminopyrazolo[1 ,5-a]pyridin-7-yl)(2- hydroxyethyl)amino]ethanol; 3-aminopyrazolo[1 ,5-a]pyridin-5-ol; 3-aminopyrazolo[1 ,5- a]pyridin-4-ol; 3-aminopyrazolo[1 ,5-a]pyridin-6-ol; 3-aminopyrazolo[1 ,5-a]pyridin-7-ol; and their addition salts.

Mention may be made, among pyrimidine derivatives, of the compounds described, for example, in patents DE 2 359 399; JP 88-169571 ; JP 05-63124;

EP 0 770 375 or patent application WO 96/15765, such as

2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6- triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and their tautomeric forms, when a tautomeric equilibrium exists.

Mention may be made, among pyrazole derivatives, of the compounds described in patents DE 3 843 892 and DE 4 133 957 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-methylpyrazole, 4,5-diamino-1-^-hydroxyethyl)pyrazole, 3,4- diaminopyrazole, 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-phenyl- pyrazole, 4-amino-1 ,3-dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3- methylpyrazole, 4,5-diamino-3-(tert-butyl)-1-methylpyrazole, 4,5-diamino-1-(tert- butyl)-3-methylpyrazole, 4,5-diamino-1-^-hydroxyethyl)-3-methylpyrazole,

4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3-(4'- methoxyphenyl)pyrazole, 4,5-diamino-1-ethyl-3-(hydroxymethyl)pyrazole, 4,5- diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1- isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2'- aminoethyl)amino-1 ,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl-3,4,5- triaminopyrazole, 3,5-diamino-1-methyl-4-(methylamino)pyrazole, 3,5-diamino-4- - hydroxyethyl)amino-1-methylpyrazole and their addition salts. Use may also be made of 4,5-diamino-1-^-methoxyethyl)pyrazole.

Use will preferably be made of a 4,5-diaminopyrazole and more preferably still of 4,5-diamino-1-^-hydroxyethyl)pyrazole and/or one of its salts.

Mention may also be made, as pyrazole derivatives, of diamino-N,N- dihydropyrazolopyrazolones, in particular those described in application

FR-A-2 886 136, such as the following compounds and their addition salts: 2,3- diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-ethylamino-6,7- dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-isopropylamino-6,7-dihydro- 1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-(pyrrolidin-1 -yl)-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 4,5-diamino-1 ,2-dimethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2-diethyl-1 ,2-dihydropyrazol-3-one, 4,5-diamino-1 ,2-di(2-hydroxyethyl)-

1 .2- dihydropyrazol-3-one, 2-amino-3-(2-hydroxyethyl)amino-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 2-amino-3-dimethylamino-6,7-dihydro-1 H,5H- pyrazolo[1 ,2-a]pyrazol-1 -one, 2,3-diamino-5,6,7,8-tetrahydro-1 H,6H-pyridazino[1 ,2- a]pyrazol-1 -one, 4-amino-1 ,2-diethyl-5-(pyrrolidin-1 -yl)-1 ,2-dihydropyrazol-3-one, 4- amino-5-[3-(dimethylamino)pyrrolidin-1 -yl]-1 ,2-diethyl-1 ,2-dihydropyrazol-3-one or

2.3- diamino-6-hydroxy-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one. It is preferable to use 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1 -one and/or one of its salts.

Use will preferably be made, as heterocyclic bases, of 4,5-diamino-1 -^- hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol- 1 -one and/or one of their salts.

Mention may in particular be made, among the couplers which can be used in the composition of the invention, of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene couplers or heterocyclic couplers and their addition salts.

