WO2012059405A1

WO2012059405A1 - Mousse dye composition comprising an associative polymer

Info

Publication number: WO2012059405A1
Application number: PCT/EP2011/068925
Authority: WO
Inventors: Caroline Goget; Richard Sabourin; Jean-Marc Ascione; Delphine Allard
Original assignee: L'oreal
Priority date: 2010-11-02
Filing date: 2011-10-28
Publication date: 2012-05-10
Also published as: FR2966729A1; FR2966729B1

Abstract

The present invention relates to a composition for dyeing human keratin fibres such as the hair, in mousse form, comprising: (a)one or more associative polymer(s); (b)one or more alkaline agent(s); (c)one or more surfactant(s); (d)one or more oxidizing agent(s); (e)one or more oxidation dye precursor(s). The invention also relates to a process for treating human keratin fibres using this composition in mousse form, and to aerosol or non-aerosol devices for generating the mousse.

Description

MOUSSE DYE COMPOSITION COMPRISING AN ASSOCIATIVE POLYMER

The present invention relates to a process for dyeing the hair, in mousse form, using a composition comprising oxidation dye precursors, and to a composition in mousse form.

Among the methods for dyeing human keratin fibres, such as the hair, mention may be made of oxidation dyeing or permanent dyeing. More particularly, this dyeing method uses one or more oxidation dyes, usually one or more oxidation bases optionally combined with one or more couplers.

In general, oxidation bases are chosen from ortho- or para-phenylenediamines, ortho- or para-aminophenols and heterocyclic compounds. These oxidation bases are colourless or weakly coloured compounds, which, when combined with oxidizing products, can give access to coloured species.

The shades obtained with these oxidation bases are often varied by combining them with one or more couplers, these couplers being chosen especially from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds.

The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained.

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

Dye compositions may be in various forms, such as lotions, gels, emulsions, creams or mousses. Colouring mousses are pleasant to use, but they often have poor fastness over time. Rapid disappearance of the mousse after application or nonuniform application along the fibres may be observed, for example.

There is a real, constant need to develop oxidation dye compositions in the form of mousses that are easy to prepare and to apply, and which remain sufficiently stable over time while at the same time imparting efficient dyeing properties.

This aim and others are achieved by the present invention, one subject of which is thus a composition for dyeing human keratin fibers such as the hair, in mousse form, comprising:

a) at least one associative polymer

b) at least one alkaline agent

c) at least one surfactant

d) at least one oxidizing agent

e) at least one oxidation dye precursor. The invention also relates to a process for dyeing human keratin fibres using this composition.

Similarly, a subject of the invention is a multi-compartment device comprising, in a first compartment, a composition containing one or more surfactant(s), one or more oxidation dye precursor(s), one or more alkaline agent(s), in a second, a composition containing one or more oxidizing agents, at least one of the two compositions comprising one or more associative polymer(s), and in a third, a container equipped with a member for delivering in mousse form the composition according to the invention obtained from the mixing of the two preceding compositions.

A subject of the invention is also a device for dyeing keratin fibres, comprising the composition of the invention in liquid form and a mousse dispenser for delivering the composition in the form of a mousse.

The composition of the invention is in the form of a mousse that is particularly pleasant to apply. It has a light, airy texture, which makes it particularly pleasant to use. The qualities of the mousse are sufficiently long-lasting to enable uniform application of the dye product, without running. The composition makes it possible to conserve particularly efficient dyeing properties such as the colour strength, the resistance to external agents (shampoos, perspiration, light) and the selectivity.

Other characteristics and advantages of the invention will emerge more clearly on reading the description and the examples that follow.

In the text hereinbelow, unless otherwise indicated, the limits of a range of values are included in that range. The term "at least one" associated with an ingredient of the composition means "one or more".

The human keratin fibers treated via the process according to the invention are preferably the hair.

The composition of the invention comprises one or more associative polymer(s). Associative polymers that may be used according to the invention

For the purposes of the present invention, the term "associative polymers" means water-soluble polymers that are capable, in an aqueous medium, of reversibly combining with each other or with other molecules.

Their chemical structure comprises at least one hydrophilic region and at least one hydrophobic region characterized by at least one C₈-C₃₀ fatty chain.

The associative polymers according to the invention may be of anionic, cationic, amphoteric or nonionic type.

Associative polymers of anionic type:

Among these, mention may be made of: - (A) those comprising at least one hydrophilic unit and at least one fatty-chain allyl ether unit, more particularly those whose hydrophilic unit is formed by an ethylenic unsaturated anionic monomer, more particularly a vinylcarboxylic acid and most particularly an acrylic acid or a methacrylic acid or mixtures thereof, the fatty- chain allyl ether unit of which corresponds to the monomer of formula (I) below:

CH₂ = C R' CH₂ O B_n R(l)

in which R' denotes H or CH₃, B denotes an ethylenoxy radical, n is zero or denotes an integer ranging from 1 to 100, R denotes a hydrocarbon-based radical chosen from alkyl, arylalkyi, aryl, alkylaryl and cycloalkyi radicals, comprising from 8 to 30 carbon atoms, preferably 10 to 24 and even more particularly from 12 to 18 carbon atoms. The unit of formula (I) that is more particularly preferred is a unit in which R' denotes H, n is equal to 10, and R denotes a stearyl radical (Ci₈).

Anionic associative polymers of this type are described and prepared, according to an emulsion polymerization process, in patent EP-0 216 479.

Among these anionic associative polymers, those that are particularly preferred according to the invention are polymers formed from 20% to 60% by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% by weight of lower alkyl

(meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether of formula (I), and from 0 to 1 % by weight of a crosslinking agent which is a well-known copolymerizable unsaturated polyethylenic monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.

Among the latter polymers, the ones that are most particularly preferred are crosslinked terpolymers of methacrylic acid, of ethyl acrylate, of polyethylene glycol (10 EO) stearyl ether (Steareth 10), especially those sold by the company Allied Colloids under the names Salcare SC 80® and Salcare SC 90®, which are aqueous emulsions containing 30% of a crosslinked terpolymer of methacrylic acid, of ethyl acrylate and of steareth-10 allyl ether (40/50/10).

-(B) polymers comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of the type such as a (Ci₀-C₃₀) alkyl ester of an unsaturated carboxylic acid.

These polymers are preferably chosen from those in which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (II) below:

CH ^~ C— C— OH (I I) in which denotes H or CH₃ or C₂H₅, i.e. acrylic acid, methacrylic acid or ethacrylic acid units, and whose hydrophobic unit of the type such as a (Ci₀-C₃₀) alkyl ester of an unsaturated carboxylic acid corresponds to the monomer of formula (III) below:

CH₂ = C— C— OR₃ (M l)

2 I I I ³ ' in which R₂ denotes H or CH₃ or C₂H₅ (i.e. acrylate, methacrylate or ethacrylate units) and preferably H (acrylate units) or CH₃ (methacrylate units), R₃ denoting a C10- C₃₀ and preferably C12-C22 alkyl radical.

(Cio-C₃₀)alkyl esters of unsaturated carboxylic acids in accordance with the invention comprise, for example, lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Anionic polymers of this type are described and prepared, for example, according to patents US 3 915 921 and US 4 509 949.

Among the anionic associative polymers of this type that will be used more particularly are polymers formed from a monomer mixture comprising:

(i) essentially acrylic acid,

(ii) an ester of formula (III) described above and in which R₂ denotes H or CH₃, R₃ denoting an alkyl radical containing from 12 to 22 carbon atoms,

(iii) and a crosslinking agent, which is a well-known copolymerizable

polyethylenic unsaturated monomer, for instance diallyl phthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycol dimethacrylate or methylenebisacrylamide.

Among the anionic associative polymers of this type, use will be made more particularly of those formed from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of Ci₀-C₃₀ alkyl acrylate (hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizable monomer, or alternatively those formed from 98% to 96% by weight of acrylic acid (hydrophilic unit), 1 % to 4% by weight of Ci₀-C₃₀ alkyl acrylate (hydrophobic unit) and 0.1 % to 0.6% by weight of crosslinking polymerizable monomer such as those described previously.

