WO2022128901A1

WO2022128901A1 - Process for dyeing keratin fibres using two different compounds that are capable of forming covalent bonds together and also a particular metal salt or a salt of a metal belonging to the rare-earth metal group or a particular organometallic compound

Info

Publication number: WO2022128901A1
Application number: PCT/EP2021/085460
Authority: WO
Inventors: Alexandra CHARRIER; Andrew Greaves; Julien PORTAL; Christian Blaise
Original assignee: L'oreal
Priority date: 2020-12-17
Filing date: 2021-12-13
Publication date: 2022-06-23

Abstract

The present invention relates to a process for dyeing keratin fibres, comprising the application to the keratin fibres of two different compositions comprising two different compounds that are capable of forming covalent bonds together, the process also including one or more compounds chosen from particular metal salts, salts of a metal belonging to the rare-earth metal group, particular organometallic compounds, and mixtures thereof, and also one or more colouring agents.

Description

PROCESS FOR DYEING KERATIN FIBRES USING TWO DIFFERENT COMPOUNDS THAT ARE CAPABLE OF FORMING COVALENT BONDS TOGETHER AND ALSO A PARTICULAR METAL SALT OR A SALT OF A METAL BELONGING TO THE RARE- EARTH METAL GROUP OR A PARTICULAR ORGANOMETALLIC COMPOUND

FIELD OF THE INVENTION

BACKGROUND OF THE INVENTION

Cosmetic products often require the use of film-forming polymers to obtain a deposit of the product on keratin materials that has good cosmetic properties. In particular, it is necessary for the film-forming deposit to have good persistence, in particular for the deposit not to transfer during contact with the fingers or clothing, and also good persistence on contact with water, notably rain or during showering or perspiration. Skin sebum may also damage the film-forming deposit.

In the field of dyeing keratin fibres, it is already known practice to dye keratin fibres via various techniques using direct dyes for non-permanent dyeing, or dye precursors for permanent dyeing.

Non-permanent dyeing or direct dyeing consists in dyeing keratin fibres with dye compositions containing direct dyes. These dyes are coloured and colouring molecules that have affinity for keratin fibres. They are applied to the keratin fibres for a time necessary to obtain the desired colouring, and are then rinsed out.

The standard dyes that are used are, in particular, dyes of the nitrobenzene, anthraquinone, nitropyridine, azo, xanthene, acridine, azine or triarylmethane type, or natural dyes.

Some of these dyes may be used under lightening conditions, which enables the production of colourings that are visible on dark hair.

It is also known practice to dye keratin fibres permanently via oxidation dyeing. This dyeing technique consists in applying to the keratin fibres a composition containing dye precursors such as oxidation bases and couplers. Under the action of an oxidizing agent, these precursors form one or more coloured substances in the hair. The variety of molecules used as oxidation bases and couplers allows a wide range of colours to be obtained, and the colourings resulting therefrom are generally permanent, strong and resistant to external agents, notably to light, bad weather, washing, perspiration and rubbing.

In order to be visible on dark hair, these two dyeing techniques require prior or simultaneous bleaching of the keratin fibres. This bleaching step performed with an oxidizing agent such as hydrogen peroxide or persalts may impair the cosmetic properties of the hair, which then has a tendency to become coarse, more difficult to disentangle and more fragile.

Another dyeing method consists in using pigments. Specifically, the use of pigment on the surface of keratin fibres generally makes it possible to obtain colourings that are visible on dark hair, since the surface pigment masks the natural colour of the fibre. The use of pigment for dyeing keratin fibres is described, for example, in patent application FR 2 741 530, which recommends using, for the temporary dyeing of keratin fibres, a composition comprising at least one dispersion of film-forming polymer particles including at least one acid function and at least one pigment dispersed in the continuous phase of said dispersion. The colourings obtained via this dyeing method have the drawback of being removed easily on shampoo washing.

It is moreover known practice from patent application FR 2 907 678 to perform coloured coating of the hair using a composition comprising a polysiloxane/polyurea block copolymer and a pigment. However, with such a composition, the coating results obtained are not always very homogeneous and the hair strand separation is not always very good.

It is also known practice from patent application FR 3 087 123 to perform a process for dyeing keratin fibres in at least two steps, comprising in a first stage the application to said fibres of an oily dispersion comprising i) particles of copolymers of alkyl acrylates and anhydride acrylics, ii) stabilizers, iii) one or more hydrocarbon-based oils and then, in a second stage, the application to said fibres of a composition comprising iv) one or more amine compounds, it being understood that the process of the invention involves v) one or more dye(s) and/or pigment(s) which may be in the oily dispersion and/or in the composition comprising the amine compound(s), and/or in another composition. This process makes it notably possible to obtain a coloured coating that is persistent with respect to shampoo washing.

However, the inventors realised that the shampoo washing protocol could vary from one user to another, notably as regards the shampoo leave-on time, a longer leave-on time possibly being the cause of poorer persistence of the colouring with respect to shampoo washing. Moreover, the selectivity of the colouring obtained by this process can occasionally be substantial, i.e. differences in colouring that are sometimes substantial may be observed along the same length of keratin fibre, which generally includes zones that are differently sensitized from its root to its end.

There is thus a real need to develop a process for dyeing keratin fibres which makes it possible to obtain a coloured coating that has better persistence with respect to shampoo washing, the persistence being independent of the shampoo washing protocol followed by the user and being notably observed for long shampoo leave-on times, i.e. at least one minute. Such a process must also make it possible to obtain colouring with little selectivity, i.e. small differences in colouring observed along the same length of keratin fibre, which generally includes zones that are differently sensitized from its root to its end. Finally, such a process must not lead to any degradation of the keratin fibres and must make it possible to conserve keratin fibres with perfectly separated strands.

The Applicant has discovered, surprisingly, that all of these objectives can be achieved by means of the process according to the present invention.