Mention may be made, by way of example, of 1 ,3-dihydroxybenzene, 1 ,3- dihydroxy-2-methylbenzene, 4-chloro-1 ,3-dihydroxybenzene, 2,4-diamino-1 - - hydroxyethyloxy)benzene, 2-amino-4-^-hydroxyethylamino)-1 -methoxybenzene, 1 ,3- diaminobenzene, 1 ,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1 - dimethylaminobenzene, sesamol, 1 ^-hydroxyethylamino-3,4- methylenedioxybenzene, oc-naphthol, 2-methyl-1 -naphthol, 6-hydroxyindole, 4- hydroxyindole, 4-hydroxy-N-methylindole, 2-amino-3-hydroxypyridine, 6-hydroxy- benzomorpholine, 3,5-diamino-2,6-dimethoxypyridine, 1 -N-^-hydroxyethyl)amino-3,4- methylenedioxybenzene, 2,6-bis(β-hydroxyethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1 H-3-methylpyrazol-5-one, 1 -phenyl-3-methylpyrazol- 5-one, 2,6-dimethylpyrazolo[1 ,5-b]-1 ,2,4-triazole, 2,6-dimethylpyrazolo[3,2-c]-1 ,2,4- triazole, 6-methylpyrazolo[1 ,5-a]benzimidazole, their addition salts with an acid and their mixtures.

The addition salts of the oxidation bases and couplers are chosen in particular from the addition salts with an acid, such as hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, lactates, tosylates, benzenesulphonates, phosphates and acetates. The oxidation base or bases are generally each present in an amount of between 0.0001 and 10% by weight, with respect to the total weight of the

composition, and preferably from 0.005 to 5% by weight, with respect to the total weight of the composition.

The coupler or couplers each generally represent from 0.0001 to 10% by weight, with respect to the total weight of the composition, and preferably from 0.005 to 5% by weight, with respect to the total weight of the composition.

The composition according to the invention can comprise synthetic or natural and cationic or nonionic direct dyes.

Mention may be made, as examples of direct dyes which are particularly suitable, of nitrobenzene dyes, azo, azomethine or methine direct dyes,

azacarbocyanines, such as tetraazacarbocyanines (tetraazapentamethines), quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes, azine, xanthene, triarylmethane, indoamine or indigoid direct dyes, phthalocyanines, porphyrins and natural direct dyes, alone or as mixtures. In particular, mention may be made of direct dyes from among: azo; methine; carbonyl; azine; nitro(hetero)aryl; tri(hetero)arylmethane; porphyrin; phthalocyanine and natural direct dyes, alone or as mixtures.

When they are present, the direct dye or dyes more particularly represent from 0.0001 to 10% by weight of the total weight of the composition and preferably from 0.005 to 5% by weight.

The composition according to the invention comprises at least one surfactant chosen from amphoteric surfactants and anionic surfactants. The surfactants of use in the composition of the invention are surfactants known per se in the field of the dyeing of keratinous fibres.

The amphoteric or zwitterionic surface-active agent or agents which can be used in the present invention can in particular be secondary or tertiary aliphatic amine derivatives which are optionally quaternized, in which the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, the said amine derivatives comprising at least one anionic group, such as, for example, a carboxylate, sulphonate, sulphate, phosphate or phosphonate group. Mention may in particular be made of (C₈-C₂o)alkylbetanes, sulfobetanes, (C8-C2o)alkylamido(CrC₆)alkylbetanes or (C8-C2o)alkylamido(CrC₆)alkylsulfobetanes, preferably (C₈-C2o)alkylamido(Cr C₆)alkylbetanes. Mention may also be made, among secondary or tertiary aliphatic amine derivatives which are optionally quaternized which can be used, as defined above, of the compounds with the following respective structures (III) and (ΙΙΓ):

Ra-CONHCH₂CH₂-N⁺(Rb)(Rc)(CH₂COO^") in which:

Ra represents a Ci₀-C₃₀ alkyl or alkenyl group derived from an acid

Ra-COOH, preferably present in hydrolysed coconut oil, a heptyl, nonyl or undecyl group,

Rb represents a β-hydroxyethyl group, and

Rc represents a carboxymethyl group; and

Ra'-CONHCH₂CH₂-N(B)(B') (III') in which:

B represents -CH₂CH₂OX',

B' represents -(CH₂)_ZY', with z = 1 or 2,

X' represents the -CH₂-COOH, -CH₂-COOZ', -CH₂CH₂-COOH or

-CH₂CH₂-COOZ' group or a hydrogen atom,

Y' represents -COOH, -COOZ', the -CH2-CHOH-S03H group or

-CH2-CHOH-S03Z' group,

Z' represents an ion resulting from an alkali metal or alkaline earth metal, such as sodium, an ammonium ion or an ion resulting from an organic amine,

Ra' represents a Ci₀-C₃₀ alkyl or alkenyl group of an acid Ra'-COOH preferably present in hydrolysed linseed oil or coconut oil, an alkyl group, in particular a C17 alkyl group and its iso form, or a Ci₇ group which is unsaturated.