Among the said above polymers, those most particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TR1 ®, Pemulen TR2® and Carbopol 1382®, and even more preferentially Pemulen TR1 ®, and the product sold by the company SEPPIC under the name Coatex SX®. -(C) maleic anhydride/C₃o-C38 oc-olefin/alkyl maleate terpolymers, such as the product (maleic anhydride/C₃o-C3₈ oc-olefin/isopropyl maleate) sold under the name Performa V 1608® by the company Newphase Technologies. -(D) acrylic terpolymers comprising:

(a) about 20% to 70% by weight of a carboxylic acid containing α,β- monoethylenic unsaturation,

(b) about 20% to 80% by weight of a non-surfactant monomer containing α,β-monoethylenic unsaturation other than (a),

(c) about 0.5% to 60% by weight of a nonionic monourethane which is the product of reaction of a monohydric surfactant with a monoisocyanate containing monoethylenic unsaturation,

such as those described in patent application EP-A-0 173 109 and more particularly the terpolymer described in Example 3, namely a methacrylic acid/methyl acrylate/behenyl alcohol dimethyl-meta-isopropenylbenzylisocyanate ethoxylated (40 EO) terpolymer, as an aqueous 25% dispersion.

- (E) copolymers comprising among their monomers a carboxylic acid containing α,β-monoethylenic unsaturation and an ester of a carboxylic acid containing α,β-monoethylenic unsaturation and of an oxyalkylenated fatty alcohol.

Preferentially, these compounds also comprise as monomer an ester of an ,β- monoethylenically unsaturated carboxylic acid and of a C C₄ alcohol.

An example of a compound of this type that may be mentioned is Aculyn 22® sold by the company Rohm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer.

- (F) associative polymers comprising at least one ethylenically unsaturated monomer bearing a sulfonic group, in free or partially or totally neutralized form and comprising at least one hydrophobic part.

Among the polymers of this type, mention may be made more especially of:

- crosslinked or non-crosslinked, neutralized or non-neutralized copolymers comprising from 15% to 60% by weight of AMPS (2-acrylamido-2- methylpropanesulfonic acid or salt) units and from 40% to 85% by weight of (C₈- Ci₆)alkyl (meth)acrylate units relative to the polymer, such as those described in patent application EP-A-750 899;

- terpolymers comprising from 10 mol% to 90 mol% of acrylamide units, from 0.1 mol% to 10 mol% of AMPS units and from 5 mol% to 80 mol% of n-(C₆- C₈)alkylacrylamide units, such as those described in patent US 5 089 578; - copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also copolymers of AMPS and of n-dodecylmethacrylamide, which are non-crosslinked and crosslinked;

- copolymers formed from AMPS units and from steareth-25 methacrylate units, such as Aristoflex HMS sold by the company Clariant.

In these anionic associative polymers, the compounds of families (B) and (E) will preferably be used. Associative polymers of cationic type

Among these, mention may be made of:

-(Α') cationic associative polyurethanes, the family of which has been described by the Applicant in French patent application No. 00/09609; it may be represented by the general formula (la) below:

R-X-(P)n-[L-(Y)_m]_rL'-(P')p-X'-R' (la)

in which:

o R and R', which may be identical or different, represent a hydrophobic group or a hydrogen atom;

o X and X', which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group, or alternatively a group L";

o L, U and L", which may be identical or different, represent a group derived from a diisocyanate;

o P and P', which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group;

o Y represents a hydrophilic group;

o r is an integer between 1 and 100 inclusive, preferably between 1 and 50 inclusive and in particular between 1 and 25 inclusive;

o n, m and p are each, independently of each other, between 0 and 1000 inclusive;

the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group. In one preferred embodiment of these polyurethanes, the only hydrophobic groups are the groups R and R' at the chain ends. One preferred family of cationic associative polyurethanes is the one corresponding to formula (la) described above and in which:

o R and R' both independently represent a hydrophobic group, o X and X' each represent a group L",

o n and p are integers that are between 1 and 1000 inclusive, and o L, U, L", P, P', Y and m have the meaning given above.

Another preferred family of cationic associative polyurethanes is the one corresponding to formula (la) above in which:

o The fact that n and p are 0 means that these polymers do not comprise units derived from a monomer containing an amine function, incorporated into the polymer during the polycondensation.

o The protonated amine functions of these polyurethanes result from the hydrolysis of excess isocyanate functions, at the chain end, followed by alkylation of the primary amine functions formed with alkylating agents containing a hydrophobic group, i.e. compounds of the type RQ or R'Q, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.

Yet another preferred family of cationic associative polyurethanes is the one corresponding to formula (la) above in which:

o R and R' both independently represent a hydrophobic group, o X and X' both independently represent a group comprising a quaternary amine,

o n and p are zero, and

o L, U, Y and m have the meaning given above.

The number-average molecular mass of the cationic associative polyurethanes is preferably between 400 and 500 000, in particular between 1000 and 400 000 and ideally between 1000 and 300 000.

The expression "hydrophobic group" means a radical or polymer containing a saturated or unsaturated, linear or branched hydrocarbon-based chain, which may contain one or more heteroatoms such as P, O, N or S, or a radical containing a perfluoro or silicone chain. When the hydrophobic group denotes a hydrocarbon- based radical, it comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferably from 18 to 30 carbon atoms.

Preferentially, the hydrocarbon-based group is derived from a monofunctional compound.

By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.

When X and/or X' denote(s) a group comprising a tertiary or quaternary amine, X and/or X' may represent one of the following formulae:

— for X

f_{or X}-

in which:

o R₂ represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;

o R and R₃, which may be identical or different, represent a linear or branched CrC₃₀ alkyl or alkenyl radical or an aryl radical, at least one of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;

o A^" is a physiologically acceptable anionic counterion such as a halide, for instance chloride or bromide, or mesylate.

The groups L, U and L" represent a group of formula:

— Z-C-NH-R ,-NH-C-Z—

I I ⁴ I I

O O

in which:

Z represents -0-, -S- or -NH-; and o R₄ represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P.

The groups P and P' comprising an amine function may represent at least one of the following formulae:

3

or ~ ~ R*_j ~~ C'H^— R₇ ^■ I ^ v. n J ₇

R₆ -N ₉

R 6 \

N

-

in which:

R₅ and R₇ have the same meanings as R₂ defined above;

R₆, Rs and R₉ have the same meanings as and R₃ defined above;

o R₁₀ represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more heteroatoms chosen from N, O, S and P; and

As regards the meaning of Y, the term "hydrophilic group" means a polymeric or non-polymeric water-soluble group.

By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol. When it is a hydrophilic polymer, in accordance with one preferred embodiment, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and especially a poly(ethylene oxide) or poly(propylene oxide).

The cationic associative polyurethanes of formula (la) that may be used according to the invention are formed from diisocyanates and from various compounds bearing functions containing a labile hydrogen. The functions containing a labile hydrogen may be alcohol, primary or secondary amine or thiol functions, giving, after reaction with the diisocyanate functions, polyurethanes, polyureas and polythioureas, respectively. The term "polyurethanes in the present invention" encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof.

A first type of compound involved in the preparation of the polyurethane of formula (la) is a compound comprising at least one unit bearing an amine function. This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to one preferential embodiment, this compound comprises two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, secondary amine or thiol function. A mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low may also be used.

As mentioned above, this compound may comprise more than one unit containing an amine function. In this case, it is a polymer bearing a repetition of the unit containing an amine function.

Compounds of this type may be represented by one of the following formulae:

HZ-(P)_n-ZH,

or

in which Z, P, Ρ', n and p are as defined above.

Examples of compounds containing an amine function that may be mentioned include N-methyldiethanolamine, N-tert-butyldiethanolamine and N- sulfoethyldiethanolamine.

The second compound included in the preparation of the polyurethane of formula (la) is a diisocyanate corresponding to the formula:

0=C=N-R₄-N=C=0

in which R₄ is as defined above. By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.

A third compound involved in the preparation of the polyurethane of formula (la) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (la).

This compound is formed from a hydrophobic group and a function containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.

By way of example, this compound may be a fatty alcohol such as, in particular, stearyl alcohol, dodecyl alcohol or decyl alcohol. When this compound comprises a polymer chain, it may be, for example, -hydroxylated hydrogenated polybutadiene.