SUMMARY OF THE INVENTION

According to a first aspect, one subject of the present invention is a process for dyeing keratin fibres, involving

■ applying to the keratin fibres a composition (A) comprising at least one compound A bearing at least one chemical function A; and

■ applying to the keratin fibres a composition (B) comprising at least one compound B bearing at least one chemical function B; compound B being different from compound A; in which:

- the chemical functions A and B are capable of forming covalent bonds together; and

- the process includes: a) one or more compounds E chosen from metal salts, salts of a metal belonging to the rare-earth metal group, organometallic compounds, and mixtures thereof, the compound(s) E being included in composition (A) and/or in composition (B) and/or in a different composition (C), composition (C) also being applied to the keratin fibres; and

P) one or more colouring agents chosen from direct dyes, oxidation dyes, pigments and mixtures thereof, the colouring agent(s) being included in composition (A) and/or in composition (B) and/or in composition (C) and/or in a different composition (D), composition (D) also being applied to the keratin fibres; it being understood that: - the metal salts are chosen from the salts of transition metals, alkali metal salts, alkaline- earth metal salts, aluminium salts, boron salts, tin salts, magnesium salts, hydrates thereof and mixtures thereof; and

- the organometallic compounds are chosen from the alkoxides of formulae (la), (lb), (Ic) and (Id) below and mixtures thereof:

M-(ORi)_n (la)

R-M-(ORi)_n-i (lb)

(RlO)n-1-M-R”-M”-(ORl)n-1 (Ic)

RR’-M-(ORi)_n-2 (Id) in which formulae (la), (lb), (Ic) and (Id):

- M and M’, independently of each other, represent an atom chosen from transition metals, metals of the lanthanide family, aluminium, boron, tin or alkaline-earth metals;

- n represents the valency of the atom;

- Ri, which may be identical or different, represent a linear or branched, saturated or unsaturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 1 to 6 carbon atoms, optionally interrupted with 1 to 20 heteroatoms chosen from O, N, S and/or P;

- R and R’, independently of each other, represent a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, optionally interrupted with 1 to 20 heteroatoms chosen from O, N, S and/or P;

- R” represents -O-, -NR²-, -S- or a linear, cyclic or branched, saturated or unsaturated divalent hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, optionally interrupted with 1 to 20 heteroatoms chosen from O, N, S and/or P, with R² representing a linear, cyclic or branched, saturated or unsaturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms.

According to a second aspect, a subject of the present invention is a composition (A0) comprising:

- the oily dispersion (A’) as defined below;

- one or more compound(s) E as defined previously;

- optionally one or more colouring agents as defined previously.

According to a third aspect, a subject of the present invention is a kit or device containing several separate compartments, comprising:

■ in a first compartment: composition (A) as defined previously;

■ in a second compartment separate from the first: composition (B) as defined previously; and

■ optionally in a third compartment separate from the other two: composition (C) as defined previously; and

■ optionally in a fourth compartment separate from the other three: composition (D) as defined previously; in which:

- at least one of the compositions of the kit comprises one or more compounds E as defined previously; and

- at least one of the compositions of the kit comprises one or more colouring agents as defined previously.

DETAILED DESCRIPTION OF THE INVENTION

For the purposes of the present invention and unless otherwise indicated:

■ the term “keratin fibres” means fibres of human or animal origin, such as head hair, bodily hair, the eyelashes, the eyebrows, wool, angora, cashmere or fur. According to the present invention, the keratin fibres are preferably human keratin fibres, more preferentially the hair;

■ the term “alkyl group” means a linear or branched saturated Ci-Cs, in particular Ci-Ce, preferably C1-C4 hydrocarbon-based group such as methyl, ethyl, isopropyl and tert-butyl;

■ the term “alkoxy group” means an alkyl-oxy group with alkyl as defined previously, preferably C1-C4 alkoxy, such as methoxy or ethoxy;

■ the term “optionally substituted” attributed to the alkyl group implies that said alkyl group may be substituted with one or more groups chosen from the following groups: i) hydroxyl, ii) C1-C4 alkoxy, iii) acylamino, iv) amino optionally substituted with one or two identical or different C1-C4 alkyl groups, said alkyl radicals possibly forming, with the nitrogen atom that bears them, a 5- to 7-membered heterocycle, optionally comprising another nitrogen or nonnitrogen heteroatom;

■ when the alkoxy group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above;

■ the term “alkylene group” means a linear or branched divalent saturated Ci-Cs, in particular Ci-Ce, preferably C1-C4 hydrocarbon-based group such as methylene, ethylene or propylene;

■ the term “cycloalkyl group” means a cyclic saturated hydrocarbon-based group comprising from 1 to 3 rings, preferably 2 rings, and comprising from 3 to 13 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, or isobornyl, the cycloalkyl group possibly being substituted with one or more (Ci-C4)alkyl groups such as methyl; preferably, the cycloalkyl group is an isobornyl group;

■ the term “cyclic group” means a cyclic, saturated or unsaturated, aromatic or non-aromatic hydrocarbon-based group comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms, such as cyclohexyl or phenyl;

■ the term “heterocyclic group” means a cyclic, saturated or unsaturated, aromatic or non- aromatic hydrocarbon-based group comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms and from 1 to 5 heteroatoms chosen from O, S and N, such as morpholinyl, piperazinyl, piperidyl, furyl, pyridyl or indolyl;

■ the term “aryl group” means a monocyclic or fused or non-fused bicyclic, unsaturated cyclic aromatic group comprising from 6 to 12 carbon atoms; preferably, the aryl group comprises 1 ring and contains 6 carbon atoms, such as phenyl;

■ the term “aryloxy group” means an aryl-oxy, i.e. aryl-O-, group, with aryl as defined previously, preferably phenoxy;

■ the term “aryl(Ci-C4)alkoxy group” means an aryl(Ci-C4)alkyl-O- group, preferably benzoxy;

■ the term “heteroaryl group” means a monocyclic or fused or non-fused polycyclic, 5- to 22- membered group, comprising from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, and at least one ring of which is aromatic; preferentially, a heteroaryl group is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl, imidazopyridyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridyl, thiazoylimidazolyl, thiopyrylyl, triazolyl and xanthylyl;

■ the “aryl” or “heteroaryl” groups or the aryl or heteroaryl part of a group may be substituted with at least one substituent borne by a carbon atom, chosen from:

- a Ci-Cs alkyl group optionally substituted with one or more groups chosen from hydroxyl, C1-C2 alkoxy, (poly)hydroxy(C2-C4)alkoxy, acylamino, amino substituted with two identical or different C1-C4 alkyl groups, optionally bearing at least one hydroxyl group, or the two groups possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered and preferably 5- or 6-membered heterocycle optionally comprising another nitrogen or non-nitrogen heteroatom;

- a halogen atom;

- a C1-C2 alkoxy group;

- a 5- or 6-membered heterocycloalkyl group;