These compounds are categorized in the CTFA dictionary, 5th edition, 1993, under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium

caprylamphodipropionate, disodium capryloamphodipropionate,

lauroamphodipropionic acid and cocoamphodipropionic acid.

By way of example, mention may be made of the cocoamphodiacetate sold by

Rhodia under the trade name Miranol^® C2M Concentrate.

Use is preferably made, among the abovementioned amphoteric or zwitterionic surface-active agents, of betaines comprising at least one saturated or unsaturated C₈-C₃₀ fatty chain and in particular of the compounds of formula (A):

Rr(CONH)_x-ArN⁺(R₂)(R₃)-A₂-Z (A)

with

x denoting 0 or 1 , Ai and A₂ denoting, independently of one another, a linear or branched C1-C1₀ alkylene radical optionally substituted with a hydroxyl radical,

denoting a linear or branched C6-C30 alkyl or alkenyl radical,

R₂ and R₃ denoting, independently of one another, a linear or branched C C₄ alkyl radical,

Z denoting a C0₂ ^" group or an S0₃ ^" group.

Preferably, R₂ and R₃ denote a methyl radical.

The amphoteric surfactant or surfactants of betaine type used in the cosmetic composition according to the present invention can in particular be (C₈.₂o)alkyl betaines, (C₈_₂₀)alkyl sulfobetaines, (C₈.₂o alkyl) amido(C₂.₈ alkyl) betaines or (C₈_₂₀ alkyl) amido(C₆-₈ alkyl) sulfobetaines.

Use is preferably made, among the abovementioned amphoteric surfactants, of (C₈.₂₀ alkyl) betaines, (C₈.₂₀ alkyl) amido(C₂_₈ alkyl)betaines and their mixtures.

More particularly, the amphoteric surfactants of betaine type ii) are selected from coco betaine and cocamidopropyl betaine.

The term "anionic surface-active agent" is understood to mean a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the following groups: C0₂H, C0₂ ^", S0₃H, S0₃ ^", OS0₃H, OSO3^", H₂P0₃, HPO3^" ,P0₃ ^2", H₂P0₂, HP0₂, HP0₂ ^", P0₂ ^", POH, PO^".

As examples of anionic surfactants that may be used in the composition according to the invention, mention may be made of alkyl sulphates, alkyl ether sulphates, alkylamido ether sulphates, alkylaryl polyether sulphates, monoglyceride sulphates, alkyl sulphonates, alkylamide sulphonates, alkylaryl sulphonates, alpha- olefin sulphonates, paraffin sulphonates, alkyl sulphosuccinates, alkyl ether sulphosuccinates, alkylamide sulphosuccinates, alkyl sulphoacetates, acyl sarcosinates, acyl glutamates, alkyl sulphosuccinamates, acyl isethionates and N-acyltaurates, salts of alkyl monoesters of polyglycoside-polycarboxylic acids, acyl lactylates, D-galactoside-uronic acid salts, alkyl ether carboxylic acid salts, alkylaryl ether carboxylic acid salts, alkylamido ether carboxylic acid salts; and the

corresponding non-salified forms of all these compounds; the alkyl and acyl groups of all these compounds comprising from 6 to 24 carbon atoms and the aryl group denoting a phenyl group.

These compounds may be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.