The hydrophobic group of the polyurethane of formula (la) may also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit. Thus, the hydrophobic group is introduced via the quaternizing agent. This quaternizing agent is a compound of the type RQ or R'Q, in which R and R' are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.

The cationic associative polyurethane may also comprise a hydrophilic block. This block is provided by a fourth type of compound involved in the preparation of the polymer. This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture in which the percentage of multifunctional compound is low.

The functions containing a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends with one of these functions containing a labile hydrogen.

By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol.

When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and especially a poly(ethylene oxide) or poly(propylene oxide).

The hydrophilic group termed Y in formula (la) is optional. Specifically, the units containing a quaternary amine or protonated function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solution.

Although the presence of a hydrophilic group Y is optional, cationic associative polyurethanes comprising such a group are, however, preferred. - (Β') quaternized cellulose derivatives.

The quaternized cellulose derivatives are, in particular:

- i) quaternized celluloses modified with groups comprising at least one fatty chain, such as linear or branched alkyl, linear or branched arylalkyl or linear or branched alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof;

- ii) quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as linear or branched alkyl, linear or branched arylalkyl or linear or branched alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof;

- iii) the hydroxyethylcelluloses of formula (lb):

in which formula (lb):

o R and R', which may be identical or different, represent an ammonium group such as R_aR_bR_cN⁺-, Q^" in which R_a, R_b and R_c, which may be identical or different, represent a hydrogen atom or a linear or branched Ci-C₃₀ and preferentially C C₂o alkyl group, such as methyl or dodecyl; and o Q^" represents an anionic counterion such as a halide, for instance a chloride or bromide;

o n, x and y, which may be identical or different, represent an integer between 1 and 10 000.

The alkyl radicals borne by the above quaternized celluloses i) or hydroxyethylcelluloses ii) preferably comprise from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.

Examples of quaternized alkylhydroxyethylcelluloses containing C₈-C₃₀ fatty chains that may be indicated include the products Quatrisoft LM 200®, Quatrisoft LM- X529-18-A®, Quatrisoft LM-X529-18B® (C₁₂ alkyl) and Quatrisoft LM-X529-8® (C₁₈ alkyl) sold by the company Amerchol and the products Crodacel QM®, Crodacel QL® (C₁₂ alkyl) and Crodacel QS® (Ci₈ alkyl) sold by the company Croda.

Mention may also be made of the hydroxyethylcelluloses of formula (lb) in which R represents a trimethylammonium halide and R' represents a dimethyldodecylammonium halide, more preferentially R represents trimethylammonium chloride (CH₃)₃N⁺ CI^" and R' represents dimethyldodecylammonium chloride (CH₃)₂(Ci2H25)N⁺ CI^". Polymers of this type are known under the trade name softCAT Polymer SL®, such as SL-100 and SL-60.

More particularly, the polymers of formula (lb) are those whose viscosity is between 2000 and 3000 cPs inclusive. Preferentially, the viscosity is between 2700 and 2800 cPs inclusive. Typically, softCAT Polymer SL-5 has a viscosity of 2500 cPs, softCAT Polymer SL-30 has a viscosity of 2700 cPs, softCAT Polymer SL-60 has a viscosity of 2700 cPs and softCAT Polymer SL-100 has a viscosity of 2800 cPs.

(C)- Cationic polyvinyllactams, the family of which has been described by the Applicant in French patent application No. 01/01106.

The said polymers comprise:

-a) at least one monomer of vinyllactam or alkylvinyllactam type;

-b) at least one monomer of structure (lc) or (lie) below:

in which formulae (lc) and (lie):

o X denotes an oxygen atom or a radical NR₆,

o R and R₆ denote, independently of each other, a hydrogen atom or a linear or branched C C₅ alkyl radical,

o R₂ denotes a linear or branched C C₄ alkyl radical, o R₃, R₄ and R₅ denote, independently of each other, a hydrogen atom, a linear or branched CrC₃₀ alkyl radical or a radical of formula (lllc):

(Y₂)_r— (CH₂-CH(R₇)-O)_x— R₈ (lllc)

- Y, Y and Y₂ denote, independently of each other, a linear or branched C₂-Ci₆ alkylene radical,

- R₇ denotes a hydrogen atom or a linear or branched C C₄ alkyl radical or a linear or branched C C₄ hydroxyalkyl radical,

- R₈ denotes a hydrogen atom or a linear or branched CrC₃₀ alkyl radical,

o p, q and r denote, independently of each other, either the value

0 or the value 1 ,

o m and n denote, independently of each other, an integer ranging from 0 to 100 inclusive, o x denotes an integer ranging from 1 to 100 inclusive, o Z denotes an anionic counterion of an organic or mineral acid, such as a halide, for instance chloride or bromide, or mesylate;

with the proviso that:

- at least one of the substituents R₃, R₄, R₅ or R₈ denotes a linear or branched C₉-C₃₀ alkyl radical,

- if m or n is other than zero, then q is equal to 1 ,

- if m or n is equal to zero, then p or q is equal to 0.

The cationic poly(vinyllactam) polymers according to the invention may be crosslinked or noncrosslinked and may also be block polymers.

Preferably, the counterion Z^" of the monomers of formula (lc) is chosen from halide ions, phosphate ions, the methosulfate ion and the tosylate ion.

Preferably, R₃, R₄ and R₅ denote, independently of each other, a hydrogen atom or a linear or branched CrC₃₀ alkyl radical.

More preferentially, the monomer b) is a monomer of formula (lc) for which, even more preferentially, m and n are equal to 0.

The vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (IVc):

CH(R₉)=C(R₁₀)-N-^O

<CH₂)_S

in which:

o s denotes an integer ranging from 3 to 6,

o R₉ denotes a hydrogen atom or a linear or branched C C₅ alkyl radical,

o R₁₀ denotes a hydrogen atom or a linear or branched C C₅ alkyl radical,

with the proviso that at least one of the radicals R₉ and R₁₀ denotes a hydrogen atom.

Even more preferentially, the monomer (IVc) is vinylpyrrolidone. The cationic poly(vinyllactam) polymers according to the invention may also contain one or more additional monomers, preferably cationic or nonionic monomers.

As compounds that are more particularly preferred according to the invention, mention may be made of the following terpolymers comprising at least: a) one monomer of formula (IVc),

b) one monomer of formula (lc) in which p=1 , q=0, R₃ and R₄ denote, independently of each other, a hydrogen atom or a C C₅ alkyl radical and R₅ denotes a linear or branched C₉-C₂₄ alkyl radical, and

c) one monomer of formula (lie) in which R₃ and R₄ denote, independently of each other, a hydrogen atom or a linear or branched C C₅ alkyl radical.

Even more preferentially, terpolymers comprising, by weight, 40% to 95% of monomer (a), 0.1 % to 55% of monomer (c) and 0.25% to 50% of monomer (b) will be used.

Such polymers are described in patent application WO 00/68282, the content of which forms an integral part of the invention.

As cationic poly(vinyllactam) polymers according to the invention, vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacrylamido- propylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacrylamido- propylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamido- propylammonium tosylate or chloride terpolymers are used in particular. The vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethylacrylamido propylammonium chloride terpolymer is sold by the company ISP under the names

Styleze W10 and Styleze W20L.

The weight-average molecular mass of the cationic poly(vinyllactam) polymers according to the present invention is preferably between 500 and 20 000 000. It is more particularly between 200 000 and 2 000 000 and even more preferentially between 400 000 and 800 000.