- an acylamino group (-NR-COR’) in which the group R is a hydrogen atom, a C1-C4 alkyl group and the group R’ is a C1-C2 alkyl group; a carbamoyl group ((R)2N-CO-) in which the groups R, which may be identical or different, represent a hydrogen atom, a C1-C4 alkyl group; an alkylsulfonylamino group (R’SC>2-NR-) in which the group R represents a hydrogen atom or a C1-C4 alkyl group and the group R’ represents a C1-C4 alkyl group or a phenyl group; an aminosulfonyl group ((R)2N-SO2-) in which the groups R, which may be identical or different, represent a hydrogen atom or a C1-C4 alkyl group;

- a carboxylic group in acid or salified form (preferably with an alkali metal or a substituted or unsubstituted ammonium);

- a cyano group;

- a polyhaloalkyl group, preferentially trifluoromethyl;

■ the cyclic or heterocyclic part of a non-aromatic group may be substituted with at least one substituent chosen from the following groups:

- C1-C4 alkoxy;

- C1-C4 alkyl;

- alkylcarbonylamino (RCO-NR’-) in which the radical R’ is a hydrogen atom or a C1-C4 alkyl group and the group R is a C1-C2 alkyl group;

* alkylcarbonyloxy (RCO-O-) in which the radical R is a C1-C4 alkyl group or an amino group optionally substituted with one or two identical or different C1-C4 alkyl groups, said alkyl groups possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle optionally comprising at least one other nitrogen or non-nitrogen heteroatom;

- alkoxycarbonyl (RG-CO-) in which the group R is a C1-C4 alkoxy group, G is an oxygen atom or an amino group optionally substituted with a C1-C4 alkyl group, said alkyl group possibly forming, with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted 5- to 7-membered heterocycle, optionally comprising at least one other nitrogen or non-nitrogen heteroatom;

■ a cyclic or heterocyclic group, or a non-aromatic part of an aryl or heteroaryl group, may also contain one or more oxo groups; ■ a hydrocarbon-based chain is unsaturated when it includes one or more double bonds and/or one or more triple bonds, preferably one or more double bonds.

Unless otherwise indicated, when compounds are mentioned in the present patent application, this also includes the optical isomers thereof, the geometrical isomers thereof, the tautomers thereof, the salts thereof or the solvates thereof, alone or as a mixture.

The terms “at least one” and “one or more” are synonymous and may be used interchangeably.

Process for dyeing keratin fibres

According to a first aspect, a subject of the present invention is a process for dyeing keratin fibres as defined previously.

The Applicant has found, surprisingly, that the process according to the invention notably makes it possible to obtain on keratin fibres coloured coatings which have a visible colouring on all types of fibres, notably on dark hair, the colouring being persistent with respect to shampoo washing independently of the shampoo washing protocol followed by the user, the persistence being notably observed for long shampoo leave-on times, i.e. at least one minute. Furthermore, the process makes it possible in particular to obtain a smooth and uniform deposit and the keratin fibre strands remain perfectly separated and could be styled without any problem. Finally, the colouring obtained via the process according to the invention is characterized by low selectivity.

The term “keratin fibres with separated strands” means keratin fibres, notably hair, which, after application of the compositions and drying, are not stuck together (or are all separate from each other) and therefore do not form clumps of fibres, since the coating is formed around virtually every fibre.

The chemical functions A and B are capable of forming covalent bonds together.

In the context of the present invention, the nature of the chemical function(s) A and the nature of the chemical function(s) B are chosen such that when placed in contact, optionally with a chemical and/or physical stimulus, the chemical function A reacts with the chemical function B to form a covalent bond.

Thus, the chemical function A can react with the chemical function B spontaneously or, for example, by activation by means of the temperature, the pH, a co-reagent or a chemical or biochemical catalyst, for instance an enzyme. Composition (A) may be applied after composition (B) or composition (B) may be applied after composition (A).

According to a preferred embodiment, composition (B) is applied after composition (A).

Composition (A)

Composition (A) comprises at least one compound A bearing at least one chemical function A.

When the compound(s) A bear several chemical functions A, the chemical functions A may be identical or different.

The compound(s) A may comprise chemical functions other than the chemical function(s) A.

Preferably, the compound(s) A do not comprise any chemical functions B.

According to a particular embodiment, composition (A) comprises less than 10% by weight of compound B, preferably less than 5% by weight of compound B, more preferentially less than 2% by weight of compound B relative to the total weight of composition (A); even more preferentially, composition (A) is free of compound B.

Preferably, the chemical function(s) A are chosen from the following functions:

- epoxide;

- vinyl and activated vinyl, in particular acrylonitrile, acrylic and methacrylic esters, crotonic acid and esters, cinnamic acid and esters, styrene and derivatives, butadiene, vinyl ethers, vinyl ketone, maleic esters, vinyl sulfones, maleimides;

- anhydride, acid chloride and carboxylic acid esters;

- aldehydes, acetals, hemiacetals, aminals, hemiaminals;

- isocyanate;

- thiocyanate;

- ketones, including a-hydroxy ketones and a-halo ketones;

- lactones, thiolactones;

- imines;

- imides;

- N-hydroxysuccinimide esters;

- imidates;

- thiosulfate;

- oxazine and oxazoline; - oxazinium and oxazolinium;

- Ci to C30 alkyl halides or Ce to C30 aryl or aralkyl halides, notably iodides, chlorides or bromides;

- halides of an unsaturated carbon-based ring or heterocycle;

- sulfonyl halides of formula RSO2X in which X = Cl or F and R is a Ci to C30 alkyl group;

- cyclic carbonates;

- diazonium;

- carbodiimide;

- and mixtures thereof.

According to a preferred embodiment, the chemical functions A are chosen from anhydride, acid chloride, carboxylic acid ester and epoxide functions, and mixtures thereof, preferably from anhydride, acid chloride and carboxylic acid ester functions, and mixtures thereof.

According to a more preferred embodiment, the chemical function(s) A are anhydride functions.

Preferably, the compound(s) A are polymers.

The polymer(s) may be synthetic or natural.

According to a particularly preferred embodiment, the polymer(s) are polymers containing the maleic anhydride unit.

The oily dispersion (A’)

According to a preferred embodiment, composition (A) comprises an oily dispersion (A’) which comprises the compound(s) A.

According to another preferred embodiment, composition (A) is an oily dispersion (A’) which comprises the compound(s) A.