The salts of Ο_δ-₂₄ alkyl monoesters of polyglycoside-polycarboxylic acids can be chosen from C₆.₂₄ alkyl polyglycoside-citrates, C₆.₂₄ alkyl polyglycoside-tartrates and C₆-₂₄ alkyl polyglycoside-sulfosuccinates. When the anionic surfactant(s) (ii) are in salt form, it/they may be chosen from alkali metal salts, such as the sodium or potassium salt and preferably the sodium salt, the ammonium salts, the amine salts and in particular amino alcohol salts, or the alkaline earth metal salts, such as the magnesium salt.

Mention may in particular be made, as examples of amino alcohol salts, of the mono-, di- and triethanolamine salts, the mono-, di- and triisopropanolamine salts and the 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1 ,3-propanediol and

tris(hydroxymethyl)aminomethane salts.

Alkali metal or alkaline earth metal salts and in particular the sodium or magnesium salts are preferably used.

It is preferable, among anionic surfactants, to use, according to the invention, the alkylsulphate and alkyl ether sulphate salts and their mixtures.

The surfactant or surfactants are preferably chosen from amphoteric surfactants.

According to a specific embodiment, the composition of the invention comprises one or more amphoteric surfactants, one or more anionic surfactants and one or more nonionic surfactants. According to this embodiment, the nonionic surfactants are chosen, for example, from mono- or polyoxyalkylenated or mono- or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units or their combination, preferably oxyethylene units.

Examples of oxyalkylenated nonionic surfactants that may be mentioned include:

• oxyalkylenated (C₈-C₂4)alkylphenols,

• saturated or unsaturated, linear or branched, oxyalkylenated C₈-C₃₀ alcohols, · saturated or unsaturated, linear or branched, oxyalkylenated C₈-C₃₀ amides,

• esters of saturated or unsaturated, linear or branched, C₈-C₃₀ acids and of polyethylene glycols,

• polyoxyethylenated esters of saturated or unsaturated, linear or branched, C₈-C₃₀ acids and of sorbitol,

· saturated or unsaturated, oxyethylenated plant oils,

• condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures;

The surfactants exhibit a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 100, preferably between 2 and 50, preferably between 2 and 30.

In accordance with a preferred embodiment of the invention, the oxyalkylenated nonionic surfactants are chosen from oxyethylenated C₈-C₃₀ alcohols comprising from 1 to 100 mol of ethylene oxide; and polyoxyethylenated esters of saturated or unsaturated, linear or branched C₈-C₃₀ acids and of sorbitol comprising from 1 to 100 mol of ethylene oxide.

As examples of monoglycerolated or polyglycerolated nonionic surfactants, monoglycerolated or polyglycerolated C₈-C₄₀ alcohols are preferably used.

In particular, the monoglycerolated or polyglycerolated C₈-C₄₀ alcohols correspond to the following formula:

RO-[CH₂-CH(CH₂OH)-0]_m-H

in which R represents a linear or branched C₈-C₄₀ and preferably C₈-C₃₀ alkyl or alkenyl radical, and m represents a number ranging from 1 to 30 and preferably from 1 to 10.

As examples of compounds that are suitable in the context of the invention, mention may be made of lauryl alcohol containing 4 mol of glycerol (I NCI name:

Polyglyceryl-4 Lauryl Ether), lauryl alcohol containing 1.5 mol of glycerol, oleyl alcohol containing 4 mol of glycerol (INCI name: Polyglyceryl-4 Oleyl Ether), oleyl alcohol containing 2 mol of glycerol (INCI name: Polyglyceryl-2 Oleyl Ether), cetearyl alcohol containing 2 mol of glycerol, cetearyl alcohol containing 6 mol of glycerol, oleocetyl alcohol containing 6 mol of glycerol, and octadecanol containing 6 mol of glycerol.

The alcohol may represent a mixture of alcohols in the same way as the value of m represents a statistical value, which means that, in a commercial product, several species of polyglycerolated fatty alcohols may coexist in the form of a mixture.

Among the monoglycerolated or polyglycerolated alcohols, it is more particularly preferred to use the C₈/Ci₀ alcohol containing 1 mol of glycerol, the C10/C12 alcohol containing 1 mol of glycerol and the C12 alcohol containing 1.5 mol of glycerol.