Associative polymers of nonionic type

According to the invention, they are preferentially chosen from:

-(1) celluloses modified with groups comprising at least one fatty chain;

examples that may be mentioned include:

- hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as linear or branched alkyl, linear or branched arylalkyl or linear or branched alkylaryl groups, or mixtures thereof, and in which the linear or branched alkyl groups are preferably C₈-C₂2, for instance the product Natrosol Plus Grade 330 CS® (Ci₆ alkyl) sold by the company Aqualon, the product Polysurf 67 CS (cetylhydroxyethylcellulose) sold by the company Ashland or the product Bermocoll EHM 100® sold by the company Berol Nobel, - hydroxyethylcelluloses modified with alkylphenyl polyalkylene glycol ether groups, such as the product Amercell Polymer HM-1500® (polyethylene glycol (15) nonylphenyl ether) sold by the company Amerchol,

- hydroxypropylmethylcelluloses modified with linear or branched C₈-C₂2 alkyl groups, for instance the product Sangelose 60L (INCI name: hydroxypropyl methylcellulose stearoxy ether) sold by the company Daido Chemical,

-(2) hydroxypropyl guars modified with groups comprising at least one fatty chain, such as the product Esaflor HM 22® (C₂2 alkyl chain) sold by the company Lamberti, and the products RE210-18® (C_M alkyl chain) and RE205-1 ® (C₂₀ alkyl chain) sold by the company Rhone-Poulenc,

-(3) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers; examples that may be mentioned include:

- the products Antaron V216® and Ganex V216®

(vinylpyrrolidone/hexadecene copolymer) sold by the company ISP.

the products Antaron V220® and Ganex V220® (vinylpyrrolidone/eicosene copolymer) sold by the company ISP, -(4) copolymers of C C₆ alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain, for instance the oxyethylenated methyl acrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208®, -(5) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer,

-(6) polyurethane polyethers comprising in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences,

-(7) polymers with an aminoplast ether backbone containing at least one fatty chain, such as the Pure Thix® compounds sold by the company Sud-Chemie.

Preferably, the polyurethane polyethers comprise at least two hydrocarbon- based lipophilic chains containing from 6 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being pendent chains or chains at the end of the hydrophilic block. In particular, it is possible for one or more pendent chains to be included. In addition, the polymer may comprise a hydrocarbon- based chain at one end or at both ends of a hydrophilic block.

The polyurethane polyethers may be multiblock, in particular in triblock form. The hydrophobic blocks may be at each end of the chain (for example: triblock copolymer containing a hydrophilic central block) or distributed both at the ends and in the chain (for example multiblock copolymer). These same polymers may also be graft polymers or star polymers.

The nonionic fatty-chain polyurethane polyethers may be triblock copolymers in which the hydrophilic block is a polyoxyethylenated chain comprising from 50 to 1000 oxyethylene groups. The nonionic polyurethane polyethers comprise a urethane bond between the hydrophilic blocks, whence arises the name.

By extension, also included among the nonionic fatty-chain polyurethane polyethers are those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.

As examples of nonionic fatty-chain polyurethane polyethers that may be used in the invention, it is also possible to use Rheolate 205® containing a urea function, sold by the company Rheox, or Rheolate® 208, 204 or 212, and also Acrysol RM 184®.

Mention may also be made of the product Elfacos T210® containing a C12-14 alkyl chain, and the product Elfacos T212® containing a Ci₈ alkyl chain, from Akzo.

The product DW 1206B® from Rohm & Haas containing a C₂o alkyl chain and a urethane bond, sold at a solids content of 20% in water, may also be used.

It is also possible to use solutions or dispersions of these polymers, especially in water or in aqueous-alcoholic medium. Examples of such polymers that may be mentioned are Rheolate® 255, Rheolate® 278 and Rheolate® 244 sold by the company Rheox. The products DW 1206F and DW 1206J sold by the company Rohm & Haas may also be used.

Mention may also be made of Luvigel Star (polyurethane-39) sold by the company BASF, which is a copolymer of PEG-140 and of hexamethylene diisocyanate terminated with C12-14 pareth-10, C16-18 pareth-11 and C18-20 pareth-1 1.

The polyurethane polyethers that may be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen - Colloid Polym. Sci. 271 , 380-389 (1993).

Even more particularly, according to the invention, it is preferred to use a polyurethane polyether that may be obtained by polycondensation of at least three compounds comprising: (i) at least one polyethylene glycol comprising from 150 to 180 mol of ethylene oxide,

(ii) stearyl alcohol or decyl alcohol and

(iii) at least one diisocyanate.

Such polyurethane polyethers are sold especially by the company Rohm &

Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81 %); Aculyn 44® is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].

Associative polymers of amphoteric type

The amphoteric associative polymers are preferably chosen from those comprising at least one non-cyclic cationic unit. Even more particularly, the ones that are preferred are those prepared from or comprising 1 to 20 mol%, preferably

1.5 to 15 mol% and even more particularly 1.5 to 6 mol% of fatty-chain monomer relative to the total number of moles of monomers.

The amphoteric associative polymers that are preferred according to the invention comprise or are prepared by copolymerizing:

1) at least one monomer of formula (XIX) or (XX):

A-

in which and R₂, which may be identical or different, represent a hydrogen atom or a methyl radical, R₃, R₄ and R₅, which may be identical or different, represent a linear or branched alkyl radical containing from 1 to 30 carbon atoms,

Z represents an NH group or an oxygen atom,

n is an integer from 2 to 5,

A^" is an anion derived from an organic or mineral acid, such as a methosulfate anion or a halide such as chloride or bromide;

2) at least one monomer of formula (XXI):

R₆— CH =CR₇— COOH

(XXI)

in which R₆ and R₇, which may be identical or different, represent a hydrogen atom or a methyl radical;

and

3) at least one monomer of formula (XXII):

R₆— CH =CR₇— COXR₈ (XXII)

in which R₆ and R₇, which may be identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and R₈ denotes a linear or branched alkyl radical containing from 1 to 30 carbon atoms; at least one of the monomers of formula (XIX), (XX), (XXI) or (XXII) comprising at least one fatty chain.

The monomers of formulae (XIX) and (XX) according to the present invention are preferably chosen from the group formed by:

- dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate,

- diethylaminoethyl methacrylate, diethylaminoethyl acrylate,

- dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate,

- dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide,

these monomers optionally being quaternized, for example with a C C₄ alkyl halide or a C C₄ dialkyl sulfate.

More particularly, the monomer of formula (XIX) is chosen from

acrylamidopropyltrimethylammonium chloride and

methacrylamidopropyltrimethylammonium chloride.

The monomers of formula (XXI) are preferably chosen from the group formed by acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid. More particularly, the monomer of formula (XXI) is acrylic acid. The monomers of formula (XXII) are preferably chosen from the group formed from C12-C22 and more particularly Ci₆-Ci₈ alkyl acrylates or methacrylates.

The monomers constituting the fatty-chain amphoteric polymers of the invention are preferably already neutralized and/or quaternized.

The ratio of the number of cationic charges/anionic charges is preferably equal to about 1.

The amphoteric associative polymers preferably comprise from 1 mol% to 10 mol% of the monomer comprising a fatty chain (monomer of formula (XIX), (XX) or (XXII)), and preferably from 1.5 mol% to 6 mol%.

The weight-average molecular weights of the amphoteric associative polymers according to the invention may range from 500 to 50 000 000 and are preferably between 10 000 and 5 000 000.

The amphoteric associative polymers may also contain other monomers such as nonionic monomers and in particular such as C C₄ alkyl acrylates or methacrylates.

Amphoteric associative polymers according to the invention are described and prepared, for example, in patent application WO 98/44012.

Among the amphoteric associative polymers, the ones that are preferred are acrylic acid/(meth)acrylamidopropyltrimethylammonium chloride/stearyl methacrylate terpolymers.

In a first variant of the invention, the associative polymers are chosen from those of families (1), (6), (E), (B) and (Β').

In one preferred composition according to the present invention, the associative polymers are chosen from those of nonionic or cationic type and even more particularly from polyurethane polyethers bearing hydrophilic and hydrophobic blocks, nonionic cellulose derivatives comprising at least one fatty chain, and quaternized cellulose derivatives comprising at least one fatty chain.

As polymers that are preferred according to the invention, mention may be made more particularly of nonionic polyurethanes such as those sold under the names Aculyn 44® and Aculyn 46®, Luvigel Star®, nonionic cellulose derivatives such as those of cetylhydroxyethylcellulose sold under the names Natrosol Plus

Grade 330 CS®, Polysurf 67 CS and hydroxypropylmethylcellulose stearoxy ether

Sangelose 60L®, cationic cellulose derivatives such as those sold under the names

Softcat Polymer SL-100® and Softcat Polymer SL-60® or Quatrisoft LM200.

In an even more particularly preferred composition according to the invention, the associative polymer is chosen from nonionic and cationic cellulose derivatives. The nonionic, anionic, amphoteric or cationic associative polymer(s) used in the composition according to the invention may be present in an amount ranging from 0.01 % to 10% by weight, preferably in an amount ranging from 0.01 % to 5% by weight and better still in a content ranging from 0.1 % to 2% by weight relative to the total weight of the composition.