The term “anhydrous dispersion or composition” refers to a dispersion or composition containing less than 2% by weight of water, preferably less than 0.5% by weight of water, and more preferentially free of water. Where appropriate, such small amounts of water may notably be introduced by ingredients of the composition that may contain residual amounts thereof.

According to one embodiment of the invention, composition (A) comprises the oily dispersion (A’) in the form of an inverse emulsion, i.e. an emulsion of water-in-oil (W/O) type and comprises one or more surfactants, preferably nonionic surfactants. Composition (A) is preferably anhydrous.

According to a preferred embodiment, the oily dispersion (A’) is an oily dispersion of i) one or more particles of at least one polymer surface-stabilized with ii) one or more stabilizers in a medium which is preferably anhydrous, also containing iii) one or more hydrocarbonbased oils. i) Polymer particle(s)

The oily dispersion (A’) comprises i) the compound(s) A in the form of one or more particles of at least one polymer.

Preferably, the polymer particle(s) i) are spherical.

The polymer particle(s) preferably have a number-mean size ranging from 5 to 500 nm, notably ranging from 10 to 400 nm and better still ranging from 20 to 300 nm.

The particle(s) i) of the oily dispersion (A’) consist of one or more ethylenic copolymers of a) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate and of b) ethylenically unsaturated anhydride compound.

The term “ethylenic copolymer¹’ means a polymer resulting from the polymerization of two monomers: of the monomer a) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate and of the monomer b) of ethylenically unsaturated anhydride compound.

The term “ethylenically unsaturated anhydride compound” means a carboxylic acid anhydride compound comprising at least one ethylenic unsaturation -(R_a)C=C(Rb)-, -C(R_a)=C(Rb)-Rc or >C=C(R_a)-Rb, with R_a, Rb, and R_c, which may be identical or different, representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl, preferably hydrogen. In particular, the ethylenically unsaturated anhydride compound is a cyclic compound, which is preferably 5- or 6-membered, and comprising an ethylenic unsaturation.

(Ci-C4)alkyl (Ci-C4)(alkyl)acrylate monomer a)

Preferably, the monomer a) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate is of formula H2C=C(R)-C(O)- O-R’ with R representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl, and R’ representing a (Ci-C4)alkyl group such as methyl or ethyl.

More preferentially, the monomer a) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate is a (Ci-C4)alkyl (meth) acrylate monomer. Even more preferentially, the monomer a) C1-C4 alkyl (Ci-C4)(alkyl)acrylate is chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate and tert-butyl (meth)acrylate.

Advantageously, a C1-C4 alkyl acrylate monomer a) is used.

According to a preferred embodiment, the monomer a) is chosen from methyl acrylate and ethyl acrylate.

Ethylenically unsaturated anhydride monomer b)

Preferably, the ethylenically unsaturated anhydride monomer b) is chosen from derivatives of maleic anhydride (lb) and of itaconic anhydride (lib):

(lb) (lib) in which formulae (lb) and (lib) R_a, Rb and R_c, which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group; preferably, R_a, Rb and R_c represent a hydrogen atom.

More preferentially, the ethylenically unsaturated anhydride monomer b) is of formula (lb). Even more preferentially, the ethylenically unsaturated anhydride monomer b) is maleic anhydride.

According to a preferred embodiment, the polymer(s) of the particles i) comprise, or consist essentially of, from 80% to 99.99% by weight of monomer a) and from 0.01% to 20% by weight of monomer b), relative to the total weight of the polymer.

The polymer of the particles i) may be chosen from:

- methyl acrylate/maleic anhydride copolymers;

- ethyl acrylate/maleic anhydride copolymers; and

- copolymers of methyl acrylate/ethyl acrylate/maleic anhydride.

Advantageously, the polymer of the particles i) is a non-crosslinked polymer. The polymer of the particles i) preferably has a number-average molecular weight ranging from 2000 to 10 000 000.

The polymer particles i) may be present in the oily dispersion (A’) in a total content ranging from 20% to 60% by weight, preferably ranging from 21% to 58.5% by weight, more preferentially ranging from 30% to 50% by weight, even more preferentially ranging from 36% to 42% by weight relative to the total weight of oily dispersion (A’). ii) Stabilizer(s)

The oily dispersion (A’) also comprises one or more stabilizers ii). Preferably, only one type of stabilizer ii) is used in the invention.

The stabilizer(s) ii) consist of ethylenic polymers chosen from c) polymers of (C3- Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate monomers; and d) copolymers of (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate and (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate.

Preferably, the stabilizer(s) ii) consist of ethylenic polymers chosen from: c) polymers of monomers of formula H2C=C(R)-C(O)-O-R” with R representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl, and R” representing a (C5-Cio)cycloalkyl group such as norbornyl or isobornyl, preferably isobornyl; and d) copolymers of H2C=C(R)-C(O)-O-R’ and of H2C=C(R)-C(O)-O-R” with R, R’ and R” as defined previously.

According to a preferred embodiment, the stabilizer(s) ii) are chosen from isobornyl (meth)acrylate polymers, preferably from isobornyl (meth)acrylate homopolymer and statistical copolymers of isobornyl (meth)acrylate and C1-C4 alkyl (meth)acrylate present in an isobornyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate weight ratio of greater than 4. Advantageously, said weight ratio ranges from 4.5 to 19.

For these statistical copolymers, the defined weight ratio makes it possible to obtain a polymer dispersion that is stable, notably after storage for seven days at room temperature.

Advantageously, the stabilizer ii) is chosen from:

- isobornyl acrylate homopolymers;

- statistical copolymers of isobornyl acrylate/methyl acrylate; - statistical copolymers of isobornyl acrylate/ethyl acrylate; and

- statistical copolymers of isobornyl acrylate/methyl acrylate/ethyl acrylate in the weight ratio described previously.

Advantageously, the sum of polymer particle(s) i) + stabilizer(s) ii) present in the oily dispersion (A’) comprises from 10% to 50% by weight of copolymers d) and from 50% to 90% by weight of polymers a) + b), relative to the total weight of the sum of polymer particle(s) i) + stabilizer(s) ii).

Preferentially, the sum of polymer particle(s) i) + stabilizer(s) ii) present in the oily dispersion (A’) comprises from 15% to 30% by weight of copolymers d) and from 70% to 85% by weight of polymers a) + b), relative to the total weight of the sum of polymer particle(s) i) + stabilizer(s) ii).

