# Patent

## Title
Dyeing process using a mixture comprising a thickening polymer, obtained from an aerosol device, and device therefor

## Abstract

The present invention relates to a process for dyeing keratin fibres in which a mixture is applied to the fibres, this mixture being obtained from: a dye composition comprising at least one oxidation dye precursor, and an oxidizing composition comprising at least one chemical oxidizing agent, at least one of the compositions being dispensed from a pressurized container, the mixture of the two compositions comprising at least one thickening polymer chosen from: associative polymer, anionic non-associative polymer chosen from anionic polymers bearing sugar units, anionic polymers not bearing sugar units chosen from crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or mixtures thereof, and mixtures thereof; and also to a device suitable for performing this process.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This is a national stage application of PCT/EP2013/058315, filed internationally on Apr. 22, 2013, which claims priority to U.S. Provisional Application Nos. 61/663,092 and 61/663,118, both filed on Jun. 22, 2012, as well as French Application Nos. 1253741 and 1253752, both filed Apr. 24, 2012, all of which are incorporated herein by their entireties.


The present invention relates to a process for dyeing the hair using a mixture comprising at least one thickening polymer, the said mixture being obtained from two compositions, at least one of which is conditioned in a pressurized container, and also to a device suitable for performing this process.
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 form of dyeing 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 entities.
Quite often, the shades obtained with these oxidation bases are 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 the 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 take various forms such as lotions, gels, emulsions, creams or foams.
These compositions, in particular compositions comprising oxidation dyes, are obviously oxidation-sensitive and consequently contain reducing agents or antioxidants. This oxidation-preventing action is also reinforced by means of the inert atmosphere that is occasionally used during the conditioning of these compositions.
The difficulty encountered with compositions of this type results, precisely, from their oxidation sensitivity. Specifically, during their use, they come into contact with atmospheric oxygen, which thus obliges them to be used quickly. If this is not done, the compositions become unusable after storage and are lost.
Compositions which are conditioned in pressurized containers that can prevent the composition from coming into contact with air during their use are known in the field of hair dyeing, as is described, for example, in US 2010/0236570 or FR 2 048 629.
However, the coverage of the hair, in particular of grey hair, still remains to be improved, as does the galenical quality of the product obtained from the pressurized container.
There is an ongoing need to develop oxidation dye compositions in foam form which are easy to prepare and to apply and which remain sufficiently stable over time, while at the same time maintaining efficient dyeing properties, especially in terms of coverage of the hair, more particularly of grey hair, but also in terms of the intensity, homogeneity and chromaticity of the coloration obtained.
This aim and others are achieved by the present invention, one subject of which is a process for dyeing keratin fibres in which a mixture is applied to the said fibres, this mixture being obtained from:

    
    
        a dye composition comprising at least one oxidation dye precursor, and
        an oxidizing composition comprising at least one chemical oxidizing agent,
        at least one of the compositions being dispensed from a pressurized device,
        the mixture of the two compositions comprising at least one thickening polymer chosen from:
        
            associative polymer,
            anionic non-associative polymer chosen from anionic polymers bearing sugar units, anionic polymers not bearing sugar units chosen from crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or mixtures thereof, and mixtures thereof.
        
        
    
    


The invention also relates to a device that is suitable for performing the process according to the invention, comprising:

    
    
        a first container containing a dye composition comprising at least one oxidation dye precursor, and
        a second container containing an oxidizing composition comprising at least one chemical oxidizing agent,
        at least one of the two containers being pressurized, and preferably both the containers being pressurized;
        a means for dispensing the compositions;
        the mixture of the two compositions comprising at least one thickening polymer chosen from:
        
            associative polymer,
            anionic non-associative polymer chosen from anionic polymers bearing sugar units, anionic polymers not bearing sugar units chosen from crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or mixtures thereof, and mixtures thereof.
        
        
    
    


Preferably, the composition used in the process according to the invention is in the form of a foam that is particularly pleasant to apply.
It has a light, airy texture, which makes it particularly pleasant to use. The qualities of the foam are sufficiently long-lasting to enable uniform application of the dye product, without running.
The composition of the invention makes it possible to retain dyeing properties, such as strength of the colour, resistance to external agents (shampooing, perspiration, light) and selectivity, and most particularly coverage of grey hair.
Other characteristics and advantages of the invention will emerge more clearly on reading the description and the examples that follow.
In the text hereinbelow, and 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 terms “oxyalkylenated”, “oxyethylenated”, “oxypropylenated” and “glycerolated” cover, respectively, mono- or poly-oxyalkylenated, oxyethylenated, oxypropylenated or glycerolated compounds, unless otherwise mentioned.
Unless otherwise indicated, the contents of the ingredients present in the compositions are indicated without taking into account the content of propellant gas(es).
The human keratin fibres treated via the process according to the invention are preferably the hair.
Thickening Polymer
As indicated previously, the mixture used in the context of the invention comprises at least one thickening polymer chosen from associative polymer, specific anionic non-associative polymer and mixtures thereof.
According to a preferred embodiment of the invention, the content of thickening polymer(s) represents from 0.001% to 40% by weight, preferably from 0.1% to 20% by weight, and better, from 0.1% to 10% relative to the weight of the mixture.
Associative thickening polymer
The associative thickening polymer can be of nonionic, anionic, cationic or amphoteric nature.
It is recalled that associative polymers are hydrophilic polymers that are capable, in an aqueous medium, of reversibly associating with each other or with other molecules. Their chemical structure more particularly comprises at least one hydrophilic region and at least one hydrophobic region. The term “hydrophobic group” means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 6 carbon atoms, preferably 8 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially 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.
These associative polymers use in their structure at least one repeating unit other than an alkylene oxide or glycidol unit, and, in this sense, are different from surfactants.
Preferably, the mixture used in the invention comprises at least one associative polymer chosen from associative polyurethanes, which are more particularly cationic or nonionic, associative cellulose derivatives, which are more particularly cationic or nonionic, associative vinyllactams, associative unsaturated polyacids, associative aminoplast ethers, and associative polymers or copolymers comprising at least one ethylenically unsaturated monomer bearing a sulfonic group, alone or as mixtures.
Among the associative thickening polymers, mention may be made of associative polyurethane derivatives, such as those obtained by polymerization:

    
    
        about 20% to 70% by weight of an α,β-monoethylenically unsaturated carboxylic acid,
        about 20% to 80% by weight of an α,β-monoethylenically unsaturated non-surfactant monomer other than the previous one,
        about 0.5% to 60% by weight of a nonionic monourethane, which is the product of reaction of a monohydroxylated surfactant with a monoethylenically unsaturated monoisocyanate.
    
    


Such polymers are especially described in EP 173 109 and more particularly in Example 3. More precisely, this polymer is a methacrylic acid/methyl acrylate/ethoxylated (40 EO) behenyl dimethyl-meta-isopropenylbenzylisocyanate terpolymer as an aqueous 25% dispersion. This product is sold under the reference Viscophobe DB1000 by the company Amerchol.
The cationic associative polyurethanes whose family was described in patent application FR 0 009 609 are also suitable for use. This polymer may be represented more particularly by the general formula (A) below:

R—X—(P)n-[L-(Y)m]r-L′-(P′)p-X′—R′  (A)

in which:
R and R′, which may be identical or different, represent a hydrophobic group or a hydrogen atom;
X and X′, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group, or alternatively the group L′′;
L, L′ and L′′, which may be identical or different, represent a group derived from a diisocyanate;
P and P′, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group;
Y represents a hydrophilic group;
r is an integer between 1 and 100, preferably between 1 and 50 and in particular between 1 and 25;
n, m and p have a value, independently of each other, between 0 and 1000;
the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.
In a very advantageous embodiment, the only hydrophobic groups of these polyurethanes are the groups R and R′ at the chain ends.
According to a first preferred embodiment, the associative polyurethane corresponds to formula (A) in which R and R′ both independently represent a hydrophobic group; X and X′ each represent a group L′′; n and p have a value between 1 and 1000, and L, L′, L′′, P, P′, Y and m have the meaning indicated in formula (A).
According to another preferred embodiment of the invention, the associative polyurethane corresponds to formula (A) in which R and R′ both independently represent a hydrophobic group, X and X′ each represent a group L′′, n and p have the value 0, and L, L′, L′′, Y and m have the meaning indicated previously in formula (A).
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. 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.
In accordance with another preferred embodiment of the invention, the associative polyurethane corresponds to formula (A) in which R and R′ both independently represent a hydrophobic group, X and X′ both independently represent a group comprising a quaternary amine; n and p have the value 0, and L, L′, Y and m have the meaning indicated in formula (A).
The number-average molecular mass of the cationic associative polyurethanes is usually between 400 and 500 000, in particular between 1000 and 400 000 and ideally between 1000 and 300 000g/mol.
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:




in which:
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;
R1 and R3, which may be identical or different, denote a linear or branched C1-C30 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;
A- is a physiologically acceptable counterion.
The groups L, L′ and L′′ represent a group of formula:




in which:
Z represents —O—, —S— or —NH—; and
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:




or





or





or





or





or





in which:
R5 and R7 have the same meanings as R2 defined above;
R6, R8 and R9 have the same meanings as R1 and R3 defined above;
R10 represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more heteroatoms chosen from N, O, S and P;
A- is a cosmetically acceptable counterion.
As regards the meaning of Y, the term “hydrophilic group” means a polymeric or nonpolymeric 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 associative polyurethanes of formula (A) 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 (A) is a compound comprising at least one unit containing 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 HZ—(P′)p—ZH

in which Z, P, P′, 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 (A) is a diisocyanate corresponding to the formula O═C═N—R4—N═C═O, in which R4 is defined above.
Mention may be made especially of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, toluene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.
A third compound involved in the preparation of the polyurethane of formula (A) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (A).
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, a-hydroxylated hydrogenated polybutadiene.
The hydrophobic group of the polyurethane of formula (A) 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 (A) 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.
The associative polyurethane derivatives of the invention may also be nonionic polyurethane polyethers. More particularly, the said polymers comprise 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.
Preferably, these polyurethane polyethers comprise at least two hydrocarbon-based lipophilic (hydrophobic) chains more particularly containing from 8 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 provided. 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 hydrophobic-chain nonionic 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 linkage between the hydrophilic blocks, whence arises the name.
By extension, also included among the nonionic polyurethane polyethers comprising a hydrophobic chain are those in which the hydrophilic blocks are linked to the hydrophobic blocks via other chemical bonds.
As examples of hydrophobic-chain nonionic 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, Rheolate FX1100 and also Acrysol RM 184®.
Mention may also be made of the product Elfacos T210® containing a C12-C14 alkyl chain, and the product Elfacos T212® containing a C18 alkyl chain, from Akzo.
The product DW 1206B® from Rohm & Haas containing a C20 alkyl chain and a urethane linkage, 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 Röhm & Haas may also be used.
The polyurethane polyethers described previously that may be used may also be chosen from 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 Röhm & 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%)].
The mixture may similarly comprise associative cellulose-based polymers such as:

    
    
        quaternized cationic celluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof,
        quaternized cationic hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof.
    
    


The alkyl radicals borne by the above quaternized celluloses or hydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
Examples of quaternized alkylhydroxyethylcelluloses containing C8-C30 hydrophobic chains that may be mentioned include the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18B® (C12 alkyl) and Quatrisoft LM-X 529-8® (C18 alkyl), and Softcat SL100, sold by the company Amerchol, and the products Crodacel QM®, Crodacel QL® (C12 alkyl) and Crodacel QS® (C18 alkyl) sold by the company Croda.

    
    
        nonionic cellulose derivatives such as hydroxyethylcelluloses modified with groups comprising at least one hydrophobic chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, for instance the product Natrosol Plus Grade 330 CS® (C16 alkyls) sold by the company Aqualon, or the product Bermocoll EHM 100® sold by the company Berol Nobel,
        cellulose derivatives modified with alkylphenyl polyalkylene glycol ether groups, such as the product Amercell Polymer HM-1500® sold by the company Amerchol.
    