The composition comprises one or more alkaline agent(s). This agent may be chosen from mineral or organic or hybrid alkaline agents, or mixtures thereof.

The mineral alkaline 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 alkaline agent(s) are preferably chosen from organic amines with a pKb 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 pKb corresponding to the function of highest basicity.

Hybrid compounds that may be mentioned include the salts of the amines mentioned previously with acids such as carbonic acid or hydrochloric acid.

The organic alkaline agent(s) are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds of formula (VI) below:

^Rx \ / ^Rz

W- N (^Vl)

Ry ^x Rt

in which W is a C C₆ alkylene residue optionally substituted with a hydroxyl group or a Ci-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 monoalkanolamines, dialkanolamines or trialkanolamines 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(hydroxymethylamino)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, sulfonic 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 (VII) below:

NH,

/ ²

R— CH₂— CH_X ^{(VI I)}

C0₂H

i enotes a group chosen from:

-(CH₂)₃NH₂

-(CH₂)₂NH₂ -(CH₂)₂NHCONH₂

-(CH₂)₂NH C— NH₂

NH

The compounds corresponding to formula (VII) 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 -sulfonic 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 one particular embodiment, the composition of the invention comprises as alkaline agent one or more alkanolamines. Preferably, the alkanolamine is ethanolamine (or monoethanolamine).

In one variant of the invention, the composition of the invention comprises as alkaline agent one or more alkanolamines (preferably ethanolamine) and aqueous ammonia. In this variant, the alkanolamine(s) are present in predominant amount relative to the aqueous ammonia.

Advantageously, the composition according to the invention has a content of alkaline 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 relative to the weight of said composition.

The composition according to the invention also comprises one or more oxidizing agent(s).

The oxidizing agents are chosen, for example, from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts, for instance persulfates, perborates, peracids and precursors thereof 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 relative to the weight of the composition.

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

Oxidation bases and couplers may be used as oxidation dye precursors.

By way of example, the oxidation bases are chosen from para- phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho- aminophenols and heterocyclic bases, and the addition salts thereof.

Among the para-phenylenediamines that may be mentioned, for example, are para-phenylenediamine, para-tolylenediamine, 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(β-hydroxyethyl)amino-2-methylaniline, 4-N,N- bis(β-hydroxyethyl)amino-2-chloroaniline, 2-β-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- ,Y-dihydroxypropyl)-para-phenylenediamine, N-(4'- aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β- hydroxyethyloxy-para-phenylenediamine, 2^-acetylaminoethyloxy-para- phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4- aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2^-hydroxyethylamino-5- aminotoluene, 3-hydroxy-1-(4'-aminophenyl)pyrrolidine, and the addition salts thereof with an acid.

Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-tolylenediamine, 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 and 2^-acetylaminoethyloxy-para-phenylenediamine, and the addition salts thereof with an acid, are particularly preferred.

Among the bis(phenyl)alkylenediamines that may be mentioned, for example, are N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1 ,3-diaminopropanol, N,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-diaminophenoxy)-3,6-dioxaoctane, and the addition salts thereof.

Among the para-aminophenols that may be mentioned, for example, are para- aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3- chlorophenol, 4-amino-3-hydroxymethylphenol, 4-amino-2-methylphenol, 4-amino-2- hydroxymethylphenol, 4-amino-2-methoxymethylphenol, 4-amino-2- aminomethylphenol, 4-amino-2-^-hydroxyethylaminomethyl)phenol and 4-amino-2- fluorophenol, and the addition salts thereof with an acid. Among the ortho-aminophenols that may be mentioned, for example, are 2- aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol and 5-acetamido-2- aminophenol, and the addition salts thereof.

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

Among the pyridine derivatives that may be mentioned are the compounds described, for example, in patents GB 1 026 978 and GB 1 153 196, for instance 2,5- diaminopyridine, 2-(4-methoxyphenyl)amino-3-aminopyridine and 3,4- diaminopyridine, and the addition salts thereof.

Other pyridine oxidation bases that are useful in the present invention are the 3- aminopyrazolo[1 ,5-a]pyridine oxidation bases or addition salts thereof described, for example, in patent application FR 2 801 308. Examples that may be mentioned include pyrazolo[1 ,5-a]pyrid-3-ylamine, 2-acetylaminopyrazolo[1 ,5-a]pyrid-3-ylamine,

2- morpholin-4-ylpyrazolo[1 ,5-a]pyrid-3-ylamine, 3-aminopyrazolo[1 ,5-a]pyridine-2- carboxylic acid, 2-methoxypyrazolo[1 ,5-a]pyrid-3-ylamine, (3-aminopyrazolo[1 ,5- a]pyrid-7-yl)methanol, 2-(3-aminopyrazolo[1 ,5-a]pyrid-5-yl)ethanol, 2-(3- aminopyrazolo[1 ,5-a]pyrid-7-yl)ethanol, (3-aminopyrazolo[1 ,5-a]pyrid-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-ylpyrazolo[1 ,5-a]pyrid-3-ylamine, pyrazolo[1 ,5- a]pyridine-3,5-diamine, 5-morpholin-4-ylpyrazolo[1 ,5-a]pyrid-3-ylamine, 2-[(3- aminopyrazolo[1 ,5-a]pyrid-5-yl)(2-hydroxyethyl)amino]ethanol, 2-[(3- aminopyrazolo[1 ,5-a]pyrid-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 and 3-aminopyrazolo[1 ,5-a]pyridin-7-ol, and the addition salts thereof.

Among the pyrimidine derivatives that may be mentioned are the compounds described, for example, in the patents DE 2359399; JP 88-169571 ; JP 05-63124; EP 0770375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4- dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and their addition salts and their tautomeric forms, when a tautomeric equilibrium exists.

Among the pyrazole derivatives that may be mentioned are the compounds described in the patents DE 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-methylpyrazole, 4,5-diamino-1-^-hydroxyethyl)pyrazole, 3,4-diaminopyrazole, 4,5- diamino-1-(4'-chlorobenzyl)pyrazole, 4,5-diamino-1 ,3-dimethylpyrazole, 4,5-diamino-

3- methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1 ,3- dimethyl-5-hydrazinopyrazole, 1-benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3- te/f-butyl-1-methylpyrazole, 4,5-diamino-1-te/f-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- arnino-5-(2'-aminoethyl)arTiino-1 ,3-dimethylpyrazole, 3,4,5-triaminopyrazole, 1-methyl- 3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4- (β-hydroxyethyl)amino-1-methylpyrazole, and their addition salts. 4,5-diamino-1- - methoxyethyl)pyrazole may also be used.

A 4,5-diaminopyrazole will preferably be used, and even more preferentially 4,5- diamino-1-^-hydroxyethyl)pyrazole and/or a salt thereof.

Pyrazole derivatives that may also be mentioned include diamino-N,N-dihydro- pyrazolopyrazolones and especially those described in patent application FR-A-2 886 136, such as the following compounds and the addition salts thereof: 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-dimethylaminopyrrolidin-1-yl)-1 ,2-diethyl-1 ,2- dihydropyrazol-3-one, 2,3-diamino-6-hydroxy-6,7-dihydro-1 H,5H-pyrazolo[1 ,2- a]pyrazol-1-one. 2,3-Diamino-6,7-dihydro-1 H,5H-pyrazolo[1 ,2-a]pyrazol-1-one and/or a salt thereof will preferably be used.

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 a salt thereof will preferentially be used as heterocyclic bases.

Among the couplers that may be used in the composition of the invention, mention may be made especially of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers and heterocyclic couplers, and also the addition salts thereof.