Mention may also be made, as nonionic surfactants, of nonoxyethylenated esters of fatty acids and of sorbitan, esters of fatty acids and of sucrose, optionally oxyalkylenated alkylpolyglycosides, alkylglucoside esters, N-alkylglucamine and N-acylmethylglucamine derivatives, aldobionamides and amine oxides.

According to this embodiment, the nonionic surfactant is preferably chosen from oxyethylenated fatty alcohols and oxyethylenated vegetable oils which are saturated or. The anionic surfactant is chosen from alkyl sulphates or alkyl ether sulphates.

The total content of surfactants in the composition of the invention is generally between 0.1 and 30% by weight, preferably from 1 to 20% by weight and better still from 1 to 10% by weight, with respect to the weight of the composition.

The composition can also include various adjuvants conventionally used in compositions for the dyeing or lightening of the hair, such as anionic, cationic nonionic polymers or their mixtures; antioxidants; penetrating agents; sequestering agents; fragrances; dispersing agents; film-forming agents; ceramides; preservatives; or opacifying agents. The above adjuvants are generally present in an amount of, for each of them, between 0.01 and 20% by weight, with respect to the weight of the composition.

Preferably, the composition according to the invention comprises one or more cationic polymers.

The composition according to the invention can comprise water and/or one or more organic solvents.

Mention may be made, as organic solvent, for example, of linear or branched and preferably saturated monoalcohols or diols, comprising from 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4- pentanediol), neopentyl glycol, 3-methyl-1 ,5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols, such as benzyl alcohol or phenylethyl alcohol; polyols comprising more than two hydroxyl functional groups, such as glycerol; polyol ethers, such as, for example, ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or its ethers, such as, for example, propylene glycol monomethyl ether, and diethylene glycol alkyl ethers, in particular C C₄ alkyl ethers, such as, for example, diethylene glycol monoethyl ether or monobutyl ether, alone or as mixtures.

The organic solvents, when they are present, generally represent between 1 % and 40% by weight relative to the total weight of the dyeing composition, and preferably between 5% and 30% by weight relative to the total weight of the dyeing composition.

Preferably, the composition is aqueous. In this case, it preferably comprises from 30 to 95% of water by weight, better still from 40 to 90% of water by weight and even better still from 50 to 85% of water by weight, with respect to the total weight of the composition.

The pH of the composition according to the invention, if it is aqueous, is generally between 3 and 12, preferably between 5 and 1 1 and preferentially between 7 and 11 , limits included.

It can be adjusted to the desired value using acidifying or basifying agents generally used in the dyeing of keratinous fibres and in particular the abovementioned basifying agents of the invention.

The composition according to the invention is provided, on application to the keratinous fibres, in the form of a foam.

The composition in the form of foam according to the invention is formed from a mixture of air or of an inert gas with the composition described above.

According to a particularly preferred embodiment, the composition according to the invention is provided in the form of a temporary foam produced immediately before use. According to this embodiment, the composition can be packaged in a foam dispenser. The products concerned can be "aerosol" products dispensed from a pressurized container, using a propellant gas, and thus forming a foam at the time of the dispensing thereof, or compositions dispensed from a container by means of a mechanical pump connected to a dispensing head, the passage of the composition into the dispensing head converting it into foam at the latest at the outlet orifice of such a head.

According to a first alternative form, the dispenser can be an aerosol comprising, in addition to the base composition, generally divided into two parts, one with the oxidizing agent or agents and the other with the dye precursor or precursors, a propellant gas. In such a configuration, the two parts are generally stored separately, each in a pressurized container. Thus, the propellant gases selected in each of the containers can be suited to the part present.

The propellant gas which can be used can be chosen from carbon dioxide, nitrogen, nitrogen oxide, dimethyl ether, volatile hydrocarbons, such as butane, isobutane, propane or pentane, and their mixtures.

In practice, for this alternative form, use will be made either of an aerosol packaging with a single container internally comprising two pockets or of a double aerosol thus comprising two containers. In both cases, the dispensing head is such that what is sprayed in the foam form is the composition according to the invention, that is to say the mixture of the composition with the oxidizing agent or agents and the composition with the oxidation dye precursor or precursors.