    


As regards the associative polyvinyllactams, examples that may be mentioned include the polymers described especially in FR 0101106. The said polymers are more particularly cationic polymers and comprise:

    
    
        a) at least one monomer of vinyllactam or alkylvinyllactam type;
        b) at least one monomer of structure (a) or (b) below:
    
    






in which:
X denotes an oxygen atom or a radical NR6,
R1 and R6 denote, independently of each other, a hydrogen atom or a linear or branched C1-C6 alkyl radical,
R2 denotes a linear or branched C1-C4 alkyl radical,
R3, R4 and R5 denote, independently of each other, a hydrogen atom, a linear or branched C1-C30 alkyl radical or a radical of formula (IV):

—(Y2)r—(CH2—CH(R7)—O)x—R8   (c)

Y, Y1 and Y2 denote, independently of each other, a linear or branched C2-C16 alkylene radical,
R7 denotes a hydrogen atom or a linear or branched C1-C4 alkyl radical or a linear or branched C1-C4 hydroxyalkyl radical,
R8 denotes a hydrogen atom or a linear or branched C1-C30 alkyl radical,
p, q and r denote, independently of each other, either the value 0 or the value 1,
m and n denote, independently of each other, an integer ranging from 0 to 100,
x denotes an integer ranging from 1 to 100,
Z denotes an organic or mineral acid anion,
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 poly(vinyllactam) polymers may be crosslinked or non-crosslinked and may also be block polymers.
Preferably, the counterion Z— of the monomers of formula (b) 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 C1-C30 alkyl radical.
More preferentially, the monomer b) is a monomer of formula (b) for which, even more preferentially, m and n are equal to zero.
The vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (d):




in which:
s denotes an integer ranging from 3 to 6,
R9 denotes a hydrogen atom or a C1-C5 alkyl radical,
R10 denotes a hydrogen atom or a C1-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 (d) is vinylpyrrolidone.
The poly(vinyllactam) polymers 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) a monomer of formula (d),
b) a monomer of formula (a) in which p=1, q=0, R3 and R4 denote, independently of each other, a hydrogen atom or a C1-C5 alkyl radical and R5 denotes a C9-C24 alkyl radical, and
c) a monomer of formula (b) in which R3 and R4 denote, independently of each other, a hydrogen atom or a C1-C5 alkyl radical.
Even more preferentially, terpolymers comprising, by weight, 40% to 95% of monomer (d), 0.1% to 55% of monomer (b) and 0.25% to 50% of monomer (b) are used.
Such polymers are especially described in patent application WO 00/68282, the content of which forms an integral part of the invention.
As poly(vinyllactam) polymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacrylamido propylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacrylamidop ropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamidopr opylammonium tosylate or chloride terpolymers are used in particular. The vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamidopr opylammonium chloride terpolymer is sold at 20% in water by the company ISP under the name Styleze W20.
The associative polyvinyllactam derivatives of the invention may also be nonionic copolymers of vinylpyrrolidone and of hydrophobic monomers bearing a hydrophobic chain, examples of which that may be mentioned include:

    
    
        the products Antaron V216® or Ganex V216® (vinylpyrrolidone/hexadecene copolymer) sold by the company I.S.P.
        the products Antaron V220® or Ganex V220® (vinylpyrrolidone/eicosene copolymer) sold by the company I.S.P,
    
    


Among the associative unsaturated polyacid derivatives that may be mentioned are those comprising at least one hydrophilic unit of olefinic unsaturated carboxylic acid type, and at least one hydrophobic unit of non-ethoxylated unsaturated carboxylic acid (C10-C30)alkyl ester type.
These polymers are especially chosen from those in which the hydrophilic unit of olefinic unsaturated carboxylic acid type corresponds to the monomer of formula (e) below:




in which R1 denotes H, CH3, or C2H5, i.e. acrylic acid, methacrylic acid or ethacrylic acid units, and in which the hydrophobic unit of unsaturated carboxylic acid (C10-C30)alkyl ester type corresponds to the monomer of formula (f) below:




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.
Unsaturated carboxylic acid (C10-C30)alkyl esters include, 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 U.S. Pat. No. 3,915,921 and U.S. Pat. No. 4,509,949.
Among the anionic associative polymers of this type that are used more particularly are polymers formed from a monomer mixture comprising:
essentially acrylic acid,
an ester of formula (f) described above in which R2 denotes H or CH3, R3 denoting an alkyl radical containing from 12 to 22 carbon atoms,
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 that are preferred are those consisting of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizable monomer, or alternatively those consisting of from 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinking polymerizable monomer such as those described above.
Among the abovesaid polymers, those most particularly preferred 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®.
The anionic associative polymers may also be copolymers comprising among their monomers an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.
Preferentially, these compounds also comprise as monomer an ester of an α,β-monoethylenically unsaturated carboxylic acid and of a C1-C4 alcohol.
An example of a compound of this type that may be mentioned is Aculyn 22® sold by the company Röhm & Haas, which is a methacrylic acid/ethyl acrylate/oxyalkylenated stearyl methacrylate terpolymer.
As regards the thickening polymers of aminoplast ether type, any product derived from the condensation of an aldehyde with an amine or an amide, and also any structural unit formed from an aminoplast residue and from a divalent hydrocarbon-based residue linked to the aminoplast residue via an ether bond, is designated.
The polymers with an aminoplast ether backbone are preferably chosen from those containing at least one unit having the structure (g) below:




in which:

    
    
        AMP is an aminoplast residue with alkylene (or divalent alkyl) units,
        R denotes a hydrogen atom, a C1-C4 alkyl radical or a C1-C4 acyl radical,
        RO1 is a divalent alkylene-oxy residue,
        p denotes a positive integer,
        the group(s) OR being linked to the alkylene units of the AMP residue.
    
    


Preferably, the polymers with an aminoplast ether backbone are chosen from those containing at least one unit having the structure (h) below:




in which:

    
    
        AMP, R, RO1 and p have the same meaning as previously,
        RO2 is a group different from RO, linked to AMP via a heteroatom and comprising at least two carbon atoms, and
        q is a positive integer.
    
    


Even more preferentially, the polymers correspond to formulae (III) and (III)bis below:




in which:

    
    
        AMP, R, RO1, RO2, p and q have the same meaning as previously,
        R2 or R3, which may be identical or different, represent an end group that may denote a hydrogen atom, a group RO1 H, a group RO2H, a group AMP(OR)p or any monofunctional group such as alkyl, cycloalkyl, aryl, aralkyl, alkylaryl, alkyloxyalkyl, aryloxyalkyl or cycloalkoxyalkyl,
        a being a number greater than 1 and preferably greater than 2.
    
    


The aminoplast residues bearing their groups OR incorporated in the polymers may be chosen, in a non-limiting manner, from structures (1) to (12) below:







in which:

    
    
        R has the same meaning as previously,
        R1 denotes C1-C4 alkyl,
        y is a number at least equal to 2,
        x denotes 0 or 1.
    
    


Preferably, the aminoplast residue(s) bearing their groups OR are chosen from those of structure (13) below:




in which R, p and x have the same meanings as previously.
The divalent alkylene-oxy residues are preferably those corresponding to the diols of general formula (14) below:

HO—(ZO)y-(Z1(Z2O)w)t-(Z′O)y-Z3OH   (14),

    
    
        y and y′ being numbers ranging from 0 to 1000,
        t and w being numbers ranging from 0 to 10,
        Z, Z′, Z2 and Z3 are C2-C4 alkylene radicals and preferably radicals —CH2-CH(Z4)- and —CH2-CH(Z4)-CH2-,
        Z1 being a linear or cyclic, branched or unbranched, aromatic or non-aromatic radical, possibly comprising one or more heteroatoms, and containing from 1 to 40 carbon atoms,
        Z4 denoting a hydrogen atom or a C1-C4 alkyl radical or a C1-C3 acyl radical, it being understood that at least one of the radicals Z4 of the radicals Z, Z′, Z2 and Z3 is other than an acyl radical.
    
    


Preferably, Z4 denotes a hydrogen atom or a methyl radical.
Even more preferentially, t=0 and Z, Z′ and Z3 denote —CH2CH2-, and at least one from among y and y′ is other than zero. The compounds of formula (14) are then polyethylene glycols.
The aminoplast ether polymers of formula (g) contain at least one saturated or unsaturated, linear or cyclic chain comprising at least 8 carbon atoms, and are described in particular in patent U.S. Pat. No. 5,914,373, to which reference may be made for further details.
As polymers with an aminoplast ether backbone of formula (g), mention may be made in particular of the products Pure-Thix® L [PEG-180/Octoxynol-40/TMMG Copolymer (INCI name)], Pure-Thix M® [PEG-180/Laureth-50/TMMG Copolymer (INCI name)], Pure-Thix® HH [Polyether-1 (INCI name)]; Pure Thix TX-1442® [PEG-18/dodoxynol-5/PEG-25 tristyrylphenol/tetramethoxymethyl glycoluril copolymer] sold by the company Süd-Chemie.
The thickening polymers included as ingredients in the mixture according to the invention may also be chosen from 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.
Preferentially, the said polymers are partially or totally neutralized with a mineral base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base such as mono-, di- or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.
These associative polymers may or may not be crosslinked, and are preferably crosslinked polymers. In this case, the crosslinking agents originate from at least one monomer bearing at least two ethylenic unsaturations (carbon-carbon double bond).
The crosslinking monomers containing at least two ethylenic unsaturations are chosen, for example, from diallyl ether, triallyl cyanurate, diallyl maleate, allyl (meth)acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, tetra- or diethylene glycol di(meth)acrylate, triallylamine, tetraallylethylenediamine, trimethylolpropane diallyl ether, trimethylolpropane triacrylate, methylenebis(meth)acrylamide or divinylbenzene, allylic ethers of alcohols of the sugar series, or other allylic or vinyl ethers of polyfunctional alcohols, and also allylic esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.
Methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate is used more particularly. The degree of crosslinking generally ranges from 0.01 mol % to 10 mol %, relative to the polymer.
The ethylenically unsaturated monomers bearing a sulfonic group are especially chosen from vinylsulfonic acid, styrenesulfonic acid, (meth)acrylamido(C1-C22)alkylsulfonic acids, N—(C1-C22)alkyl(meth)acrylamido(C1-C22)alkylsulfonic acids such as undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.
(Meth)acrylamido(C1-C22)alkylsulfonic acids, for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, are more particularly used.
2-Acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially or totally neutralized forms thereof, are preferably used.
The amphiphilic polymers present in dispersion (A) according to the invention may also be chosen from random amphiphilic AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or di-n-alkylamine, and such as those described in patent application WO 00/31154.
The hydrophobic monomers constituting the hydrophobic part of the polymer are preferably chosen from the acrylates or acrylamides of formula (k) below:




in which R1 and R3, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y denotes O or NH; R2 denotes a hydrophobic hydrocarbon-based radical as defined previously; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.
The R2 radical is advantageously chosen from linear C6-C18 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl or n-dodecyl radicals); branched C6-C18 alkyl radicals; cyclic C6-C18 alkyl radicals (for example cyclododecane (C12) or adamantane (C10) radicals); C6-C18 alkylperfluoro radicals (for example the group of formula —(CH2)2-(CF2)9-CF3); the cholesteryl (C27) radical or a cholesterol ester residue, such as the cholesteryl oxyhexanoate group; or polycyclic aromatic groups, such as naphthalene or pyrene. Among these radicals, the ones that are more particularly preferred are linear alkyl radicals and more particularly the n-dodecyl radical.
According to a particular form of the invention, the monomer of formula (k) comprises at least one alkylene oxide unit (x≧1) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain is preferably constituted of ethylene oxide units and/or of propylene oxide units and even more particularly constituted of ethylene oxide units. The number of oxyalkylene units generally ranges from 3 to 100, more preferably from 3 to 50 and even more preferably from 7 to 25.
The copolymers may also contain other ethylenically unsaturated hydrophilic monomers chosen, for example, from (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
These copolymers are described especially in documents EP 750 899 and U.S. Pat. No. 5,089,578, and in the following publications from Yotaro Morishima: Self-assembling amphiphilic polyelectrolytes and their nanostructures—Chinese Journal of Polymer Science Vol. 18, No. 40, (2000), 323-336; Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering—Macromolecules 2000, Vol. 33, No. 10-3694-3704; Solution properties of micelle networks formed by nonionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behaviour—Langmuir, 2000, Vol. 16, No. 12, 5324-5332; Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers—Polym. Preprint, Div. Polym. Chem. 1999, 40(2), 220-221.
The distribution of the monomers in the copolymer may be in random or block form.
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 units and from 40% to 85% by weight of (C8-C16)alkyl(meth)acrylamide units or of (C8-C16)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-C18)alkylacrylamide units, such as those described in patent U.S. Pat. No. 5,089,578;
        copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.
    