Mention may be made, for example, of 1 ,3-dihydroxybenzene, 1 ,3-dihydroxy-2- methylbenzene, 4-chloro-1 ,3-dihydroxybenzene, 2,4-diamino-1-(B-hydroxyethyloxy)- benzene, 2-amino-4-(B-hydroxyethylamino)-1-methoxybenzene, 1 ,3-diaminobenzene, 1 ,3-bis(2,4-diaminophenoxy)propane, 3-ureidoaniline, 3-ureido-1-dimethylamino- benzene, sesamol, 1-B-hydroxyethylamino-3,4-methylenedioxybenzene, oc-naphthol, 2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 2- amino-3-hydroxypyridine, 6-hydroxybenzomorpholine, 3,5-diamino-2,6-dimethoxy- pyridine, 1-N-(B-hydroxyethyl)amino-3,4-methylenedioxybenzene, 2,6-bis(B-hydroxy- ethylamino)toluene, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1-H-3-methyl- pyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo-[1 ,5-b]-1 ,2,4- triazole, 2,6-dimethyl-[3,2-c]-1 ,2,4-triazole and 6-methylpyrazolo[1 ,5- a]-benzimidazole, the addition salts thereof with an acid, and mixtures thereof.

The addition salts of the oxidation bases and couplers are especially chosen from the addition salts with an acid such as the hydrochlorides, hydrobromides, sulfates, citrates, succinates, tartrates, lactates, tosylates, benzenesulfonates, phosphates and acetates.

The oxidation base(s) are each generally present in an amount of from 0.0001 % to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition.

The coupler(s) each generally represent from 0.0001 % to 10% by weight relative to the total weight of the composition, and preferably from 0.005% to 5% by weight relative to the total weight of the composition.

The composition according to the invention may contain cationic or nonionic synthetic or natural direct dyes.

Examples of particularly suitable direct dyes that may be mentioned include nitrobenzene dyes; azo direct dyes; azomethine direct dyes; methine direct dyes; azacarbocyanin direct dyes, for instance tetraazacarbocyanins (tetraazapentamethines); quinone and in particular anthraquinone, naphthoquinone or benzoquinone direct dyes; azine direct dyes; xanthene direct dyes; triarylmethane direct dyes; indoamine direct dyes; indigoid direct dyes; phthalocyanine direct dyes, porphyrin direct dyes 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(s) more particularly represent from

0.0001 % to 10% by weight and preferably from 0.005% to 5% by weight of the total weight of the composition.

The composition according to the invention comprises one or more surfactants. The surfactant(s) may be cationic, amphoteric, nonionic and/or anionic surfactants. The surfactants that are useful in the composition of the invention are surfactants that are known per se in the field of dyeing keratin fibres.

The amphoteric or zwitterionic surfactant(s) that may be used in the present invention may especially be optionally quaternized, secondary or tertiary aliphatic amine derivatives, in which the aliphatic group is a linear or branched chain containing from 8 to 22 carbon atoms, the said amine derivatives containing at least one anionic group such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. In particular, mention may be made of (C₈-C₂o)alkylbetaines, sulfobetaines, (C₈-C₂o alkyl)amido(C₃.₈ alkyl)betaines or (C₈-C₂o alkyl)amido(C₆-C₈ alkyl)sulfobetaines. Among the optionally quaternized, secondary or tertiary aliphatic amine derivatives that can be used, as defined above, mention may also be made of the compounds having the respective structures (VIII) and (VIII') below: Ra-CONHCH2CH2- N+(Rb)(Rc)(CH2COO-) (VIII) 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') (VIII') in which:

B represents -CH₂CH₂OX',

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

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

COOZ', or a hydrogen atom,

Y' represents -COOH, -COOZ', the group -CH₂-CHOH-S0₃H or -CH₂-CHOH- S0₃Z',

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

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

These compounds are classified 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 the company Rhodia under the trade name Miranol^® C2M Concentrate.

Among the amphoteric or zwitterionic surfactants mentioned above, use is preferably made of betaines comprising at least one saturated or unsaturated C₈-C₃₀ fatty chain and in particular the compounds of formula (A):

Rr(CONH)x-Ar N+(R₂)(R₃)-A₂-Z (A)

with

x denoting 0 or 1 ,

A 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 C1-C4 alkyl radical,

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

Preferably, R₂ and R₃ denote a methyl radical.

The amphoteric surfactant(s) of betaine type used in the cosmetic composition according to the present invention may especially be (C₈_ 2₀)alkylbetaines, (C₈_₂₀)alkylsulfobetaines, (C₈_₂₀ alkyl)amido(C₂.₈ alkyl)betaines or (C₈_₂₀ alkyl)amido(C₆-₈ alkyl)sulfobetaines.

Among the amphoteric surfactants mentioned above that are preferably used are (C₈.₂₀ alkyl)betaines and (C₈.₂₀ alkyl)amido(C₂.₈ alkyl)betaines, and mixtures thereof.

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

The term "anionic surfactant" means 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, OS0₃ ^", H₂P0₃, HP0₃ ^" , 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 sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkyl sulfonates, alkylamide sulfonates, alkylaryl sulfonates, alpha-olefin sulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acyl sarcosinates, acyl glutamates, alkyl sulfosuccinamates, 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 C6-24 alkyl monoesters of polyglycoside-polycarboxylic acids may be chosen from C₆-24 alkyl polyglycoside citrates, C₆-24 alkyl polyglycoside tartrates and Ce-24 alkyl polyglycoside sulfosuccinates.

When the anionic surfactant(s) (ii) are in salt form, 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.

Examples of amino alcohol salts that may especially be mentioned include monoethanolamine, diethanolamine and triethanolamine salts,

monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino- 2-methyl-1-propanol salts, 2-amino-2-methyl-1 ,3-propanediol salts and

tris(hydroxymethyl)aminomethane salts.

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

Among the anionic surfactants, it is preferred, according to the invention, to use alkyl sulfate salts and alkyl ether sulfate salts and mixtures thereof.

The term "cationic surfactant" means a surfactant that is positively charged when it is contained in the composition according to the invention. This surfactant may bear one or more positive permanent charges or may contain one or more cationizable functions within the composition according to the invention.

The cationic surfactant(s) that may be used as conditioning agents according to the present invention are preferably selected from optionally polyoxyalkylenated primary, secondary or tertiary fatty amines, or salts thereof, quaternary ammonium salts, and mixtures thereof.

The fatty amines generally comprise at least one C₈-C₃₀ hydrocarbon- based chain. Among the fatty amines that may be used according to the invention, examples that may be mentioned include stearylamidopropyldimethylamine and distearylamine. Examples of quaternary ammonium salts that may especially be mentioned include:

- those corresponding to the general formula (IX) below:

(IX)

in which the groups R₈ to Rn , which may be identical or different, represent a linear or branched aliphatic group containing from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups R₈ to Rn denoting a group containing from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms. The aliphatic groups may comprise heteroatoms such as, in particular, oxygen, nitrogen, sulfur and halogens. The aliphatic groups are chosen, for example, from Ci.₃₀ alkyl, Ci.₃₀ alkoxy, polyoxy(C₂-C₆)alkylene, Ci.₃₀ alkylamide, (Ci₂-C₂₂)alkylamido(C₂-C₆)alkyl, (Ci₂-C₂₂)alkylacetate and Ci.₃₀ hydroxyalkyl; X is an anion chosen from the group of halides, phosphates, acetates, lactates, (C C₄)alkyl sulfates, and (C C₄)alkyl- or (C C₄)alkylaryl- sulfonates.