The dispersion (A) preferably comprises a total content of particle(s) i) + stabilizer(s) ii) ranging from 1 % to 50% by weight, preferably ranging from 2% to 30% by weight, relative to the total weight of composition (A). iii) Hydrocarbon-based oil(s)

The oily dispersion (A’) comprises one or more hydrocarbon-based oils.

The term “oil” means a fatty substance that is liquid at room temperature (25°C) and at atmospheric pressure.

The term “hydrocarbon-based oil” means an oil formed essentially from, or even consisting of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing any silicon or fluorine atoms. It may contain hydroxyl, ester, ether, carboxylic acid, amine and/or amide groups.

The hydrocarbon-based oil(s) may be volatile or non-volatile.

According to a preferred embodiment of the invention, the hydrocarbon-based oil(s) are volatile.

According to another particular embodiment, the hydrocarbon-based oil(s) are a mixture of a volatile oil and a non-volatile oil.

The term “volatile oil” means an oil (or non-aqueous medium) that can evaporate on contact with the skin in less than one hour, at room temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil, which is liquid at room temperature, notably having a non-zero vapour pressure, at room temperature and at atmospheric pressure, in particular having a vapour pressure ranging from 0.13 Pa to 40 000 Pa (10^-3 to 300 mmHg), preferably ranging from 1.3 Pa to 13000 Pa (0.01 to 100 mmHg) and preferentially ranging from 1.3 Pa to 1300 Pa (0.01 to 10 mmHg).

The term “non-volatile oil” means an oil with a vapour pressure of less than 0.13 Pa.

The hydrocarbon-based oil(s) may be chosen from:

■ hydrocarbon-based oils containing from 8 to 14 carbon atoms, and notably:

- branched Cs-Cu alkanes, for instance Cs-Cu isoalkanes of petroleum origin (also known as isoparaffins), for instance isododecane (also known as 2,2,4,4,6-pentamethylheptane), isodecane and, for example, the oils sold under the trade names Isopar or Permethyl,

- linear alkanes, for instance n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the respective references Parafol 12-97 and Parafol 14-97, and also mixtures thereof, the undecane-tridecane mixture, the mixtures of n-undecane (C11) and of n-tridecane (C13) obtained in Examples 1 and 2 of patent application WO 2008/155 059 from the company Cognis, and

- mixtures thereof;

■ short-chain esters (containing from 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate or n-butyl acetate;

■ hydrocarbon-based oils of plant origin such as triglycerides consisting of fatty acid esters of glycerol, the fatty acids of which may have chain lengths ranging from C4 to C24, these chains possibly being linear or branched, and saturated or unsaturated; these oils are notably heptanoic acid or octanoic acid triglycerides, or alternatively wheatgerm oil, sunflower oil, grapeseed oil, sesame seed oil, corn oil, apricot oil, castor oil, shea oil, avocado oil, olive oil, soybean oil, sweet almond oil, palm oil, rapeseed oil, cotton oil, hazelnut oil, macadamia oil, jojoba oil, alfalfa oil, poppy oil, pumpkin oil, sesame seed oil, marrow oil, rapeseed oil, blackcurrant oil, evening primrose oil, millet oil, barley oil, quinoa oil, rye oil, safflower oil, candlenut oil, passion flower oil or musk rose oil; shea butter; or else caprylic/capric acid triglycerides, for instance those sold by the company Stearinerie Dubois or those sold under the names Miglyol 810®, 812® and 818® by the company Dynamit Nobel;

■ synthetic ethers containing from 10 to 40 carbon atoms;

■ linear or branched hydrocarbons of mineral or synthetic origin, such as petroleum jelly, polydecenes, hydrogenated polyisobutene such as Parleam®, squalane and liquid paraffins, and mixtures thereof; ■ synthetic esters such as oils of formula RIC(O)-O-R2 in which Ri represents a linear or branched fatty acid residue including from 1 to 40 carbon atoms and R2 represents a, notably branched, hydrocarbon-based chain containing from 1 to 40 carbon atoms, on condition that R1 + R2 s 10, for instance purcellin oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, Ci2 to C15 alkyl benzoates, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethylhexyl palmitate, isostearyl isostearate, 2-hexyldecyl laurate, 2-octyldecyl palmitate, 2-octyldodecyl myristate, alcohol or polyalcohol heptanoates, octanoates, decanoates or ricinoleates such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, diisostearyl malate and 2-octyldodecyl lactate; polyol esters and pentaerythritol esters;

■ fatty alcohols that are liquid at room temperature, with a branched and/or unsaturated carbon-based chain containing from 12 to 26 carbon atoms, for instance octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol and 2- undecylpentadecanol.

The oily dispersion (A’) may comprise a silicone oil in addition to the hydrocarbon-based oil(s). If the silicone oil is in the oily dispersion (A’), it is preferably in an amount which does not exceed 10% by weight relative to the weight of the oily dispersion (A’), more particularly in an amount of less than 5%.

The term “silicone oil” means an oil comprising at least one silicon atom and notably at least one Si-0 group. The silicone oil may be volatile or non-volatile.

Volatile silicone oils that may be mentioned include volatile linear or cyclic silicone oils, notably those with a viscosity < 8 centistokes (cSt) (8 x 10'⁶ m²/s), and notably containing from 2 to 10 silicon atoms and in particular from 2 to 7 silicon atoms, these silicones optionally including alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that may be used in the invention, mention may notably be made of dimethicones with viscosities of 5 and 6 cSt, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane, and mixtures thereof.

As non-volatile silicone oils, mention may be made of linear or cyclic non-volatile polydimethylsiloxanes (PDMSs); polydimethylsiloxanes including alkyl, alkoxy and/or phenyl groups, which are pendent or at the end of a silicone chain, these groups containing from 2 to 24 carbon atoms; phenyl silicones, for instance phenyl trimethicones, phenyl dimethicones, phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones, diphenylmethyldiphenyltrisiloxanes, 2-phenylethyl trimethylsiloxysilicates and pentaphenyl silicone oils.

According to a particular embodiment, the oily dispersion (A’) comprises a hydrocarbonbased oil in a content ranging from 60% to 100% by weight relative to the total weight of the oils present in the dispersion and from 0 to 40% by weight of silicone oil relative to the total weight of the oils present in the dispersion. According to a preferred embodiment of the invention, the composition contains as oil only a hydrocarbon-based oil.