    


Mention will be made more particularly of the copolymers formed from AMPS units of formula (XXX) below:




in which X+ has the same definition as previously,
and of units of formula (XXXI) below:




in which x denotes an integer ranging from 3 to 100, preferably from 5 to 80, and more preferentially from 7 to 25; R1 has the same meaning as that indicated above in formula (j) and R4 denotes a linear or branched C6-C22, especially C8-C22 and more preferentially C10-C22 alkyl.
The polymers that are particularly preferred are those for which x=25, R1 denotes methyl and R4 represents n-dodecyl; they are described in the Morishima articles mentioned above.
The polymers for which X+ denotes sodium or ammonium are more particularly preferred.
As such associative polymers bearing a sulfonic group, mention may thus be made of the product sold under the name Aristoflex HMS by the company Clariant.
The associative polymers of the invention are preferably anionic or cationic.
In one preferred variant, these associative polymers are celluloses or polyurethanes, preferably celluloses.
According to a preferred embodiment of the invention, the content of associative polymer(s) represents from 0.001% to 20% by weight and preferably from 0.1% to 2% by weight, relative to the weight of the mixture.
The non-associative polymer(s) present in the mixture used in the invention may be in the dye composition, in the oxidizing composition or in both compositions simultaneously.
Anionic Non-Associative Thickening Polymers
As indicated previously, the mixture used in the context of the invention may comprise one or more anionic non-associative thickening polymers chosen from:

    
    
        anionic polymers bearing sugar units,
        anionic polymers not bearing sugar units chosen from crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or mixtures thereof,
        and mixtures thereof.
    
    


For the purposes of the present invention, the term “non-associative polymer” means any polymer not containing in its structure a saturated or unsaturated hydrocarbon-based fatty chain comprising from 8 to 30 carbon atoms.
The anionic non-associative thickening polymer is in the dye composition, in the oxidizing composition or in both compositions simultaneously.
The anionic non-associative thickening polymer bearing sugar units may be chosen from:
I. natural gums of anionic nature such as those belonging to the following families:

    a) tree or shrub exudates, including:
    
        gum arabic (branched polymer of galactose, arabinose, rhamnose and glucuronic acid);
        ghatti gum (polymer derived from arabinose, galactose, mannose, xylose and glucuronic acid);
        karaya gum (polymer derived from galacturonic acid, galactose, rhamnose and glucuronic acid);
        gum tragacanth (or tragacanth) (polymer of galacturonic acid, galactose, fucose, xylose and arabinose);
    
    
    b) gums derived from algae, including:
    
        alginates (polymers of mannuronic acid and of glucuronic acid);
        carrageenans and furcellerans (polymers of galactose sulfate and of anhydrogalactose sulfate);
    
    
    c) microbial gums, including:
    
        xanthan gum (polymer of glucose, mannose acetate, mannose/pyruvic acid and glucuronic acid);
        gellan gum (polymer of partially acylated glucose, rhamnose and glucuronic acid);
    
    


II.—anionic cellulose derivatives
Among the anionic cellulose ethers, mention may be made of carboxyalkylcelluloses and salts thereof. Examples that may be mentioned include carboxymethylcelluloses, carboxymethylmethylcelluloses (for example Blanose 7M from the company Aqualon) and carboxymethylhydroxyethylcelluloses, and the sodium salts thereof.
III. anionic starch derivatives
These compounds are obtained from natural starches, which are macromolecules in the form of polymers consisting of elemental units that are anhydroglucose units. The number of these units and their assembly make it possible to distinguish amylose (linear polymer) and amylopectin (branched polymer). The relative proportions of amylose and of amylopectin, and their degree of polymerization, vary as a function of the plant origin of the starches.
The starch molecules used in the present invention may originate from a plant source such as cereals, tubers, roots, legumes and fruit. Thus, the starch(es) may originate from a plant source chosen from corn, pea, potato, sweet potato, banana, barley, wheat, rice, oat, sago, tapioca and sorghum. The starch is preferably derived from potato.
It is also possible to use the starch hydrolysates mentioned above.
Starches are generally in the form of a white powder, which is insoluble in cold water, whose elemental particle size ranges from 3 to 100 microns.
The anionic starches used in the invention are chemically modified via one or more of the following reactions: pregelatinization, oxidation, crosslinking, esterification, heat treatments, at least one of these reactions leading to the formation of anionic sites.
More particularly, these reactions may be performed in the following manner:

    
    
        pregelatinization by splitting the starch granules (for example drying and cooking in a drying drum);
        oxidation with strong oxidizing agents, leading to the introduction of carboxyl groups into the starch molecule and to depolymerization of the starch molecule (for example by treating an aqueous starch solution with sodium hypochlorite);
        crosslinking with functional agents capable of reacting with the hydroxyl groups of the starch molecules, which will thus bond together (for example with glyceryl and/or phosphate groups);
        esterification in alkaline medium for the grafting of functional groups, especially C1-C6 acyl (acetyl), C1-C6 hydroxyalkyl (hydroxyethyl or hydroxypropyl) or carboxyalkyl.
    
    


Monostarch phosphates (of the type Am—O—PO—(OX)2), distarch phosphates (of the type Am—O—PO—(OX)—O—Am) or even tristarch phosphates (of the type Am—O—PO—(O—Am)2) or mixtures thereof (Am meaning starch) may especially be obtained by crosslinking with phosphorus compounds.
X especially denotes alkali metals (for example sodium or potassium), alkaline-earth metals (for example calcium or magnesium), ammonium salts, amine salts, for instance those of monoethanolamine, diethanolamine, triethanolamine, 3-amino-1,2-propanediol, or ammonium salts derived from basic amino acids such as lysine, arginine, sarcosine, ornithine or citrulline.
The phosphorus compounds may be, for example, sodium tripolyphosphate, sodium orthophosphate, phosphorus oxychloride or sodium trimetaphosphate.
Starch phosphates, in particular hydroxypropyl starch phosphates, or compounds rich in starch phosphate and in particular in hydroxypropyl starch phosphate may thus be used, for instance the products sold under the references Prejel VA-70-T AGGL (gelatinized hydroxypropyl cassava distarch phosphate), Prejel TK1 (gelatinized cassava distarch phosphate) and Prejel 200 (gelatinized acetyl cassava distarch phosphate) by the company Avebe, or Structure Zea from National Starch (gelatinized hydroxypropyl corn distarch phosphate).
When the starches are chemically modified via an esterification reaction, carboxyalkyl starches may be obtained.
The carboxyalkyl starches are preferably carboxy(C1-C4)alkyl starches and salts thereof, and more particularly carboxymethyl starches and salts thereof.
The salts are especially salts of alkali metals or alkaline-earth metals such as Na, K 1⁄2, Li, NH4, or salts of a quaternary ammonium or of an organic amine such as monoethanolamine, diethanolamine or triethanolamine.
Carboxyalkyl starches are obtained by grafting carboxyalkyl groups onto one or more alcohol functions of starch, especially by reaction of starch and of sodium monochloroacetate in alkaline medium.
The carboxyalkyl groups are generally attached via an ether function, more particularly to carbon 1.
The degree of substitution preferably ranges from 0.1 to 1 and more particularly from 0.15 to 0.5. The degree of substitution is defined according to the present invention as being the mean number of hydroxyl groups substituted with an ester or ether group (in the present case ether for the carboxymethyl starches) per monosaccharide unit of the polysaccharide.
The carboxyalkyl starches preferably comprise units having the following formula:




X denotes a hydrogen atom, an alkali metal or alkaline-earth metal such as Na, K 1⁄2, Li or NH4, a quaternary ammonium or an organic amine. Preferably, X denotes an Na+ ion.
The carboxyalkyl starches that may be used according to the present invention are preferably non-pregelatinized carboxyalkyl starches.
The carboxyalkyl starches that may be used according to the present invention are preferably partially or totally crosslinked carboxyalkyl starches.
The carboxyalkyl starches that may be used according to the present invention are preferably sodium salts of carboxyalkyl starches, in particular a sodium salt of potato carboxymethyl starch, sold especially under the name Primojel by the company DMV International. More than 95% of the particles of this starch have a diameter of less than 100 microns and more particularly less than 65 microns.
The non-associative thickening polymers not bearing sugar units are chosen from crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or mixtures thereof.
A first family of non-associative thickening polymers that is suitable for use is represented by crosslinked acrylic acid homopolymers.
Among the homopolymers of this type, mention may be made of those crosslinked with an allyl alcohol ether of the sugar series, such as, for example, the products sold under the names Carbopol 980, 981, 954, 2984 and 5984 by the company Noveon or the products sold under the names Synthalen M and Synthalen K by the company 3 VSA.
The non-associative thickening polymers may also be crosslinked copolymers of (meth)acrylic acid and of C1-C4 alkyl(meth)acrylates such as the polymer sold under the name Aqua SF1 by the company Noveon or Aculyn 33 by the company Röhm & Haas.
The non-associative thickening polymers may also be crosslinked copolymers of (meth)acrylic acid and of acrylamide.
The non-associative thickening polymers may be chosen from crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and the crosslinked acrylamide copolymers thereof.
As regards these homopolymers and copolymers, which may be partially or totally neutralized, mention may be made of polymers comprising from 90% to 99.9% by weight, relative to the total weight of the polymer, of units of formula (j) below:




in which X+ denotes a cation or a mixture of cations, or a proton.