Among the quaternary ammonium salts of formula (IX), those that are preferred are, on the one hand, tetraalkylammonium salts, for instance

dialkyldimethylammonium or alkyltrimethylammonium salts in which the alkyl group contains approximately from 12 to 22 carbon atoms, in particular

behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts, or, on the other hand, the

palmitylamidopropyltrimethylammonium salt, the

stearamidopropyltrimethylammonium salt, the

stearamidopropyldimethylcetearylammonium salt, or the

stearamidopropyldimethyl(myristyl acetate)ammonium salt sold under the name Ceraphyl® 70 by the company Van Dyk. It is particularly preferred to use the chloride salts of these compounds;

- quaternary ammonium salts of imidazoline, for instance those of formula (X) below:

(X) in which R₁₂ represents an alkyl or alkenyl group containing from 8 to 30 carbon atoms, derived for example from tallow fatty acids, R₁₃ represents a hydrogen atom, a C C₄ alkyl group or an alkyl or alkenyl group containing from 8 to 30 carbon atoms, R₁₄ represents a C C₄ alkyl group, R₁₅ represents a hydrogen atom or a C C₄ alkyl group, X^" is an anion selected from the group consisting of halides, phosphates, acetates, lactates, alkyl sulfates, alkylsulfonates or alkylarylsulfonates in which the alkyl and aryl groups each preferably comprise from 1 to 20 carbon atoms and from 6 to 30 carbon atoms. R₁₂ and R₁₃ preferably denote a mixture of alkyl or alkenyl groups comprising from 12 to 21 carbon atoms, for example tallow fatty acid derivatives, R₁₄ denotes a methyl group, and R₁₅ denotes a hydrogen atom. Such a product is sold, for example, under the name Rewoquat® W 75 by the company Rewo;

- quaternary diammonium or triammonium salts, in particular of formula

in which R₁₆ denotes an alkyl radical containing approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted by one or more oxygen atoms, R₁₇ is selected from hydrogen and an alkyl radical containing from 1 to 4 carbon atoms or a group (Ri₆a)(Ri7a)(Ri8a)N-(CH₂)3, Rie_a, Ri7a, Risa, Ri8, Ri9, R20 and R₂i, which are identical or different, are selected from hydrogen and an alkyl radical containing from 1 to 4 carbon atoms, and X is an anion selected from the group of halides, acetates, phosphates, nitrates and methyl sulfates. Such compounds are, for example, Finquat CT-P, available from the company Finetex (Quaternium 89), and Finquat CT, available from the company Finetex (Quaternium 75), - quaternary ammonium salts containing at least one ester function, such as those of formula (XII) below:

R 24 -0)x — 23 X

(XII)

in which:

R22 is selected from C C₆ alkyl radicals and C C₆ hydroxyalkyl or dihydroxyalkyl radicals;

R₂3 is chosen from:

0

R₂₆ C

- the group

- groups R₂₇, which are linear or branched, saturated or unsaturated d- C₂2 hydrocarbon-based groups,

- a hydrogen atom,

R25 is chosen from:

0

R C

- the group ^{' 28}

- groups R₂g, which are linear or branched, saturated or unsaturated C C₆ hydrocarbon-based groups,

- a hydrogen atom,

R24, R26 and R₂8, which are identical or different, are selected from linear or branched, saturated or unsaturated C₇-C₂i hydrocarbon radicals;

r, s and t, which may be identical or different, are integers ranging from 2 to 6;

r1 and t1 , which may be identical or different, are equal to 0 or 1 , and r2+r1 =2r and t1 +t2=2t, y is an integer ranging from 1 to 10;

x and z, which may be identical or different, are integers ranging from 0 to

10;

X^" is a simple or complex organic or inorganic anion; with the proviso that the sum x + y + z is from 1 to 15, that when x is 0, then R₂3 denotes R₂₇ and that when z is 0, then R₂₅ denotes R₂₉.

The alkyl groups R₂₂ may be linear or branched, and more particularly linear.

Preferably, R₂₂ denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.

Advantageously, the sum x + y + z is from 1 to 10.

When R₂₃ is a hydrocarbon group R₂₇, it may be long and may have 12 to 22 carbon atoms, or may be short and may have from 1 to 3 carbon atoms.

When R₂₅ is a hydrocarbon group R₂₉, it has preferably 1 to 3 carbon atoms.

Advantageously, R24, R26 and R₂8, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C11-C21 hydrocarbon- based groups, and more particularly from linear or branched, saturated or unsaturated C11-C21 alkyl and alkenyl groups.

Preferably, x and z, which may be identical or different, are equal to 0 or

1.

Advantageously, y is equal to 1.

Preferably, r, s and t, which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.

The anion X^" is preferably a halide (chloride, bromide or iodide) or an alkyl sulfate, more particularly methyl sulfate. However, methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion that is compatible with the ammonium containing an ester function, may be used.

The anion X^" is even more particularly chloride or methyl sulfate.

Use is made more particularly, in the composition according to the invention, of the ammonium salts of formula (VII) in which:

R₂₂ denotes a methyl or ethyl group,

x and y are equal to 1 ;

z is equal to 0 or 1 ;

r, s and t are equal to 2;

R₂₃ is chosen from:

O the group ²⁶

methyl, ethyl or Ci₄-C₂₂ hydrocarbon-based groups, - a hydrogen atom;

R25 is chosen from:

0

- the group ²⁸

- a hydrogen atom;

R24, R26 and R₂s, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.

The hydrocarbon-based groups are advantageously linear.

Mention may be made, for example, of the compounds of formula (VI) such as the diacyloxyethyldimethylammonium,

diacyloxyethylhydroxyethylmethylammonium,

monoacyloxyethyldihydroxyethylmethylammonium,

triacyloxyethylmethylammonium and

monoacyloxyethylhydroxyethyldimethylammonium salts (chloride or methyl sulfate in particular), and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.

These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an

alkyldiisopropanolamine, which are optionally oxyalkylenated, with Ci₀-C₃₀ fatty acids or with mixtures of Ci₀-C₃₀ fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by a quaternization using an alkylating agent such as an alkyl halide (preferably a methyl or ethyl halide), a dialkyl sulfate (preferably dimethyl or diethyl sulfate), methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.

Such compounds are sold, for example, under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company Ceca or Rewoquat® WE 18 by the company Rewo-Witco.

The composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts. It is also possible to use the ammonium salts containing at least one ester function that are described in patents US-A-4 874 554 and US-A-4 137 180.

Use may be made of behenoylhydroxypropyltrimethylammonium chloride sold by KAO under the name Quatarmin BTC 131.

Preferably, the ammonium salts containing at least one ester function contain two ester functions.

Among the quaternary ammonium salts containing at least one ester function, which may be used, it is preferred to use

dipalmitoylethylhydroxyethylmethylammonium salts.

The nonionic surfactants are more particularly chosen from monooxyalkylenated or polyoxyalkylenated, monoglycerolated or polyglycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, 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 contain a number of moles of ethylene oxide and/or of propylene oxide of between 1 and 100, preferably between 2 and 50 and preferably between 2 and 30.

In accordance with one 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; polyoxyethylenated esters of linear or branched, saturated or unsaturated 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 that 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.

Nonionic surfactants that may also be mentioned include non-oxyethylenated fatty acid esters of sorbitan, fatty acid esters of sucrose, optionally oxyalkylenated alkylpolyglycosides, alkylglucoside esters, derivatives of N-alkylglucamine and of N- acylmethylglucamine, aldobionamides and amine oxides.

The surfactant(s) are preferably chosen from amphoteric, nonionic and anionic surfactants.

More preferentially, the surfactant(s) are selected from amphoteric and anionic surfactants.

Even more preferentially, the surfactant(s) are selected from amphoteric surfactants.

According to one particular embodiment, the composition of the invention comprises one or more amphoteric surfactants, one or more nonionic surfactants and one or more anionic surfactants. According to this embodiment, the nonionic surfactant is preferably chosen from oxyethylenated fatty alcohols and oxyethylenated plant oils, which may be saturated or unsaturated. The anionic surfactant is chosen from alkyl sulfates and alkyl ether sulfates.

The total amount of surfactants in the cosmetic composition of the invention generally ranges from 0.1 % to 30% by weight, preferably from 1 % to 20% by weight and better still from 1 % to 10% by weight relative to the total weight of the composition.

The composition may also contain various adjuvants conventionally used in compositions for dyeing or lightening the hair, such as anionic, cationic or nonionic polymers or mixtures thereof; antioxidants; penetrants; sequestrants; fragrances; dispersants; film-forming agents; ceramides; preserving agents; opacifiers.

The above adjuvants are generally present in an amount for each of them of between 0.01 % and 20% by weight relative to the weight of the composition.

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

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

Examples of organic solvents that may be mentioned include linear or branched and preferably saturated monoalcohols or diols, comprising 2 to 10 carbon atoms, such as ethanol, isopropanol, hexylene glycol (2-methyl-2,4-pentanediol), neopentyl glycol and 3-methyl-1 ,5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as benzyl alcohol or phenylethyl alcohol; polyols containing more than two hydroxyl functions, such as glycerol; polyol ethers, for instance ethylene glycol monomethyl, monoethyl or monobutyl ether, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether; and also diethylene glycol alkyl ethers, especially C C₄ alkyl ethers, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.