According to another embodiment, the composition can occur in a foam dispenser of "pump-action spray" type. These dispensers comprise a dispensing head for delivering the composition, a pump and a dip pipe for transferring the composition from the container into the head for delivering the product. The foam is formed by forcing the composition to pass through a material comprising a porous substance, such as a sintered material, a plastic or metal filtering screen or similar structures.

Such dispensers are well known to a person skilled in the art and are described in Patents U.S. Pat No. 3,709,437 (Wright), U.S. Pat. No. 3,937,364 (Wright), U.S.

Pat No. 4,022,351 (Wright), U.S. Pat No. 4, 147,306 (Bennett), U.S. Pat No. 4, 184,615 (Wright), U.S. Pat No. 4,598,862 (Rice), U.S. Pat No. 4,615,467 (Grogan et al.), and U.S. Pat No. 5,364,031 (Tamiguchi et al.).

In practice, for this alternative form, the oxidizing agent or agents are packaged in a first container equipped with a stopper and the oxidation dye precursor or precursors are packaged in a second container, separate from the first, also closed by a closure member. The closure member can be a pump dispensing mechanism. The composition according to the invention is then formed by mixing, before use, a composition with the oxidizing agent or agents and a composition with the oxidation dye precursor or precursors. To this end, in order to limit the number of containers provided, one of the first container or of the second container defines an internal volume sufficient to receive therein the whole of the two compositions. The mixture of the compositions can be homogenized by closing this container and by shaking the container. The closing of the container is advantageously carried out directly with the dispensing head. This dispensing head comprises a mechanical pump held in a hoop intended for fitting by snapping or screwing to the neck of the container comprising the mixture. The pump comprises a pump body connected to a dip pipe in order to make it possible to dispense the whole of the mixture. The pump also comprises a pushbutton for the actuation of the pump body, such that, at each actuation, a dose of composition is sucked up inside the dip pipe and ejected in the foam form at the dispensing orifice of the head.

In this example, the containers are preferably made of a thermoplastic and are obtained by extrusion/blow moulding or injection/blow moulding processes. In particular, the container intended for the packaging of the composition with the oxidation dye precursor or precursors is made of a material comprising a nonzero proportion of EVOH. The pump is, for example, the "F2 - L9" standard model provided by Rexam.

According to this preferred embodiment, a subject-matter of the invention is a non aerosol device comprising the composition of the invention.

The dyeing method according to the invention consists in applying the composition according to the invention to dry or wet human keratinous fibres for a time sufficient to develop the desired colouring. According to the invention, the composition applied to the keratinous fibres is in the foam form. The dyeing method is generally carried out at ambient temperature (between 15 and 25°C) and up to temperatures which can reach from 60°C to 80°C.

After a leave-in time from one minute to one hour, preferably from 5 minutes to 30 minutes, the keratinous fibres are rinsed with water and are optionally subjected to washing with a shampoo, followed by rinsing with water.

The following examples serve to illustrate the invention without, however, exhibiting a limiting nature.

EXAMPLES

The following compositions are prepared (the amounts are expressed as g% of active materials) Composition E1 E2

Oxidation dye precursors (base(s) and coupler(s)) Qs Qs

nuance nuance

Coco betaine 1 1

Sodium laureth sulphate 1 1

Aqueous ammonia (expressed as NH₃) 0.6

Monoethanolamine 2 2

Sorbitol 4 4

Polyquaternium-6 0.5 0.5

Merquat 3330 0.05 0.05

Hydrogenated castor oil comprising 40 oxyethylene units 0.4 0.4

Hydrogen peroxide 4.5 4.5

Glycerol 3 3

Cetearyl alcohol 0.2 0.2

Erythorbic acid 0.2 0.2

Sodium metabisulphite 0.2 0.2

Sodium salicylate 0.021 0.021

Tetrasodium pyrophosphate 0.024 0.024

Tetrasodium etidronate 0.036 0.036

EDTA 0.08 0.08

Phosphoric acid Qsp. pH Qsp. pH

Water Qs. 100 Qs. 100

The above compositions E1 and E2 are obtained by mixing, before use, two compositions: A1 and B for the composition E1 , and A2 and B for the composition E2:

Composition Composition A1 A2

Oxidation dye precursors (base(s) and coupler(s)) Qs nuance Qs nuance

Coco betaine 2.5 2.5

Aqueous ammonia (expressed as NH₃) 1.5

Monoethanolamine 5 5

Sorbitol 10 10

Polyquaternium-6 1.25 1.25

Hydrogenated castor oil comprising 40 1 1

oxyethylene units

Erythorbic acid 0.5 0.5 Sodium metabisulphite 0.5 0.5

EDTA 0.2 0.2

Water Qs. 100 Qs. 100

The mixture is introduced in a proportion of 65 g (26 g of composition A + 39 g of composition B) into a pump-action spray (L9 Rexam) equipped with a dip pipe. The device makes it possible, by pumping, to obtain a foam which is sufficiently compact to be applied to grey hair comprising 90% of natural or permed white hairs and not to immediately break up. The comfort on application is very good. After leaving for 30 minutes, the locks are rinsed, washed with a standard shampoo, again rinsed and then dried to result in the desired colouring. This colouring is powerful and not very selective.

Claims

Dyeing composition in the foam form, comprising:

(a) at least one amphoteric polymer obtained from

- at least one monomer chosen from acrylic acid and methacrylic acid,

- at least one monomer chosen from acrylamide or one of its derivatives,

- at least one monomer chosen from monomers comprising one or more quaternary ammonium groups;

(b) at least one basifying agent;

(c) at least one surfactant chosen from amphoteric surfactants and anionic surfactants;

(d) at least one oxidizing agent;

(e) at least one oxidation dye precursor.

Composition according to Claim 1 , in which the surfactant or surfactants are chosen from amphoteric surfactants.

Composition according to Claim 1 or 2, in which the surfactant is an amphoteric surfactant chosen from (C₈-C₂o)alkyl betaines, sulfobetaines, (C₈-C₂o)alkyl amido(CrC₆)alkyl betaines or (C₈-C₂o)alkyl amido(CrC₆)alkyl sulphobetaines, preferably (C₈-C₂o)alkyl amido(CrC₆)alkyl betaines.

Composition according to any one of the preceding claims, comprising one or more amphoteric surfactants, one or more nonionic surfactants and one or more anionic surfactants.

Composition according to any one of Claims 1 to 4, in which the surfactant or surfactants are present in a total amount ranging from 0.1 to 30% by weight, preferably from 1 to 20% by weight and better still from 1 to 10% by weight, with respect to the weight of the composition.

Composition according to any one of the preceding claims, in which the basifying agent is chosen from aqueous ammonia, alkanolamines and amino acids.

Composition according to any one of the preceding claims, in which the basifying agent is chosen from alkanolamines and in particular

monoethanolamine.

Composition according to any one of the preceding claims, in which the basifying agent or agents represent a content ranging from 0.01 to 30% by weight, preferably from 0.1 to 20% by weight and better still from 1 to 10% by weight, with respect to the weight of the said composition.

9. Composition according to any one of the preceding claims, in which the amphoteric terpolymer is an acrylic acid/diallyldimethylammonium chloride/ acrylamide terpolymer.

10. Composition according to any one of the preceding claims, in which the

amphoteric terpolymer or terpolymers are present in an amount ranging from

0.01 to 3% by weight, with respect to the total weight of the composition.

11. Composition according to any one of the preceding claims, in which the

oxidizing agent is hydrogen peroxide.

12. Composition according to any one of the preceding claims, comprising one or more oxidation bases and one or more couplers.

13. Aerosol device comprising a means for generating, in the foam form, a

composition as defined in any one of Claims 1 to 12.

14. Aerosol device according to Claim 13, comprising just one container provided with 2 pockets or comprising two containers.

15. Non-aerosol device comprising a pump-action spray equipped with a

mechanical pumping system and comprising a composition as defined in any one of Claims 1 to 12 and a dispensing system which makes it possible to deliver it in the foam form.