More particularly, the cations are chosen from alkali metals (for instance sodium or potassium), ammonium ions optionally substituted with 1 to 3 alkyl radicals, which may be identical or different, containing from 1 to 6 carbon atoms, optionally bearing at least one hydroxyl radical, cations derived from N-methylglucamine or from basic amino acids, for instance arginine and lysine. Preferably, the cation is an ammonium or sodium ion.
Moreover, the polymer comprises from 0.01% to 10% by weight, relative to the total weight of the polymer, of crosslinking units derived from at least one monomer containing at least two ethylenic unsaturations (carbon-carbon double bond).
The crosslinking monomers containing at least two ethylenic unsaturations are chosen, for example, from diallyl ether, triallyl cyanurate, diallyl maleate, allyl(meth)acrylate, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane, tetra- or diethylene glycol di(meth)acrylate, triallylamine, tetraallylethylenediamine, trimethylolpropane diallyl ether, trimethylolpropane triacrylate, methylenebis(meth)acrylamide or divinylbenzene, allylic ethers of alcohols of the sugar series, or other allylic or vinyl ethers of polyfunctional alcohols, and also allylic esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.
For further details regarding these polymers, reference may be made to document EP 815 828.
Among the partially or totally neutralized crosslinked copolymers of 2-acrylamido-2-methylpropanesulfonic acid and of acrylamide, mention may be made in particular of the product described in Example 1 of document EP 503 853, and reference may be made to said document as regards these polymers.
These polymers should be considered as anionic.
Preferably, the anionic non-associative thickening polymers used in the process according to the invention are crosslinked acrylic or methacrylic acid homopolymers or copolymers.
By way of example, mention may be made of the commercial product Carbopol 980 Polymer sold by the company Lubrizol.
The anionic non-associative thickening polymer(s) preferably represent from 0.01% to 40% by weight and better still from 0.1% to 10% by weight relative to the total weight of the mixture.
Dye Composition
Dyes
The dye composition used in the process according to the invention comprises at least one oxidation dye precursor.
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-toluenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis((β-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis((β-hydroxyethyl) amino-2-methylaniline, 4-N,N-bis((β-hydroxyethyl)amino-2-chloroaniline, 2-6-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(β-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N-ethyl-N-(βhydroxyethyl)-para-phenylenediamine, N-((β,y-dihydroxypropyl)-para-phenylenediamine, N-(4′-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2-β-acetylaminoethyloxy-para-phenylenediamine, N-(β-methoxyethyl)-para-phenylenediamine, 4-aminophenylpyrrolidine, 2-thienyl-para-phenylenediamine, 2-β-hydroxyethylamino-5-aminotoluene and 3-hydroxy-1-(4′-aminophenyl) pyrrolidine, and the addition salts thereof with an acid.
Among the para-phenylenediamines mentioned above, para-phenylenediamine, para-toluenediamine, 2-isopropyl-para-phenylenediamine, 2-β-hydroxyethyl-para-phenylenediamine, 2-β-hydroxyethyloxy-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-paraphenylenediamine, N,N-bis((β-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine and 2-β-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-(β-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 the addition salts thereof described, for example, in patent application FR 2 801 308. Mention may be made, by way of example, of pyrazolo[1,5-a]pyrid-3-ylamine, 2-(acetylamino)pyrazolo[1,5-a]pyrid-3-ylamine, 2-(morpholin-4-yl)pyrazolo[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-yl)pyrazolo[1,5-a]pyrid-3-ylamine, pyrazolo[1,5-a]pyridine-3,5-diamine, 5-(morpholin-4-yl)pyrazolo[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, 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 patents DE 2359399, JP 88-169571, JP 05-63124 and EP 0 770 375 or patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine and addition salts thereof, and tautomeric forms thereof, when a tautomeric equilibrium exists.
Among the pyrazole derivatives that may be mentioned are the compounds described in 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-(β-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-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4,5-diamino-1-(β-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-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3-methyl-1-isopropylpyrazole, 4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole, 3,4,5-triamino-pyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole, 3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and addition salts thereof. Use may also be made of 4,5-diamino-1-(β-methoxyethyl)pyrazole.
A 4,5-diaminopyrazole will preferably be used, and even more preferentially 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or a salt thereof.
Pyrazole derivatives that may also be mentioned include diamino-N,N-dihydropyrazolopyrazolones 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-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-ethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-isopropylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-(pyrrolidin-1-yl)-6,7-dihydro-1H,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-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2-amino-3-dimethylamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one, 2,3-diamino-5,6,7,8-tetrahydro-1H,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-1H,5H-pyrazolo[1,2-a]pyrazol-1-one. 2,3-Diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a salt thereof will preferably be used.
Use will preferably be made, as heterocyclic bases, of 4,5-diamino-1-(β-hydroxyethyl)pyrazole and/or 2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and/or a salt thereof.
Among the couplers that may be used in the composition used in the process according to the invention, mention may be made especially of meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based couplers, heterocyclic couplers, for instance indole derivatives, indoline derivatives, sesamol and derivatives thereof, pyridine derivatives, pyrazolotriazole derivatives, pyrazolones, indazoles, benzimidazoles, benzothiazoles, benzoxazoles, 1,3-benzodioxoles and quinolines, and the addition salts of these compounds with an acid.
These couplers are more particularly chosen from 2,4-diamino-1-(β-hydroxyethyloxy)benzene, 2-methyl-5-aminophenol, 5-N-(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxybenzene, 2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)propane, sesamol, 1-amino-2-methoxy-4,5-methylenedioxybenzene, α-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine, 3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole and 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 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 dye 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 dye composition.
The dye composition used in the process according to the invention may contain synthetic or natural, cationic or nonionic, 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; phthalocyanin 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 relative to the total weight of the dye composition.
Alkaline Agent
According to a preferred variant of the invention, the dye composition comprises at least one alkaline agent.
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 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.
Mention may be made, as hybrid compounds, of the salts of the abovementioned amines with acids, such as carbonic acid or hydrochloric acid.
The organic alkaline agent(s) are chosen, for example, from alkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines, amino acids and the compounds having the following formula:




in which W is a C1-C6 alkylene residue optionally substituted with a hydroxyl group or a C1-C6 alkyl radical; Rx, Ry, Rz and Rt, which may be identical or different, represent a hydrogen atom or a C1-C6 alkyl, C1-C6 hydroxyalkyl or C1-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 C1-C8 alkyl groups bearing one or more hydroxyl radicals.
Alkanolamines such as monoalkanolamines, dialkanolamines or trialkanolamines comprising from one to three identical or different C1-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 more particularly chosen from carboxylic acid, sulfonic acid, phosphonic acid and phosphoric acid functions. The amino acids can be in the neutral or ionic form.
Mention may in particular be made, as amino acids which can be used in the present invention, 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 the following formula:




in which R denotes a group chosen from:




The compounds corresponding to the above formula 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 can 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 balenine.
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 guanidine carbonate or monoethanolamine hydrochloride as hybrid compounds.
More particularly, the dye composition used in the process of the invention contains, as alkaline agent, aqueous ammonia and/or at least one alkanolamine and/or at least one basic amino acid, more advantageously aqueous ammonia and/or at least one alkanolamine. Preferably, the alkaline agent is chosen from aqueous ammonia and monoethanolamine, or a mixture thereof.
Advantageously, the dye composition 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 the said dye composition. It should be noted that this content is expressed as NH3 in the case where the alkaline agent is aqueous ammonia.
Surfactants
The dye composition may also comprise one or more surfactants.
In particular, the surfactant(s) are chosen from anionic, amphoteric, zwitterionic, cationic and nonionic surfactants, and preferentially nonionic surfactants.
The term “anionic surfactant” means a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are preferably chosen from the groups —C(O)OH, —C(O)O—, —SO3H, —S(O)2O—, —OS(O)2OH, —OS(O)2O—, —P(O)OH2, —P(O)2O—, —P(O)O2—, —P(OH)2, ═P(O)OH, —P(OH)O—, ═P(O)O—, ═POH and ═PO—, the anionic parts comprising a cationic counterion such as an alkali metal, an alkaline-earth metal or an ammonium.
As examples of anionic surfactants that may be used in the dye composition according to the invention, mention may be made of alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylarylpolyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamidesulfonates, alkylarylsulfonates, α-olefin sulfonates, paraffin sulfonates, alkylsulfosuccinates, alkylether sulfosuccinates, alkylamide sulfosuccinates, alkylsulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N-acyltaurates, salts of alkyl monoesters of polyglycoside-polycarboxylic acids, acyllactylates, 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 40 carbon atoms and the aryl group denoting a phenyl group.
These compounds can be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.
The salts of C6-C24 alkyl monoesters of polyglycoside-polycarboxylic acids can be chosen from C6-C24 alkyl polyglycoside-citrates, C6-C24 alkyl polyglycoside-tartrates and C6-C24 alkyl polyglycoside-sulfosuccinates.
When the anionic surfactant(s) are in salt form, they may be chosen from alkali metal salts such as sodium or potassium salt and preferably sodium salt, ammonium salts, amine salts and in particular amino alcohol salts or alkaline-earth metal salts such as magnesium salts.
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 sodium or magnesium salts, are preferably used.
Use is preferably made, among the anionic surfactants mentioned, of (C6-C24)alkyl sulfates, (C6-C24)alkyl ether sulfates comprising from 2 to 50 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds.
In particular, it is preferable to use (C12-C20)alkyl sulfates, (C12-C20)alkyl ether sulfates comprising from 2 to 20 ethylene oxide units, in particular in the form of alkali metal, ammonium, amino alcohol and alkaline-earth metal salts, or a mixture of these compounds. Better still, it is preferred to use sodium lauryl ether sulfate containing 2.2 mol of ethylene oxide.
The amphoteric or zwitterionic surfactant(s), which are preferably (a) non-silicone surfactant(s), which can be used in the present invention may in particular be derivatives of optionally quaternized secondary or tertiary aliphatic amines, in which derivatives the aliphatic group is a linear or branched chain comprising from 8 to 22 carbon atoms, the said amine derivatives comprising at least one anionic group, such as, for example, a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may be made in particular of (C8-C20)alkylbetaines, sulfobetaines, (C8-C20)alkylamido(C3-C8)alkylbetaines and (C8-C20)alkylamido(C6-C8)alkylsulfobetaines.
Among the optionally quaternized secondary or tertiary aliphatic amine derivatives that may be used, as defined above, mention may also be made of the compounds having the respective structures (B1) and (B2) below:

Ra—C(O)—NH—CH2—CH2—N+(Rb)(Rc)—CH2C(O)O−, M+, X−  (B1)

in which formula:

    
    
        Ra represents a C10-C30 alkyl or alkenyl group derived from an acid Ra—COOH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group;
        Rb represents a β-hydroxyethyl group; and
        Rc represents a carboxymethyl group;
        M+ represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine; and
        X− represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (C1-C4)alkyl sulfates, (C1-C4)alkyl- or (C1-C4)alkylarylsulfonates, in particular methyl sulfate and ethyl sulfate; or alternatively M+ and X− are absent;

Ra′—C(O)—NH—CH2—CH2—N(B)(B′)   (B2)

    
    


in which formula:

    
    
        B represents the group —CH2—CH2—O—X′;
        B′ represents the group —(CH2)zY′, with z=1 or 2;
        X′ represents the group —CH2—C(O)OH, —CH2—C(O)OZ′, —CH2—CH2—C(O)OH, —CH2—CH2—C(O)OZ′, or a hydrogen atom;
        Y′ represents the group —C(O)OH, —C(O)OZ′, —CH2—CH(OH)—SO3H or the group —CH2—CH(OH)—SO3—Z′;
        Z′ represents a cationic counterion 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 C10-C30 alkyl or alkenyl group of an acid Ra′—C(O)OH preferably present in coconut oil or in hydrolysed linseed oil, an alkyl group, especially of C17 and its iso form, or an unsaturated C17 group.
    
    


These compounds of formula (B1) or (B2) 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.
Use may also be made of compounds of formula (B′2):

Ra′′—NH—CH(Y′′)—(CH2)n-C(O)—NH—(CH2)n′-N(Rd)(Re)   (B′2)

in which formula:

    
    
        Y′′ represents the group —C(O)OH, —C(O)OZ′′, —CH2—CH(OH)—SO3H or the group —CH2—CH(OH)—SO3—Z′′;
        Rd and Re, independently of each other, represent a C1-C4 alkyl or hydroxyalkyl radical;
        Z′′ represents a cationic counterion 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 C10-C30 alkyl or alkenyl group of an acid Ra′′C(O)OH preferably present in coconut oil or in hydrolysed linseed oil.
        n and n′ denote, independently of each other, an integer ranging from 1 to 3.
    
    


Among the compounds of formula (B′2), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by the company Chimex under the name Chimexane HB.
Among the amphoteric or zwitterionic surfactants mentioned above, use is preferably made of (C8-C20)alkylbetaines such as cocoylbetaine, (C8-C20)alkylamido(C3-C8)alkylbetaines such as cocoylamidopropylbetaine, and the compounds of formula (B′2) such as the sodium salt of diethylaminopropyl laurylaminosuccinamate (INCI name: sodium diethylaminopropyl cocoaspartamide), and mixtures thereof.
More preferentially, the amphoteric or zwitterionic surfactant(s) are chosen from cocamidopropylbetaine, cocoylbetaine and the sodium salt of diethylaminopropyl laurylaminosuccinamate, and mixtures thereof.
The cationic surfactant(s) that may be used in the dye composition according to the invention comprise, for example, salts of optionally polyoxyalkylenated primary, secondary or tertiary fatty amines, quaternary ammonium salts, and mixtures thereof.
Examples of quaternary ammonium salts that may especially be mentioned include:

    
    
        those corresponding to the general formula (B3) below:
    
    






in which formula:

    
    
        R8 to R11, which may be identical or different, represent a linear or branched aliphatic group comprising from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, it being understood that at least one of the groups R8 to R11 comprises from 8 to 30 carbon atoms and preferably from 12 to 24 carbon atoms; and
        X− represents an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (C1-C4)alkyl sulfates, (C1-C4)alkyl or (C1-C4)alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate.
    