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

The composition is preferably aqueous. In this case, it preferably comprises from 30% to 95% by weight of water, better still from 40% to 90% by weight of water and even better still from 50% to 85% by weight of water relative 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 and preferably between 5 and 11. Preferably, between 7 and 1 1 limits included.

It may be adjusted to the desired value by means of acidifying or basifying agents usually used in the dyeing of keratin fibres, and in particular the alkaline agents of the invention mentioned above.

The composition according to the invention is presented for application to keratin fibres in the form of a mousse.

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

According to one particularly preferred embodiment, the composition according to the invention is in the form of a temporary mousse produced just before use. According to this embodiment, the composition may be conditioned in a mousse dispenser. They may be either "aerosol" products dispensed from a pressurized container, by means of a propellant gas and thus forming a mousse when they are dispensed, or compositions dispensed from a container by means of a mechanical pump connected to a dispensing head, the passage of the composition through the dispensing head transforming it into a mousse at the latest at an outlet orifice of such a head.

According to a first variant, the dispenser may be an aerosol, containing, besides the base composition, generally divided into two parts, one with the oxidizing agent(s) and the other with the dye precursor(s), a propellant gas. In such a configuration, the two parts are generally stored separately, each in a container under pressure. Thus, the propellant gases selected in each of the containers may be adapted to the part contained.

The propellant gas that may be used may be chosen from carbon dioxide, nitrogen, nitrogen oxide, dimethyl ether, volatile hydrocarbons such as butane, isobutane, propane and pentane, and mixtures thereof.

In practice, for this variant, either an aerosol conditioning with a single container containing two internal pockets or a twin aerosol thus containing two containers will be used. In both cases, the dispensing head is such that the substance that is sprayed in mousse form is the composition according to the invention, i.e. the mixture of the composition with the oxidizing agent(s) and the composition with the oxidation dye precursor(s).

According to another embodiment, the composition may be in a mousse dispenser of "pump-action bottle" type. These dispensers comprise a dispensing head for delivering the composition, a pump and a dip tube for transferring the composition from the container into the head to deliver the product. A mousse 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 grille, or similar structures.

Such dispensers are well known to those skilled in the art and are described in US patent No. 3 709 437 (Wright), US patent No. 3 937 364 (Wright), US patent No. 4 022 351 (Wright), US patent No. 4 1 147 306 (Bennett), US patent No. 4 184 615 (Wright), US patent No. 4 598 862 (Rice), US patent No. 4 615 467 (Grogan et al.), and US patent No. 5 364 031 (Tamiguchi et al.).

In practice, for this variant, the oxidizing agent(s) are conditioned in a first container equipped with a stopper, and the oxidation dye precursor(s) are conditioned in a second container, separate from the first, and also closed with a closing member. The closing member may be a pump-action dispensing mechanism. The composition according to the invention is then formed by mixing, before use, a composition with the oxidizing agent(s) and a composition with the oxidation dye precursor(s). To this end, to limit the number of containers provided, one from among the first and second container defines an internal volume that is sufficient to receive therein all of the two compositions. The mixture of the compositions may be homogenized by closing this container and shaking the container. The closing of the container is advantageously performed directly with the dispensing head. This dispensing head comprises a mechanical pump held in a brace intended for mounting by click-fastening or screwing onto the neck of the container containing the mixture. The pump comprises a pump body connected to a dip tube for dispensing all of the mixture. The pump also comprises a push button for actuating the pump body, such that each time it is actuated, a dose of composition is sucked into the dip tube and ejected in mousse form at the dispensing orifice of the head.

In this example, the containers are preferentially made of a thermoplastic material, and obtained via extrusion blow-moulding or injection blow-moulding processes. In particular, the container for conditioning the composition with the oxidation dye precursor(s) is made of a material comprising a non-zero proportion of EVOH. The pump is, for example, the standard model "F2-L9" sold by the company Rexam.

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

A subject of the invention is also a multi-compartment device comprising, in a first compartment, a composition containing one or more surfactant(s), one or more oxidation dye precursor(s), one or more alkaline agent(s), in a second, a composition containing one or more oxidizing agents, at least one of the two compositions comprising one or more associative polymer(s), and in a third, a container equipped with a member for applying in mousse form the composition according to the invention obtained from the mixing of the two preceding compositions.

The dyeing process according to the invention consists in applying the composition according to the invention to wet or dry human keratin fibres for a time that is sufficient to develop the desired coloration. According to the invention, the composition applied to the keratin fibres is in mousse form. The dyeing process is generally performed at room temperature (between 15 and 25°C) and up to temperatures that may be as high as 60°C to 80°C. After a leave-on time of from one minute to one hour and preferably from 5 minutes to 30 minutes, the human keratin fibres are rinsed with water, and optionally washed with a shampoo and then rinsed with water.

The examples that follow serve to illustrate the invention without, however, being limiting in nature.

EXAMPLES

The following compositions are prepared (the amounts are expressed in g% of active material):

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

Composition Composition A1 A2

Oxidation dye precursors (base(s) and qs shade qs shade coupler(s)) Cocoylbetaine 2.5 2.5

Aqueous ammonia (expressed as NH₃) 1.5 -

Monoethanolamine 5 5

Sorbitol 10 10

Cetylhydroxyethylcellulose (Natrosol Plus 0.3 0.3

Grade 330 CS®)

Polyquaternium-6 1.25 1.25

Oxyethylenated (40 EO) hydrogenated castor 1 1 oil

Erythorbic acid 0.5 0.5

Sodium metabisulfite 0.5 0.5

EDTA 0.2 0.2

Water qs 100 qs 100

The mixture is introduced in an amount of 65 g (26 g of composition A + 39 g of composition B) into a pump-action bottle (L9 Rexam) equipped with a dip tube. The device makes it possible by pumping to obtain a mousse that is sufficiently compact to be applied to natural or permanent-waved grey hair containing 90% white hairs, and not to disintegrate immediately. The comfort on application is very good. After a leave-on time of 30 minutes, the locks are rinsed, washed with a standard shampoo, rinsed again and then dried to give the desired coloration. This coloration is strong and sparingly selective.

Claims

CLAIMS 1. Dye composition in mousse form, comprising:

(a) at least one associative polymer;

(b) at least one alkaline agent;

(c) at least one surfactant;

(d) at least one oxidizing agent;

(e) at least one oxidation dye precursor.

2. Composition according to Claim 1 , in which the surfactant(s) are chosen from cationic, amphoteric, nonionic and anionic surfactants, preferably from amphoteric, nonionic and anionic surfactants, more preferentially from amphoteric and anionic surfactants and better still from amphoteric surfactants.

3. Composition according to Claim 1 or 2, in which the amphoteric surfactant is chosen from (C₈-C₂o)alkylbetaines, sulfobetaines, (C₈-C2o)alkylamido(Cr C₆)alkylbetaines and (C8-C2o)alkylamido(CrC₆)alkylsulfobetaines, and preferably from (C8-C2o)alkylamido(CrC₆)alkylbetaines.

4. 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.

5. Composition according to any one of the preceding claims, in which the surfactant(s) 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, relative to the total weight of the composition.

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

7. Composition according to any one of the preceding claims, in which the alkaline agent is chosen from alkanolamines and in particular is monoethanolamine.

8. Composition according to any one of the preceding claims, in which the alkaline agent(s) represent a total amount 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, relative to the total weight of the said composition.

9. Composition according to any one of the preceding claims, in which the associative polymer is chosen from nonionic and cationic associative polymers.

10. Composition according to the preceding claim, in which the nonionic associative polymer is chosen from polyurethane polyethers bearing hydrophilic and hydrophobic blocks, and nonionic cellulose derivatives comprising at least one fatty chain.

11. Composition according to Claim 9, in which the cationic associative polymer is chosen from quaternized cellulose derivatives comprising at least one fatty chain.

12. Composition according to any one of the preceding claims, in which the oxidizing agent is hydrogen peroxide.

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

14. Aerosol device comprising a means for generating in mousse form a composition as defined in any one of Claims 1 to 13.

15. Aerosol device according to Claim 15, comprising a single container equipped with two pockets or comprising two containers.

16. Non-aerosol device comprising a bottle equipped with a mechanical pumping system and comprising a composition as defined in any one of Claims 1 to 13 and a dispensing system for delivering it in mousse form.