Advantageously, the hydrocarbon-based oil(s) are apolar, i.e. formed solely from carbon and hydrogen atoms.

The hydrocarbon-based oil(s) are preferably chosen from hydrocarbon-based oils containing from 8 to 14 carbon atoms, which are in particular volatile, more particularly the apolar oils, described previously.

According to a preferred embodiment, the hydrocarbon-based oil(s) are chosen from isododecane and octyldodecanol.

More preferentially, the hydrocarbon-based oil is isododecane.

According to another advantageous embodiment of the invention, the hydrocarbon-based oil(s) are a mixture of non-volatile and volatile oil; preferably, the mixture comprises isododecane as volatile oil. In particular, in the mixture, the non-volatile oil is a phenyl silicone oil, preferably chosen from pentaphenyl silicone oils.

Process for preparing the oily dispersion (A’)

Without this being limiting, in general, the oily dispersion (A’) according to the invention may be prepared in the following manner:

The polymerization is performed in “dispersion”, i.e. by precipitation of the polymer being formed, with protection of the particles formed with one or more stabilizers, preferably one stabilizer. - In a first step, the stabilizing polymer (or stabilizer ii)) is prepared by mixing the constituent monomer(s) of the stabilizing polymer c) or d) with iv) a free-radical initiator, in a solvent known as the synthesis solvent, and by polymerizing these monomers;

- In a second step, the constituent monomer(s) of the polymer of the particles i) are added to the stabilizing polymer formed in the preceding step and polymerization of these added monomers is performed in the presence of the free-radical initiator.

When the non-aqueous medium is a non-volatile hydrocarbon-based oil iii), the polymerization may be performed in an apolar organic solvent (synthesis solvent), followed by adding the non-volatile hydrocarbon-based oil (which should be miscible with said synthesis solvent) and selectively distilling off the synthesis solvent.

The colouring agent(s) may be added during the first step. According to another variant, the colouring agent(s) are added during the second step or after the second step.

A synthesis solvent which is such that the monomers of the stabilizing polymer and the free- radical initiator are soluble therein, and the polymer particles obtained are insoluble therein, so that they precipitate therein during their formation, is thus chosen.

In particular, the synthesis solvent chosen is one which is apolar and organic, preferably chosen from alkanes such as heptane or cyclohexane.

When the non-aqueous medium is a volatile hydrocarbon-based oil iii), the polymerization may be performed directly in said oil, which thus also acts as synthesis solvent. The monomers should also be soluble therein, as should the free-radical initiator, and the polymer of the particles which is obtained should be insoluble therein.

The monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of from 5% to 45% by weight. The total amount of the monomers may be present in the solvent before the start of the reaction, or a portion of the monomers may be added gradually as the polymerization reaction proceeds.

The polymerization is preferentially performed in the presence vi) of one or more free-radical initiators, notably of the type such as: - peroxide, in particular chosen from tert-butyl peroxy-2-ethylhexanoate: Trigonox 21S; 2,5- dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane: Trigonox 141 ; tert-butyl peroxypivalate: Trigonox 25C75 from AkzoNobel; or

- azo, in particular chosen from AIBN: azobisisobutyronitrile; V50: 2,2’-azobis(2- amidinopropane) dihydrochloride.

The polymerization is preferably performed at a temperature ranging from 70°C to 110°C and at atmospheric pressure.

The polymer particles i) are surface-stabilized, when they are formed during the polymerization, by means of the stabilizer ii).

The stabilization may be performed by any known means, and in particular by direct addition of the stabilizer ii), during the polymerization.

The stabilizer ii) is preferably also present in the mixture before polymerization of the monomers of the polymer of the particles i). However, it is also possible to add it continuously, notably when the monomers of the polymer of the particles i) are also added continuously.

From 10% to 30% by weight and preferably from 15% to 25% by weight of the stabilizer(s) may be used relative to the total weight of monomers used (stabilizers ii) + polymer particles i)).

The oily dispersion of polymer particles (A’) obtained via this preparation process advantageously comprises from 30% to 65% by weight of solids relative to the total weight of said dispersion and preferably from 40% to 60% by weight relative to the total weight of said dispersion.

Composition (B) comprises at least one compound B bearing at least one chemical function B. Compound B is different from compound A.

When the compound(s) B bear several chemical functions B, the chemical functions B may be identical or different. The compound(s) B may comprise chemical functions other than the chemical function(s) B.

Preferably, the compound(s) B do not comprise any chemical functions A.

According to a particular embodiment, composition (B) comprises less than 10% by weight of compound A, preferably less than 5% by weight of compound A, more preferentially less than 2% by weight of compound A relative to the total weight of composition (B); even more preferentially, composition (B) is free of compound A.

Preferably, the chemical function(s) B are chosen from hydroxyl, primary amine, secondary amine, thiol and carboxylic acid functions, and mixtures thereof.

More preferentially, the chemical function(s) B are chosen from hydroxyl, primary amine and thiol functions, and mixtures thereof.

According to a particular variant, the chemical function(s) B are chosen from carboxylic acid functions.

The compound(s) B may be chosen from synthetic or natural polymers.

According to a preferred embodiment, composition (B) comprises as compound(s) B: iv) one or more amine compounds chosen from polyamine compounds containing at least two primary amine and/or secondary amine groups; and/or v) one or more organic or mineral, polymeric or non-polymeric, preferably organic or silicone-based, hydroxylated compounds chosen from polyhydroxylated compounds containing at least two hydroxyl groups; and/or vi) one or more organic or mineral, polymeric or non-polymeric, preferably organic or silicone-based, thiol compounds chosen from polythiol compounds containing at least two thiol groups. iv) amine compound(s)

According to a particularly preferred embodiment, composition (B) comprises as compound(s) B: iv) one or more amine compounds chosen from polyamine compounds containing at least two primary amine and/or secondary amine groups.

The polyamine compounds may be chosen from diamine compounds, triamine compounds and mixtures thereof.

The polyamine compounds may be polymeric or non-polymeric. The term “non-polymeric compound(s)” refers to one or more compounds which are not directly obtained via a monomer polymerization reaction.

According to a particular embodiment of the invention, the polyamine compounds particularly comprise from 2 to 20 carbon atoms; the polyamine compounds are notably non-polymeric.