    


The aliphatic groups of R8 to R11 may also comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens.
The aliphatic groups of R8 to R11 are chosen, for example, from C1-C30 alkyl, C1-C30 alkoxy, polyoxy(C2-C6)alkylene, C1-C30 alkylamide, (C12-C22)alkylamido(C2-C6)alkyl, (C12-C22)alkyl acetate and C1-C30 hydroxyalkyl groups, X− is an anionic counterion chosen from the group of halides, phosphates, acetates, lactates, (C1-C4)alkyl sulfates and (C1-C4)alkyl- or (C1-C4)alkylarylsulfonates.
Among the quaternary ammonium salts of formula (B3), preference is given firstly to tetraalkylammonium chlorides, for instance dialkyldimethylammonium or alkyltrimethylammonium chlorides in which the alkyl group comprises approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride, benzyldimethylstearylammonium chloride, or else, secondly, distearoylethylhydroxyethylmethylammonium methosulfate, dipalmitoylethylhydroxyethylammonium methosulfate or distearoylethylhydroxyethylammonium methosulfate, or else, lastly, palmitylamidopropyltrimethylammonium chloride or stearamidopropyldimethyl(myristyl acetate)ammonium chloride, sold under the name Ceraphyl® 70 by the company Van Dyk;

    
    
        quaternary ammonium salts of imidazoline, for instance those of formula (B4) below:
    
    






in which formula:

    
    
        R12 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, for example fatty acid derivatives of tallow;
        R13 represents a hydrogen atom, a C1-C4 alkyl group or an alkenyl or alkyl group comprising from 8 to 30 carbon atoms;
        R14 represents a C1-C4 alkyl group;
        R15 represents a hydrogen atom or a C1-C4 alkyl group;
        X− represents an organic or inorganic anionic counterion, such as that chosen from halides, phosphates, acetates, lactates, (C1-C4)alkyl sulfates, (C1-C4)alkyl or (C1-C4)alkylaryl sulfonates.
    
    


R12 and R13 preferably denote a mixture of alkyl or alkenyl groups containing 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 (B5) below:
    
    






in which formula:

    
    
        R16 denotes an alkyl group comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms;
        R17 is chosen from hydrogen, an alkyl group comprising from 1 to 4 carbon atoms or a group —(CH2)3—N+(R16a)(R17a)(R18a), X−;
        R16a, R17a, R18a, R18, R19, R20 and R21, which may be identical or different, are chosen from hydrogen and an alkyl group comprising from 1 to 4 carbon atoms; and
        X−, which may be identical or different, represent an organic or inorganic anionic counterion, such as that chosen from halides, acetates, phosphates, nitrates, (C1-C4)alkyl sulfates, (C1-C4)alkyl or (C1-C4)alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate.
    
    


Such compounds are, for example, Finquat CT-P, sold by the company Finetex (Quaternium 89), and Finquat CT, sold by the company Finetex (Quaternium 75);

    
    
        quaternary ammonium salts containing one or more ester functions, such as those of formula (B6) below:
    
    






in which formula:

    
    
        R22 is chosen from C1-C6 alkyl groups and C1-C6 hydroxyalkyl or C1-C6 dihydroxyalkyl groups,
        R23 is chosen from:
        
            the group
        
        
    
    






    
    
        
        
            linear or branched, saturated or unsaturated C1-C22 hydrocarbon-based groups R27,
            a hydrogen atom,
        
        
        R25 is chosen from:
        
            the group
        
        
    
    






    
    
        
        
            linear or branched, saturated or unsaturated C1-C6 hydrocarbon-based groups R29,
            a hydrogen atom,
        
        
        R24, R26 and R28, which are identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon groups;
        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, with 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− represents an organic or inorganic anionic counterion, with the proviso that the sum x +y +z equals 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 an R27 hydrocarbon-based group, it may be long and may contain from 12 to 22 carbon atoms, or may be short and may contain from 1 to 3 carbon atoms.
When R25 is an R29 hydrocarbon-based group, it preferably contains 1 to 3 carbon atoms.
Advantageously, R24, R26 and R28, which are identical or different, are selected 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.
y is advantageously equal to 1.
Preferably, r, s and t, which may be identical or different, equal 2 or 3, and even more particularly are equal to 2.
The anionic counterion X− is preferably a halide, such as chloride, bromide or iodide; a (C1-C4)alkyl sulfate or a (C1-C4)alkyl- or (C1-C4)alkylarylsulfonate. However, it is possible to use 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.
The anionic counterion X− is even more particularly chloride, methyl sulfate or ethyl sulfate.
Use is made more particularly in the dye composition according to the invention of the ammonium salts of formula (B6) 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:
        
            the group
        
        
    
    






    
    
        
        
            methyl, ethyl or C14-C22 hydrocarbon-based groups,
            a hydrogen atom,
        
        
        R25 is chosen from:
        
            the group
        
        
    
    






    
    
        
        
            a hydrogen atom,
        
        
        R24, R26 and R28, 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.
    
    


Advantageously, the hydrocarbon-based radicals are linear.
Among the compounds of formula (B6), examples that may be mentioned include salts, especially the chloride or methyl sulfate, of diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium or monoacyloxyethylhydroxyethyldimethylammonium, and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and originate 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 fatty acids or with fatty acid mixtures of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by a quaternization by means of an alkylating agent such as an alkyl halide, preferably 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 dye 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 U.S. Pat. No. 4,874,554 and U.S. Pat. No. 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 cationic surfactants that may be present in the dye composition according to the invention, it is more particularly preferred to choose cetyltrimethylammonium, behenyltrimethylammonium and dipalmitoylethyl-hydroxyethylmethylammonium salts, and mixtures thereof, and more particularly behenyltrimethylammonium chloride, cetyltrimethylammonium chloride, and dipalmitoylethylhydroxyethylammonium methosulfate, and mixtures thereof.
Examples of nonionic surfactants that may be used in the dye composition used according to the invention are described, for example, in the Handbook of Surfactants by M. R. Porter, published by Blackie & Son (Glasgow and London), 1991, pp. 116-178. They are especially chosen from alcohols, a-diols and (C1-C20)alkylphenols, these compounds being etherified with ethoxylated, propoxylated and/or glycerolated groups, and containing at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, it being possible for the number of ethylene oxide and/or propylene oxide groups to range especially from 1 to 100, more particularly from 2 to 50 and even more particularly from 2 to 30, and for the number of glycerol groups to range especially from 1 to 30.

    
    
        Mention may also be made of copolymers of ethylene oxide and propylene oxide, optionally oxyethylenated fatty acid esters of sorbitan, fatty acid esters of sucrose, oxyalkylenated fatty acid esters, optionally oxyalkylenated alkyl polyglycosides, alkyl glucoside esters, derivatives of N-alkyl glucamine and of N-acyl methylglucamine, aldobionamides and amine oxides.
    
    


The nonionic surfactants are more particularly chosen from oxyalkylenated or glycerolated nonionic surfactants. The oxyalkylene units are more particularly oxyethylene or oxypropylene units, or a combination thereof, preferably oxyethylene units.
Examples of oxyalkylenated or glycerolated nonionic surfactants that may be mentioned include:

    
    
        oxyalkylenated (C8-C24)alkylphenols;
        saturated or unsaturated, linear or branched, oxyalkylenated or glycerolated 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;
        oxyethylenated esters of saturated or unsaturated, linear or branched C8-C30 acids and of sorbitol;
        saturated or unsaturated oxyethylenated vegetable oils;
        condensates of ethylene oxide and/or of propylene oxide, inter alia, alone or as mixtures;
        oxyethylenated and/or oxypropylenated silicones.
    
    


The surfactants contain a number of moles of ethylene oxide and/or of propylene oxide ranging from 1 to 100, preferably from 2 to 50 and preferably between 2 and 30. Advantageously, the nonionic surfactants do not comprise any oxypropylene units.
In accordance with a preferred embodiment of the invention, the oxyalkylenated nonionic surfactants are chosen from oxyethylenated C8-C30 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and more particularly from 2 to 30 mol of ethylene oxide; oxyethylenated 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 glycerolated nonionic surfactants, glycerolated C8-C40 alcohols are preferably used.
Examples of compounds of this type that may be mentioned include lauryl alcohol containing 4 mol of glycerol (INCI 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.
Among the glycerolated alcohols, it is more particularly preferred to use the C8/C10 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.
Preferably, the surfactant(s) are chosen from nonionic, anionic and amphoteric surfactants. More particularly, the additional surfactant(s) present in the composition are chosen from nonionic surfactants.
Preferably, the surfactant(s), when they are present, are chosen from oxyalkylenated, particularly oxyethylenated or oxypropylenated, nonionic surfactants, or a combination thereof, more particularly oxyethylenated; glycerolated, or mixtures thereof.
Even more preferentially, the nonionic surfactants are chosen from oxyethylenated sorbitol esters, oxyethylenated fatty alcohols and glycerolated fatty alcohols, and mixtures thereof.
In the dye composition, the amount of surfactant(s), when they are present, preferably ranges from 0.1% to 50% by weight and better still from 0.5% to 20% by weight relative to the total weight of the said composition.
Medium
The medium of the dye composition according to the invention is advantageously an aqueous medium. It may also comprise 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 ethyl alcohol, isopropyl alcohol, 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 C1-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 dye 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 dye composition.
The pH of the dye composition, if it is aqueous, is generally between 3 and 12 and preferably between 5 and 11. Preferentially between 7 and 11, 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.
Fatty Substances
The dye composition may optionally comprise one or more fatty substances.
The term “fatty substance” means an organic compound that is insoluble in water at ordinary temperature (25° C.) and at atmospheric pressure (760 mmHg) (solubility of less than 5%, preferably less than 1% and even more preferentially less than 0.1%). They exhibit, in their structure, at least one hydrocarbon chain comprising at least 6 carbon atoms or a sequence of at least two siloxane groups. In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, dichloromethane, carbon tetrachloride, ethanol, benzene, toluene, tetrahydrofuran (THF), liquid petroleum jelly or decamethylcyclopentasiloxane.
The fatty substances of the invention do not contain any salified or unsalified carboxylic acid groups (COOH or COO—).
Particularly, the fatty substances of the invention are neither (poly)oxyalkylenated nor (poly)glycerolated.
The term “oil” means a “fatty substance” that is liquid at room temperature (25° C.) and at atmospheric pressure (760 mmHg).
The term “non-silicone oil” means an oil not containing any silicon atoms (Si) and the term “silicone oil” means an oil containing at least one silicon atom.
More particularly, the fatty substances are chosen from C6-C16 hydrocarbons, hydrocarbons containing more than 16 carbon atoms, non-silicone oils of animal origin, plant oils of triglyceride type, synthetic triglycerides, fluoro oils, fatty alcohols, fatty acid and/or fatty alcohol esters other than triglycerides and plant waxes, non-silicone waxes and silicones, and mixtures thereof.
It is recalled that the fatty alcohols, esters and acids more particularly have at least one linear or branched, saturated or unsaturated hydrocarbon-based group comprising 6 to 30 and better still from 8 to 30 carbon atoms, which is optionally substituted, in particular with one or more hydroxyl groups (in particular 1 to 4). If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
As regards the C6-C16 hydrocarbons, they are linear, branched or optionally cyclic, and are preferably alkanes. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane.
A hydrocarbon-based oil of animal origin that may be mentioned is perhydrosqualene.
The triglyceride oils of plant or synthetic origin are preferably chosen from liquid fatty acid triglycerides containing from 6 to 30 carbon atoms, for instance heptanoic or octanoic acid triglycerides, or alternatively, for example, sunflower oil, corn oil, soybean oil, marrow oil, grapeseed oil, sesame seed oil, hazelnut oil, apricot oil, macadamia oil, arara oil, castor oil, avocado oil, caprylic/capric acid triglycerides, for instance those sold by the company Stéarineries Dubois or those sold under the names Miglyol® 810, 812 and 818 by the company Dynamit Nobel, jojoba oil and shea butter oil.
The linear or branched hydrocarbons of mineral or synthetic origin having more than 16 carbon atoms are preferably chosen from liquid paraffins, petroleum jelly, liquid petroleum jelly, polydecenes or hydrogenated polyisobutene, such as Parleam®.
As regards the C6-C16 alkanes, they are linear or branched, and possibly cyclic. Examples that may be mentioned include hexane, dodecane and isoparaffins such as isohexadecane and isodecane.
As oils of animal, vegetable, mineral or synthetic origin that may be used in the composition of the invention, examples that may be mentioned include: the fluoro oils that may be chosen from perfluoromethylcyclopentane and perfluoro-1,3-dimethylcyclohexane, sold under the names Flutec® PC1 and Flutec® PC3 by the company BNFL Fluorochemicals; perfluoro-1,2-dimethylcyclobutane; perfluoroalkanes such as dodecafluoropentane and tetradecafluorohexane, sold under the names PF 5050® and PF 5060® by the company 3M, or bromoperfluorooctyl sold under the name Foralkyl® by the company Atochem; nonafluoromethoxybutane and nonafluoroethoxyisobutane; perfluoromorpholine derivatives such as 4-trifluoromethyl perfluoromorpholine sold under the name PF 5052® by the company 3M.
The fatty alcohols which are suitable for the implementation of the invention are more particularly chosen from saturated or unsaturated, linear or branched alcohols comprising from 6 to 30 carbon atoms and preferably from 8 to 30 carbon atoms. Mention may be made, for example, of cetyl alcohol, stearyl alcohol and the mixture thereof (cetearyl alcohol), octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleyl alcohol or linoleyl alcohol.
As regards the esters of a fatty acid and/or of fatty alcohols, which are advantageously different from the triglycerides mentioned previously, mention may be made especially of esters of saturated or unsaturated, linear or branched C1-C26 aliphatic monoacids or polyacids and of saturated or unsaturated, linear or branched C1-C26 aliphatic monoalcohols or polyalcohols, the total carbon number of the esters being greater than or equal to 6 and more advantageously greater than or equal to 10.
Among the monoesters, mention may be made of dihydroabietyl behenate; octyldodecyl behenate; isocetyl behenate; cetyl lactate; C12-C15 alkyl lactate; isostearyl lactate; lauryl lactate; linoleyl lactate; oleyl lactate; (iso)stearyl octanoate; isocetyl octanoate; octyl octanoate; cetyl octanoate; decyl oleate; isocetyl isostearate; isocetyl laurate; isocetyl stearate; isodecyl octanoate; isodecyl oleate; isononyl isononanoate; isostearyl palmitate; methylacetyl ricinoleate; myristyl stearate; octyl isononanoate; 2-ethylhexyl isononanoate; octyl palmitate; octyl pelargonate; octyl stearate; octyldodecyl erucate; oleyl erucate; ethyl and isopropyl palmitates, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl, 2-octyldodecyl, myristyl or stearyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate.
Still within the context of this variant, esters of C4-C22 dicarboxylic or tricarboxylic acids and of C1-C22 alcohols and esters of mono-, di- or tricarboxylic acids and of C2-C26 di-, tri-, tetra- or pentahydroxy alcohols may also be used.
Mention may be made especially of: diethyl sebacate; diisopropyl sebacate; diisopropyl adipate; di-n-propyl adipate; dioctyl adipate; diisostearyl adipate; dioctyl maleate; glyceryl undecylenate; octyldodecyl stearoyl stearate; pentaerythrityl monoricinoleate; pentaerythrityl tetraisononanoate; pentaerythrityl tetrapelargonate; pentaerythrityl tetraisostearate; pentaerythrityl tetraoctanoate; propylene glycol dicaprylate; propylene glycol dicaprate; tridecyl erucate; triisopropyl citrate; triisostearyl citrate; glyceryl trilactate; glyceryl trioctanoate; trioctyldodecyl citrate; trioleyl citrate; propylene glycol dioctanoate; neopentyl glycol diheptanoate; diethylene glycol diisononanoate; and polyethylene glycol distearates.
Among the esters mentioned above, it is preferred to use ethyl, isopropyl, myristyl, cetyl or stearyl palmitate, 2-ethylhexyl palmitate, 2-octyldecyl palmitate, alkyl myristates such as isopropyl, butyl, cetyl or 2-octyldodecyl myristate, hexyl stearate, butyl stearate, isobutyl stearate; dioctyl malate, hexyl laurate, 2-hexyldecyl laurate, isononyl isononanoate or cetyl octanoate.
The dye composition may also comprise, as fatty ester, sugar esters and diesters of C6-C30 and preferably C12-C22 fatty acids. It is recalled that the term “sugar” means oxygen-bearing hydrocarbon-based compounds which have several alcohol functions, with or without aldehyde or ketone functions, and which comprise at least 4 carbon atoms. These sugars can be monosaccharides, oligosaccharides or polysaccharides.
Mention may be made, as suitable sugars, for example, of sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose and lactose, and derivatives thereof, in particular alkyl derivatives, such as methyl derivatives, for instance methylglucose.
The sugar esters of fatty acids may be chosen in particular from the group comprising the esters or mixtures of esters of sugars described previously and of linear or branched, saturated or unsaturated C6-C30 and preferably C12-C22 fatty acids. If they are unsaturated, these compounds may comprise one to three conjugated or unconjugated carbon-carbon double bonds.
The esters according to this variant may also be chosen from mono-, di-, tri- and tetraesters, polyesters, and mixtures thereof.
These esters can, for example, be oleates, laurates, palmitates, myristates, behenates, cocoates, stearates, linoleates, linolenates, caprates, arachidonates or mixtures thereof, such as, in particular, oleate/palmitate, oleate/stearate or palmitate/stearate mixed esters.
More particularly, use is made of monoesters and diesters and in particular mono- or di-oleate, -stearate, -behenate, -oleate/palmitate, -linoleate, -linolenate or -oleate/stearate of sucrose, of glucose or of methylglucose.
An example that may be mentioned is the product sold under the name Glucate® DO by the company Amerchol, which is a methylglucose dioleate.
Examples of esters or mixtures of esters of sugar and of fatty acid that may also be mentioned include:

    
    
        the products sold under the names F160, F140, F110, F90, F70 and SL40 by the company Crodesta, respectively denoting sucrose palmitostearates formed from 73% monoester and 27% diester and triester, from 61% monoester and 39% diester, triester and tetraester, from 52% monoester and 48% diester, triester and tetraester, from 45% monoester and 55% diester, triester and tetraester, from 39% monoester and 61% diester, triester and tetraester, and sucrose monolaurate;
        the products sold under the name Ryoto Sugar Esters, for example, referenced B370 and corresponding to sucrose behenate formed from 20% monoester and 80% diester-triester-polyester;
        the sucrose mono-di-palmito-stearate sold by the company Goldschmidt under the name Tegosoft® PSE.
    
    


The non-silicone wax(es) are chosen in particular from carnauba wax, candelilla wax, esparto wax, paraffin wax, ozokerite, vegetable waxes, such as olive tree wax, rice wax, hydrogenated jojoba wax or absolute flower waxes, such as the blackcurrant blossom essential wax sold by Bertin (France), or animal waxes, such as beeswaxes or modified beeswaxes (cerabellina); other waxes or waxy starting materials which can be used according to the invention are in particular marine waxes, such as that sold by Sophim under the reference M82, polyethylene waxes or polyolefin waxes in general.
The silicones that may be used in the dye composition of the present invention are volatile or non-volatile, cyclic, linear or branched silicones, which are unmodified or modified with organic groups, having a viscosity from 5×10−6 to 2.5 m2/s at 25° C., and preferably 1×10−5 to 1 m2/s.
The silicones that may be used in accordance with the invention may be in the form of oils, waxes, resins or gums.
Preferably, the silicone is chosen from polydialkylsiloxanes, especially polydimethylsiloxanes (PDMS), and organomodified polysiloxanes comprising at least one functional group chosen from amino groups and alkoxy groups.
Organopolysiloxanes are defined in greater detail in Walter Noll's Chemistry and Technology of Silicones (1968), Academic Press. They may be volatile or non-volatile.
When they are volatile, the silicones are more particularly chosen from those having a boiling point of between 60° C. and 260° C., and more particularly still from:
(i) cyclic polydialkylsiloxanes containing from 3 to 7 and preferably from 4 to 5 silicon atoms. These are, for example, octamethylcyclotetrasiloxane sold in particular under the name Volatile Silicone° 7207 by Union Carbide or Silbione® 70045 V2 by Rhodia, decamethylcyclopentasiloxane sold under the name Volatile Silicone° 7158 by Union Carbide, and Silbione® 70045 V5 by Rhodia, and mixtures thereof.
Mention may also be made of cyclocopolymers of the dimethylsiloxane/methylalkylsiloxane type, such as Volatile Silicone® FZ 3109 sold by the company Union Carbide, of formula:




Mention may also be made of mixtures of cyclic polydialkylsiloxanes with organosilicon compounds, such as the mixture of octamethylcyclotetrasiloxane and tetra(trimethylsilyl)pentaerythritol (50/50) and the mixture of octamethylcyclotetrasiloxane and oxy-1,1′-bis(2,2,2′,2′,3,3′-hexatrimethylsilyloxy)neopentane;
(ii) linear volatile polydialkylsiloxanes containing 2 to 9 silicon atoms and having a viscosity of less than or equal to 5×10−6 m2/s at 25° C. An example is decamethyltetrasiloxane sold in particular under the name SH 200 by the company Toray Silicone. Silicones belonging to this category are also described in the article published in Cosmetics and Toiletries, Vol. 91, Jan. 76, pp. 27-32, Todd & Byers, Volatile Silicone Fluids for Cosmetics. 
Use is preferably made of non-volatile polydialkylsiloxanes, polydialkylsiloxane gums and resins, polyorganosiloxanes modified with the organofunctional groups above, and mixtures thereof.
These silicones are more particularly chosen from polydialkylsiloxanes, among which mention may be made mainly of polydimethylsiloxanes having trimethylsilyl end groups. The viscosity of the silicones is measured at 25° C. according to ASTM standard 445 Appendix C.
Mention may be made, among these polydialkylsiloxanes, without implied limitation, of the following commercial products:

    
    
        the Silbione® oils of the 47 and 70 047 series or the Mirasil® oils sold by Rhodia, such as, for example, the oil 70 047 V 500 000;
        the oils of the Mirasil® series sold by Rhodia;
        the oils of the 200 series from the company Dow Corning, such as DC200 with a viscosity of 60 000 mm2/s;
        the Viscasil® oils from General Electric and certain oils of the SF series (SF 96, SF 18) from General Electric.
    
    


Mention may also be made of polydimethylsiloxanes bearing dimethylsilanol end groups known under the name dimethiconol (CTFA), such as the oils of series 48 from the company Rhodia.
In this category of polydialkylsiloxanes, mention may also be made of the products sold under the names Abil Wax® 9800 and 9801 by the company Goldschmidt, which are polydi(C1-C20)alkylsiloxanes.
The silicone gums that may be used in accordance with the invention are in particular polydialkylsiloxanes and preferably polydimethylsiloxanes with high number-average molecular weights of between 200 000 and 1 000 000, used alone or as a mixture in a solvent. This solvent can be chosen from volatile silicones, polydimethylsiloxane (PDMS) oils, polyphenylmethylsiloxane (PPMS) oils, isoparaffins, polyisobutylenes, methylene chloride, pentane, dodecane, tridecane or their mixtures.
Products which can be used more particularly in accordance with the invention are mixtures such as:

    
    
        the mixtures formed from a polydimethylsiloxane hydroxylated at the chain end, or dimethiconol (CTFA), and from a cyclic polydimethylsiloxane, also known as cyclomethicone (CTFA), such as the product Q2 1401 sold by Dow Corning;
        the mixtures of a polydimethylsiloxane gum and of a cyclic silicone, such as the product SF 1214 Silicone Fluid from General Electric; this product is an SF 30 gum corresponding to a dimethicone, having a number-average molecular weight of 500 000, dissolved in the oil SF 1202 Silicone Fluid corresponding to decamethylcyclopentasiloxane;
        the mixtures of two PDMSs with different viscosities, and more particularly of a PDMS gum and a PDMS oil, such as the product SF 1236 from General Electric. The product SF 1236 is a mixture of a gum SE 30 defined above, with a viscosity of 20 m2/s, and of an oil SF 96 with a viscosity of 5×10−6 m2/s. This product preferably comprises 15% of gum SE 30 and 85% of an oil SF 96.
    
    


The organopolysiloxane resins that may be used in accordance with the invention are crosslinked siloxane systems containing the following units:
R2SiO2/2, R3SiO1/2, RSiO3/2 and SiO4/2,
in which R represents an alkyl containing 1 to 16 carbon atoms. Among these products, those that are particularly preferred are those in which R denotes a C1-C4 lower alkyl group, more particularly methyl.
Mention may be made, among these resins, of the product sold under the name Dow Corning 593 or those sold under the names Silicone Fluid SS 4230 and SS 4267 by General Electric, which are silicones of dimethyl/trimethylsiloxane structure.
Mention may also be made of the resins of the trimethylsiloxysilicate type, sold especially under the names X22-4914, X21-5034 and X21-5037 by the company Shin-Etsu.
The organomodified silicones that may be used in accordance with the invention are silicones as defined above and comprising in their structure one or more organofunctional groups attached via a hydrocarbon-based group.
In addition to the silicones described above, the organomodified silicones can be polydiarylsiloxanes, in particular polydiphenylsiloxanes, and polyalkylarylsiloxanes functionalized by the abovementioned organofunctional groups.
The polyalkylarylsiloxanes are chosen particularly from linear and/or branched polydimethyl/methylphenylsiloxanes and polydimethyl/diphenylsiloxanes with a viscosity of from 1×10−5 to 5×10−2 m2/s at 25° C.
Among these polyalkylarylsiloxanes, examples that may be mentioned include the products sold under the following names:

    
    
        the Silbione® oils of the 70 641 series from Rhodia;
        the oils of the Rhodorsil® 70 633 and 763 series from Rhodia;
        the oil Dow Corning 556 Cosmetic Grade Fluid from Dow Corning;
        the silicones of the PK series from Bayer, such as the product PK20;
        the silicones of the PN and PH series from Bayer, such as the products PN1000 and PH1000;
        certain oils of the SF series from General Electric, such as SF 1023, SF 1154, SF 1250 and SF 1265.
    
    


Mention may be made, among the organomodified silicones, of polyorganosiloxanes comprising:

    
    
        substituted or unsubstituted amine groups, such as the products sold under the name GP 4 Silicone Fluid and GP 7100 by the company Genesee, or the products sold under the names Q2 8220 and Dow Corning 929 or 939 by the company Dow Corning. The substituted amine groups are, in particular, C1-C4 aminoalkyl groups;
        alkoxylated groups, such as the product sold under the name Silicone Copolymer F-755 by SWS Silicones, and Abil Wax® 2428, 2434 and 2440 by the company Goldschmidt.
    
    


More particularly, the fatty substances are chosen from compounds that are liquid or pasty at room temperature (25° C.) and at atmospheric pressure.
Preferably, the fatty substance is a compound that is liquid at a temperature of 25° C. and at atmospheric pressure.
The fatty substances are advantageously chosen from C6-C16 alkanes, non-silicone oils of plant, mineral or synthetic origin, fatty alcohols, and esters of a fatty acid and/or of a fatty alcohol, or mixtures thereof.
Preferably, the fatty substance is chosen from liquid petroleum jelly, C6-C16 alkanes, polydecenes, liquid esters of a fatty acid and/or of a fatty alcohol, and liquid fatty alcohols, or mixtures thereof.
In a first variant of the invention, the total content of fatty substances is less than 20% by weight relative to the total weight of the composition. It then preferably ranges from 0 to 19%, better still from 0 to 15% and even better still from 0 to 10% by weight relative to the total weight of the composition (mixture of the dye and oxidizing compositions).
In a second variant of the invention, the total content of fatty substances is greater than or equal to 20% by weight relative to the total weight of the composition (mixture of the dye and oxidizing compositions). It then preferably ranges from 20% to 80%, better still from 30% to 75% and even better still from 50% to 70% by weight relative to the total weight of the composition (mixture of the dye and oxidizing compositions).
Other Adjuvants
The dye composition may also contain various adjuvants other than the thickening polymers of the invention, which adjuvants are conventionally used in hair dye compositions, for instance anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof; thickeners such as mineral thickeners especially such as clays; ammonium salts such as ammonium chloride or ammonium acetate; antioxidants or reducing agents such as ascorbic acid, erythorbic acid, ammonium sulfite, bisulfite or metabisulfite, or ammonium thiolactate; penetrants, sequestrants such as ethylenediaminetetraacetic or salts thereof; fragrances; titanium oxides; buffers; dispersants; and preserving agents, or mixtures thereof.
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 dye composition.
Oxidizing Composition
Chemical Oxidizing Agent
The second composition used in the process according to the invention also comprises at least one chemical oxidizing agent.
It should be noted that the oxidizing agents present in the oxidizing composition are termed “chemical” to distinguish them from atmospheric oxygen.
In particular, the chemical oxidizing agent(s) that are suitable for use in the present invention 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 oxidizing composition.
Surfactants
The oxidizing composition may also comprise one or more surfactants. In particular, the surfactant(s) are chosen from anionic, amphoteric, zwitterionic, cationic and nonionic surfactants, and preferentially nonionic surfactants. Reference may be made to the list of compounds of this type given in the context of the description of the dye composition.
Preferably, these surfactants, if they are present, are chosen from nonionic surfactants.
Even more preferably, the oxyalkylenated nonionic surfactants are chosen from oxyethylenated C8-C30 alcohols comprising from 1 to 100 mol of ethylene oxide, preferably from 2 to 50 and better still from 2 to 30 mol of ethylene oxide; oxyethylenated esters of linear or branched, saturated or unsaturated C8-C30 acids and of sorbitol comprising from 1 to 100 mol of ethylene oxide.
In the oxidizing composition, the amount of surfactant(s), when they are present, preferably ranges from 0.1% to 50% by weight and better still from 0.5% to 20% by weight relative to the total weight of the said composition.
Medium
The oxidizing composition is advantageously an aqueous composition. It may also comprise one or more organic solvents chosen from those listed previously, these solvents more particularly representing, when they are present, from 1% to 40% by weight and preferably from 5% to 30% by weight relative to the weight of the oxidizing composition.
The oxidizing composition also preferably comprises one or more acidifying agents. Among the acidifying agents, examples that may be mentioned include mineral or organic acids, for instance hydrochloric acid, orthophosphoric acid, sulfuric acid, carboxylic acids, for instance acetic acid, tartaric acid, citric acid or lactic acid, and sulfonic acids.
Usually, the pH of the oxidizing composition, when it is aqueous, is less than 7.
Other adjuvants
The oxidizing composition may also contain various conventionally used adjuvants other than the abovementioned associative and non associative thickening polymers, for instance anionic, cationic, nonionic, amphoteric or zwitterionic polymers or mixtures thereof; sequestrants such as ethylenediaminetetraacetic or salts thereof; fragrances; and preserving agents, or mixtures thereof.
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 oxidizing composition.
Propellant Gas
As has been indicated previously, at least one of the dye and/or oxidizing compositions used in the process according to the invention is dispensed from a pressurized container. In other words, the mixture used in the process according to the invention comprises (initially) one or more propellant gases.
It should be noted that, in the context of the invention, the propellant gas may be employed to enable the expulsion of the composition(s), but also to facilitate or bring about their expansion.
As indicated previously, at least one of the compositions comprises at least one propellant gas, and preferably both the compositions comprise at least one propellant gas. In other words, the gas(es) are mixed with the composition.
As propellant gases that are suitable for use in the invention, mention may be made of the gases usually used in the cosmetic field, in particular optionally halogenated volatile hydrocarbons, for example n-butane, propane, isobutane or pentane, and halogenated derivatives thereof; carbon dioxide, nitrous oxide, dimethyl ether and nitrogen, alone or as mixtures.
Preferably, the propellant gas(es) are chosen from alkanes and in particular from n-butane, propane and isobutane, and mixtures thereof.
The gases are under pressure, more particularly at least partially in liquid form.
In the preferred case in which each of the compositions comprises at least one propellant gas, these gases may be identical or different from one composition to another, whether as regards the nature of the gas(es) or as regards the respective proportions thereof if it is a case of mixtures.
Preferably, the content of propellant gas(es) represents a content ranging from 1% to 30% by weight relative to the weight of the composition, and preferably from 2% to 15% by weight relative to the weight of the composition in which they are present.
Device
The mixture applied to the fibres is thus obtained from the mixing of the dye and oxidizing compositions described previously.
The mixture may be obtained from a single pressurized container comprising either the oxidizing composition or the dye composition as described previously, the said composition being mixed before use with a composition (the dye composition or the oxidizing composition, respectively) obtained from a non-pressurized container such as a bottle or a tube, the mixture of the two compositions comprising

    
    
        at least one thickening polymer chosen from:
        
            associative polymer,
            anionic non-associative polymer chosen from anionic polymers bearing sugar units, anionic polymers not bearing sugar units chosen from crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or mixtures thereof,
            and mixtures thereof.
        
        
    
    


The mixture may also be obtained from a single pressurized container comprising the oxidizing composition and the dye composition as described previously in two separate pockets, the mixture of the two compositions comprising at least one associative thickening polymer.
Preferably, the said mixture used in the context of the invention is obtained from a device comprising:

    
    
        a first container containing the dye composition described previously, and
        a second container containing the oxidizing composition also described previously,
        at least one of the containers being pressurized, and preferably both the containers being pressurized;
        a means for dispensing the compositions; the mixture of the two compositions comprising at least one thickening polymer chosen from:
        
            associative polymer,
            anionic non-associative polymer chosen from anionic polymers bearing sugar units, anionic polymers not bearing sugar units chosen from crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, or copolymers of ammonium acrylate and of acrylamide, alone or mixtures thereof,
            
                and mixtures thereof.
            
            
        
        
    
    


Preferably, a means for dispensing each composition is mounted on each container.
One or both the containers may have rigid walls and directly contain the composition.
As a variant, one or both the containers may have rigid walls and include a flexible-walled pocket which contains the composition.
According to this embodiment, either the dye composition is in a pocket, or the oxidizing composition is in a pocket, or both of them are.
According to this configuration, the composition in the pocket may comprise no propellant gas, this gas being located in the volume defined between the rigid walls of the container and the pocket.
Preferably, the composition contained in the pocket comprises itself also at least one propellant gas.
According to another variant, the device comprises a first rigid-walled container which contains one or the other of the dye or oxidizing compositions, the first rigid-walled container including a flexible pocket which itself contains the other of the dye or oxidizing compositions and which constitutes a second container.
According to another variant, which is preferred, the device comprises two rigid-walled containers, preferably without a pocket, each containing a composition.
The device comprises a means for dispensing the compositions, the means comprising at least one dispensing valve mounted on the container(s).
Preferably, the means for dispensing the compositions comprises two dispensing valves, each valve being mounted on a container.
The valve(s) are in selective fluid communication with the interior of the container(s) via an inlet orifice of the valve, the communication being established in response to the actuation of an actuating means, such as a push button.
When the device comprises a first rigid-walled container which includes a flexible pocket, only one valve is provided for dispensing the two compositions. The
valve is then equipped with two inlet orifices, one of the orifices being able to communicate with the interior of the pocket and the other with the volume defined between the pocket and the rigid walls of the container.
When the containers do not include a pocket, they are equipped with a dip tube for conveying the composition to the inlet orifice of the dispensing valve.
When the containers include a pocket, the valve inlet orifice opens into the pocket.
The device may comprise at least one diffuser which caps the valve(s). According to a first variant, the device comprises a single diffuser which caps the two valves. According to a second variant, the device comprises two diffusers, each independently capping a valve.
The push button may form part of the diffuser.
The diffuser may be equipped with one or more dispensing ducts provided to convey the composition(s) to one or more dispensing orifices.
When the device comprises two diffusers, each of the diffusers is equipped with a duct for conveying the composition between the valve outlet orifice and a dispensing orifice.
When the device comprises a single diffuser, it may be equipped with two ducts for conveying the compositions, each duct communicating with the outlet orifice of a valve.
According to a first embodiment, the two ducts each arrive at a dispensing orifice (not communicating with each other before the dispensing orifice). According to this configuration, the mixing of the compositions does not take place until after they have been dispensed (and thus after the dispensing orifices).
According to a second embodiment, the two ducts arrive in a mixing chamber, from which a single duct is directed towards a single dispensing orifice. According to this configuration, the mixing of the compositions takes place just before the mixture is expelled from the device.
Preferably, the two ducts each open directly onto a dispensing orifice.
When the device comprises two diffusers, namely when it comprises two containers, on each of which is mounted a valve and a diffuser specific thereto, the two containers may be free relative to each other, i.e. not integrally attached.
As a variant, the two containers may be integrally attached, for example by means of an outer envelope partly covering the containers (especially a thermoformed film or a metallic or plasticized rigid envelope), or alternatively by means of notches made in the outer wall of each container, enabling them to be fastened together.
When the device comprises a single diffuser which caps the two valves, this diffuser enables the two containers to be integrally attached. In this case, an outer envelope partly covering the containers may also be envisaged.
In accordance with a particular embodiment of the invention, the device comprises two integrally attached containers, the device enabling the compositions to be dispensed concomitantly, via one or, preferably, two dispensing orifices.
Preferably, according to this embodiment, the containers have rigid walls, a dispensing valve being mounted on each of the containers, a single diffuser capping the two valves, and the two containers being integrally attached.
Needless to say, the devices are designed such that the dye and oxidizing compositions come into contact at the time of application of the mixture obtained.
Mixture
Advantageously, the mixture of the dye composition and of the oxidizing composition, used in the process according to the invention, and which is applied to the fibres, is in the form of a foam, which is thus produced just before it is applied.
More particularly, the dye composition which is dispensed (obtained) from a pressurized container is in the form of a cream, a gel or a foam, preferably in the form of a foam.
Moreover, the oxidizing composition which is dispensed (obtained) from a pressurized container is in the form of a cream, a gel or a foam, preferably in the form of a foam.
The pH of the mixture of the dye and oxidizing compositions is advantageously between 3 and 12, preferably between 5 and 11 and preferentially between 7 and 11, limits inclusive.
It should be noted that the dispensing valve(s), and similarly the content of propellant gas(es), are adapted so as to enable the compositions to be dispensed in suitable respective proportions.
In practice, the dye composition/oxidizing composition weight ratio in the dispensed mixture ranges from 0.25 to 4 and preferably from 0.5 to 2.
Even more preferentially, this ratio is 1.
The dyeing process according to the invention consists in applying the mixture thus obtained to wet or dry human keratin fibres for a time sufficient to develop the desired coloration.
According to the invention, the mixture obtained according to the process of the invention is applied to keratin fibres preferably in the form of a foam.
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 example that follows serves to illustrate the invention without, however, being limiting in nature.