Polyamine compounds that may notably be mentioned include N-methyl-1 ,3- diaminopropane, N-propyl-1 ,3-diaminopropane, N-isopropyl-1 ,3-diaminopropane, N-cyclohexyl-1 ,3-diaminopropane, 2-(3-aminopropylamino)ethanol, 3-(2- aminoethyl)aminopropylamine, bis(3-aminopropyl)amine, methylbis(3-aminopropyl)amine, N-(3-aminopropyl)-1 ,4-diaminobutane, N,N-dimethyldipropylenetriamine, 1 ,2-bis(3- aminopropylamino)ethane, N,N’-bis(3-aminopropyl)-1 ,3-propanediamine, ethylenediamine, 1 ,3-propylenediamine, 1 ,4-butylenediamine, lysine, cystamine, xylenediamine, tris(2- aminoethyl)amine and spermidine.

The polyamine compounds may have a weight-average molecular weight ranging from 500 to 1 000 000, preferably ranging from 500 to 500 000 and more preferentially from 500 to 100 000.

The polyamine compound(s) may be chosen from:

■ poly((C2-C5)alkyleneimines), and in particular polyethyleneimines and polypropyleneimines, notably poly(ethyleneimine)s (for example the product sold under the reference 46,852-3 by the company Aldrich Chemical);

■ poly(allylamines) (for example the poly(allylamine) sold under the reference 47,913-6 by the company Aldrich Chemical);

■ polyvinylamines and copolymers thereof, notably with vinylamides; mention may notably be made of vinylamine/vinylformamide copolymers, such as those sold under the name Lupamin® 9030 by the company BASF;

■ polyamino acids containing NH2 groups such as polylysine, for example the product sold by the company JNC Corporation (formerly Chisso);

■ aminodextran, such as the product sold by the company CarboMer Inc;

■ amino polyvinyl alcohol, such as the product sold by the company CarboMer Inc;

■ copolymers based on acrylamidopropylamine;

■ chitosans; and ■ polydi(Ci-C4)alkylsiloxanes, in particular polydimethylsiloxanes, comprising amine groups at the chain end or on side chains, in particular terminal or side amino(Ci-Ce)alkyl groups such as aminopropyl, more particularly those of formula (IVb) or (IVc) or (IVd):

in which formula (IVb) R^a and R^b, which may be identical or different, preferably identical, represent a group from among: (Ci-C4)alkyl such as methyl, (Ci-C4)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(Ci-C4)alkyl such as benzyl, or aryl(Ci- C4)alkoxy such as benzoxy, preferably (Ci-C4)alkyl such as methyl, R^c and R’^c, which may be identical or different, preferably identical, represent a hydrogen atom, a (Ci-C4)alkyl group, an amino(Ci-C4)alkyl group or a (Ci-C4)alkylamino(Ci-C4)alkyl group, preferably a hydrogen atom or an amino(Ci-C4)alkyl group such as aminoethyl; X represents a covalent bond, an oxygen atom, preferably a covalent bond, ALK and ALK’, which may be identical or different, preferably identical, represent a (Ci-Ce)alkylene group, preferably (Ci- C4)alkylene group such as propylene; n representing an integer greater than 2 and more particularly the value of n is such that the weight-average molecular weight of the silicone is between 500 and 55 000.

Preferentially, the polydi(Ci-C4)alkylsiloxanes of formula (IVb) are of formula (IV’b) or (IV”b) below:

in which formula (IV’b) the value of n is such that the weight-average molecular weight of the silicone is between 500 and 55 000. As examples of aminosilicones (IVb) or (IV’b), mention may be made of those sold under the names DMS-A11 , DMS-A12, DMS-A15, DMS-A21 , DMS-A31 , DMS-A32 and DMS-A35 by the company Gelest; formula (IV’b) with R^c, R’^c, ALK, ALK’ and n as defined previously for (IVb). Preferably, ALK and ALK’ are identical and represent a (Ci-C4)alkylene group such as propylene, R^c and R’^c are identical and represent an amino(Ci-C4)alkyl group such as aminoethyl.

Mention may be made particularly of Dimethoxysilyl Ethylenediaminopropyl Dimethicone (RN: 71750-80-6), under the trade name GP-RA-157, sold by Genesee Polymers.

in which formula (IVc) R^a, R^b and R^d, which may be identical or different, preferably identical, represent a group from among: (Ci-C4)alkyl such as methyl, (Ci-C4)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(Ci-C4)alkyl such as benzyl, or aryl(Ci- C4)alkoxy such as benzoxy, preferably (Ci-C4)alkyl such as methyl, R^d may also represent a (Ci-Ce)alkyl group substituted with a (Ci-C4)alkylamino or amino group, R^c represents a hydrogen atom or a (Ci-C4)alkyl group, preferably a hydrogen atom; ALK represents a (Ci- Ce)alkylene group, preferably (Ci-C4)alkylene such as propylene; n and m, which may be identical or different, represent an integer greater than 2 and more particularly the values of m and n are such that the weight-average molecular weight of the silicone is between 1000 and 55 000.

Preferentially, the polydi(Ci-C4)alkylsiloxanes of formula (IVc) have the formula (IV’c) below:

in which formula (IV’c) the values of n and m are such that the weight-average molecular weight of the silicone is between 1000 and 55 000. As examples of silicones (IVc), mention may be made of those sold under the names AMS-132, AMS-152, AMS-162, AMS-163, AMS-191 and AMS-1203 by the company Gelest;

in which formula (IVd) R^a and R^b, which may be identical or different, preferably identical, represent a group from among: (Ci-C4)alkyl such as methyl, (Ci-C4)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(Ci-C4)alkyl such as benzyl, or aryl(Ci- C4)alkoxy such as benzoxy, preferably (Ci-C4)alkyl such as methyl, and R^d represents a (Ci-Ce)alkyl group optionally substituted with a (Ci-C4)alkylamino or amino group, preferably (Ci-C4)alkyl such as isobutyl, tert-butyl or n-butyl, R^c represents a hydrogen atom or a (Ci-C4)alkyl group, preferably a hydrogen atom; ALK represents a (Ci-Ce)alkylene group, preferably (Ci-C4)alkylene such as propylene, n representing an integer greater than 2 and more particularly the value of n is such that the weight-average molecular weight of the silicone is between 500 and 5000.