EXAMPLE
Dye Composition (Contents Expressed in g % in Native Form):











Ingredients
Concentration
















Cocoylbetaine as an aqueous 30% solution 
10


(Mirataine BB/FLA sold by the company Rhodia)



Oxyethylenated (40 OE) hydrogenated castor oil 
0.8


(Eumulgin HRE 40)



Crystalline sorbitol (Neosorb P 60 sold by 
5


the company Roquette)



Polydimethyldiallylammonium chloride at 
2


40% in water



Fragrance
0.4


Erythorbic acid
0.5


Ethylenediaminetetraacetic acid
0.2


Sodium metabisulfite
0.5


Monoethanolamine
4.5


1-Methyl-2,5-diaminobenzene
0.2


1-Hydroxy-4-aminobenzene
1.25


1,3-Dihydroxybenzene
0.75


1-Hydroxy-3-aminobenzene
0.30


1-Methyl-2-hydroxy-4-β-hydroxyethylaminobenzene
0.15


2-Methyl-1,3-dihydroxybenzene
0.65


Aqueous ammonia (ammonia concentration of 20%)
6


(C14/16)alkyl hydroxyethylcellulose 
0.3


(Natrosol Plus 330 sold by



the company Ashland)



Oxyethylenated (100 OE) stearyl alcohol 
2


(Brij S100-PA-(SG) sold



by the company Croda)



Sucrose (Sucrose Ultra Pure Grade sold 
1.33


by the company Amresco)



Deionized water
63.35









Oxidizing Composition (Contents Expressed in g % in Native Form):















Chemical name
Concentration



















Mixture of cetylstearyl alcohol/oxyethylenated 
2.85



(33 OE) cetylstearyl alcohol (Sinnowax AO sold 




by the company Cognis)




(50% linear 70/30 C13/C15)alkyl ether carboxylic 
0.85



acid monoethanolamide (2 OE)




Glycerol
0.5



Tetrasodium pyrophosphate decahydrate
0.02



Disodium tin hexahydroxide
0.04



Diethylenetriaminepentaacetic acid, pentasodium 
0.15



salt as an aqueous 40% solution




50% hydrogen peroxide solution
12



Phosphoric acid
q.s. for pH 2.2



deionized water
q.s. for 100










Each of the above compositions is conditioned in an aerosol container in the presence of the following propellant gases, in a composition/propellant gases weight ratio of 94/6.

    
    
        Dye composition: 50% propane, 35% n-butane,15% i-butane
        Oxidizing composition: 25% propane, 40% n-butane,35% i-butane
    
    


The two aerosols are integrally attached via a dispensing head incorporating the two dispensing channels deriving from the two pressurized containers, the mixing of the two compositions in a weight ratio of 1/1 not taking place until immediately after exiting the dispensing head.
The resulting mixture is left on the fibres for 30 minutes at room temperature (25° C.).
A natural dark shade, which covers grey hair well, is obtained.
Dye Composition (Contents Expressed in g % in Native Form):











Nom chimique
Concentration
















Lauric acid
3


oxyethylenated Lauryl alcohol I (12 OE)1)
7


cetylstearyl alcohol (C16/C18 50/50)2)
11.5


distearate de glycol
2


alcool oléocétylique oxyéthyléné (30 OE)3)
4


Oxyethylenated decyl alcohol (3 OE) 90% 4)
10


Fumed hydrophobic silica 5)
1.2


pure monoethanolamine
1.2


poly[dichloride (dimethyliminio)-1,3-propanediyl-
5


(dimethyliminio)-1,6-



hexanediyl] as an aqueous 60% solution



dimethyl diallyl ammonium chloride/acrylic acid 
3.7


copolymer (80/20) aqueous solution7)



propylene glycol
10


Carboxyvinylic polymer (98% in ethyle 
0.4


acetate/cyclohexane 8)



Diethylenetriaminepentacetic acid aqueous solution 40%
2


C vitamine
0.25


Titanium oxide (anatase) c poly dimethylsiloxane (98/2) 
0.15


Fragrance
0.75


sodium metabisulfite (powder)
0.71


1,4-diamino-benzene
0.45


1-hydroxy-4-amino-benzene
0.7


1,3-dihydroxybenzene
0.15


1-hydroxy-3-amino-benzene
0.2


2-amino-3-hydroxypiridine
0.1


1-methyl-2-hydroxy-4-beta-hydroxyethylamino-benzene
0.1


2-methyl-1,3-dihydroxybenzene
0.7


Aqueous ammonia (20% concentration of ammonia)
11.1


Deionized water
QSP





1)sold under the reference REWOPAL 12 by the company EVONIK


2)sold under the reference LANETTE O OR by the company COGNIS


3)sold under the reference EUMULGIN O 30 by the company COGNIS


4) sold under the reference EUMULGIN BL 309 by the company COGNIS


5) sold under the reference AEROSIL R 972 by the company EVONIK


6) sold under the reference MEXOMERE PO by the company CHIMEX


7)sold under the reference MERQUAT 280 by the company NALCO


8) sold under the reference CARBOPOL 980 POLYMER by the company LUBRIZOL






Oxidizing Composition (Contents Expressed in g % in Native Form):












Nom chimique
Concentration
















ACID ALKYL (C13/C15 70/30 50% LINEAR)
1.3


MONOETHANOLAMIDE 



CARBOXYLIC ETHER (2 OE) 9)



GLYCEROL
0.5


PYROPHOSPHATE TETRA-SODIQUE, 10 H2O
0.04


SALICYLATE DE SODIUM
0.035


Etidronic acid, tetrasodium salt as an aqueous 30%
0.6


solution



Hydrogen peroxyde as a 50% solution
12


PHOSPHORIC ACID
0


Deionized water
QSP


CETYLSTEARYLIQUE ALCOHOL (C16/C18 30/70) 10) 
8


OXYETHYLENATED CETYLSTEARYLIQUE 
1.4


ALCOHOL (33 OE) 11)





9) sold under the reference AMIDET A15/LAO 55 by the company KAO


10) sold under the reference NAFOL 1618 S by the company SASOL


11) sold under the reference SIMULSOL CS ECAILLES by the company SEPIC






Each of the above compositions is conditioned in an aerosol container in the presence of the following propellant gases, in a composition/propellant gases weight ratio of 94/6.

    
    
        Dye composition: 50% propane, 35% n-butane,15% i-butane
        Oxidizing composition: 25% propane, 40% n-butane,35% i-butane
    
    


The two aerosols are integrally attached via a dispensing head incorporating the two dispensing channels deriving from the two pressurized containers, the mixing of the two compositions in a weight ratio of 1/1 not taking place until immediately after exiting the dispensing head.
The resulting mixture is left on the fibres for 30 minutes at room temperature (25° C.).
A natural light blond shade, which covers grey hair well, is obtained.

## Claims

1. A process for dyeing keratin fibers, comprising:
(a) preparing a cosmetic mixture by mixing:
a dye composition comprising at least one oxidation dye precursor, and
a oxidizing composition comprising at least one chemical oxidizing agent; and

(b) applying said mixture to said keratin fibers;
wherein the cosmetic mixture further comprises at least one thickening polymer chosen from:
associative polymers,
anionic non-associative polymers chosen from anionic non-associative polymers not bearing sugar units chosen from crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, copolymers of ammonium acrylate and of acrylamide, or mixtures thereof,
or mixtures thereof,
wherein the dye composition and oxidizing composition are dispensed from separate pressurized containers contained in a single device.

2. The process according to claim 1, wherein the at least one associative thickening polymer is chosen from associative polyurethanes, associative cellulose derivatives, associative vinyllactams, associative unsaturated polyacids, anionic associative polymers, associative aminoplast ethers, and associative polymers or copolymers comprising at least one ethylenically unsaturated monomer bearing a sulfonic group, or mixtures thereof.

3. The process according to claim 1, wherein the at least one associative thickening polymer is nonionic or cationic.

4. The process according to claim 2, wherein the at least one anionic associative polymers are chosen from copolymers comprising an α,β-monoethylenically unsaturated carboxylic acid and an ester of an α,β-monoethylenically unsaturated carboxylic acid and of an oxyalkylenated fatty alcohol.

5. The process according to claim 1, wherein the at least one associative thickening polymer is present in the cosmetic mixture in an amount ranging from about 0.001% to about 20% by weight, relative to the weight of the cosmetic mixture.

6. The process according to claim 1, wherein the anionic non-associative thickening polymers are present in the cosmetic mixture in an amount ranging from about 0.01% to about 40% by weight, relative to the total weight of the cosmetic mixture.

7. The process according to claim 1, wherein the at least one oxidation dye precursor is chosen from oxidation bases and couplers.

8. The process according to claim 1, wherein the pressurized container comprises at least one propellant gas chosen from optionally halogenated volatile hydrocarbons and halogenated derivatives thereof.

9. The process according to claim 8, wherein the at least one propellant gas is chosen from n-butane, propane, isobutene, pentane, carbon dioxide, nitrous oxide, dimethyl ether, nitrogen, compressed air, and mixtures thereof.

10. The process according to claim 1, wherein the dye composition and the oxidizing composition each comprise at least one propellant gas, which may be the same or different,
wherein the at least one propellant gas is present in an amount ranging from about 1% to about 30%, relative to the weight of the composition in which it is present.

11. The process according to claim 1, wherein the at least one chemical oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates or ferricyanides, peroxygenated salts and peracids, and precursors thereof.

12. The process according to claim 1, wherein the dye composition comprises at least one alkaline agent, said alkaline agent chosen from aqueous ammonia, alkanolamines, amino acids, or mixtures thereof.

13. The process according to claim 12, wherein the at least one alkaline agent is present in the dye composition an amount ranging from about 0.01% to about 30% by weight, relative to the weight of the dye composition.

14. The process according to claim 1, wherein the dye composition and/or the oxidizing composition comprises at least one surfactant chosen from cationic, amphoteric, nonionic and anionic surfactants.

15. The process according to claim 1, wherein the dye composition and the oxidizing composition are each in a different pressurized container and the containers are optionally integrally attached and configured to dispense the compositions concomitantly, via one or two dispensing orifices.

16. The process according to claim 1, wherein the cosmetic mixture of the dye composition and the oxidizing composition is dispensed from the separate pressurized containers in the form of a foam.

17. A device for dispensing a cosmetic mixture for dyeing keratin fibers, said cosmetic mixture comprising:
a dye composition comprising at least one oxidation dye precursor,
a oxidizing composition comprising at least one chemical oxidizing agent, and
at least one thickening polymer chosen from:
associative polymers,
anionic non-associative polymers chosen from anionic non-associative polymers not bearing sugar units chosen from crosslinked acrylic or methacrylic acid homopolymers or copolymers, crosslinked 2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinked acrylamide copolymers thereof, ammonium acrylate homopolymers, copolymers of ammonium acrylate and of acrylamide, or mixtures thereof,
or mixtures thereof;

wherein the device is configured to dispense the dye composition and the oxidizing composition from separate pressurized containers contained within the device.