Preferentially, the polydi(Ci-C4)alkylsiloxanes of formula (IVd) have the formula (IV’d) below:

in formula (IV’d), the value of n is such that the weight-average molecular weight of the silicone is between 500 and 3000. As examples of silicones (IVd), mention may be made of the products sold under the names MCR-A11 and MCR-A12 by the company Gelest;

■ the amodimethicones of formula (IVe):

in which formula (IVe):

R^a and R^b, which may be identical or different, preferably identical, represent a group from among: (Ci-C4)alkyl such as methyl, (Ci-C4)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(Ci-C4)alkyl such as benzyl, or aryl(Ci-C4)alkoxy such as benzoxy, preferably (Ci-C4)alkyl such as methyl;

R^c represents a hydrogen atom or a (Ci-C4)alkyl group, preferably a hydrogen atom;

R^e represent a hydroxyl, (Ci-C4)alkoxy, amino or (Ci-C4)alkylamino group;

R^f represents a (Ci-C4)alkyl group such as methyl, a (Ci-C4)alkoxy group such as methoxy, a hydroxyl or -O-(SiR2)_xR’ group with R representing a (Ci-C4)alkyl or (Ci-C4)alkoxy group and R’ representing a (Ci-C4)alkoxy or hydroxyl group; preferably, R^f represents a (Ci- C4)alkyl, (Ci-C4)alkoxy or -O-(SiR2)_xR’ group with R representing a (Ci-C4)alkyl group such as methyl and R’ a hydroxyl or (Ci-C4)alkoxy group such as methoxy;

ALK and ALK’, which may be identical or different, represent a (Ci-Ce)alkylene group, preferably (Ci-C4)alkylene such as ethylene or propylene; n and m, which may be identical or different, represent an integer greater than 2, p and x are integers greater than or equal to 0; preferably, p is between 2 and 20 and more particularly the values of m, n, p and x are such that the weight-average molecular weight of the silicone is between 2000 and 700 000, preferentially between 5000 and 500 000.

Preferentially, the amodimethicones of formula (IVe) are of formula (IV’e) or (IV”e) below:

in which formula (IV’e) ALK represents a (Ci-Ce)alkylene group, preferably ethylene, ALK’ represents a (Ci-Ce)alkylene group, preferably propylene, and m, n and p represents an integer greater than 2, with m, n and p such that the weight-average molecular mass of the compound is approximately between 5000 and 500 000; preferably, p represents an integer between 8 and 20;

in which formula (IV’e):

R^a and R^b, which may be identical or different, preferably identical, represent a (Ci-C4)alkyl group such as methyl or a (Ci-C4)alkoxy group such as methoxy, preferably a (Ci-C4)alkyl group such as methyl;

R⁹ represents a hydrogen atom or a (Ci-C4)alkyl group;

R^f represents a (Ci-C4)alkyl group such as methyl, a (Ci-C4)alkoxy group such as methoxy, or -O-(SiR2)x- ’ with R representing a (Ci-C4)alkyl group such as methyl and R’ a hydroxyl or (Ci-C4)alkoxy group such as methoxy;

ALK represents a (Ci-Ce)alkylene group, preferably ethylene;

ALK’ represents a (Ci-Ce)alkylene group, preferably propylene; n and m, which may be identical or different, representing an integer greater than 2, x is an integer greater than or equal to 0; preferably, the values of m, n and x are such that the weight-average molecular weight of the silicone is between 2000 and 700000, preferentially between 5000 and 500 000.

Even more preferentially, the amodimethicones of formula (IVe) are of formula (IV”’e) below:

(IV”’e) in which formula (IV”’e):

R^f, R⁹, ALK, ALK’, m and n are as defined for (IV”e). The amodimethicones and trimethylsiloxyamodimethicones belonging to formula (IV”e) and to formula (IV”’e) above are, for example, the amodimethicones and trimethylsiloxyamodimethicones of ADM type sold by the company Wacker-Belsil®; mention may also be made of polydimethylsiloxanes bearing aminoethylaminopropyl groups, bearing a methoxy and/or hydroxyl function and a-co silanols as a cationic 60% aqueous emulsion (supplier reference: Xiameter MEM-8299 Emulsion by Dow Corning or under the supplier reference: Belsil ADM 4000 E by Wacker); polydimethylsiloxanes bearing aminoethyl iminopropyl groups, as a stored nonionic 15% microemulsion (supplier reference: Belsil ADM Log 1);

■ the polyether amines known notably under the reference Jeffamine from the company Huntsman; and notably: polyethylene glycol and/or polypropylene glycol a,co-diamines (bearing a chain-end amine function), such as those sold under the names Jeffamine D- 230, D-400, D-2000, D-4000, ED-600, ED-9000, ED-2003;

■ polytetrahydrofuran (or polytetramethylene glycol) a,co-diamines, polybutadiene a, codiamines;

■ polyamidoamine (PAMAM) dendrimers bearing amine terminal functions;

■ poly(meth)acrylates or poly(meth)acrylamides bearing primary or secondary amine side functions, such as poly(3-aminopropyl)methacrylamide or poly(2-aminoethyl) methacrylate; and ■ mixtures thereof.

As polyamine compounds bearing at least two primary amine and/or secondary amine groups, use is preferably made of polydi(Ci-C4)alkylsiloxanes comprising primary amine groups at the chain end and/or on side chains.

More preferentially, the amine compound(s) iv) included in composition (B) are chosen from those of formulae (IVb) and (IVe) as defined previously and even more preferentially from those of formulae (IV’b) and (IV’e) as defined previously. v) hydroxylated compound(s)

According to one embodiment, composition (B) comprises as compound(s) B: v) one or more organic or mineral, polymeric or non-polymeric, preferably organic or silicone, hydroxylated compounds chosen from polyhydroxylated compounds containing at least two hydroxyl groups.

The term “non-polymeric compound(s)” refers to one or more compounds which are not directly obtained via a monomer polymerization reaction.

The hydroxylated compound(s) of the invention may be organic or mineral, preferably organic.

According to an advantageous variant, the hydroxylated compound(s) are silicone compounds, i.e. they include at least two hydroxyl groups, and at least one siloxane chain.

According to a particular embodiment of the invention, the hydroxylated compound(s) are mineral.

The polyhydroxylated compounds may comprise other non-reactive chemical functions such as ester, amide, ketone or urethane functions. It is possible to use a mixture of different polyhydroxylated compounds such as a mixture of organic and mineral polyhydroxylated compounds.

Non-polymeric hydroxylated compounds

According to a preferred embodiment of the invention, the hydroxylated compound(s) are non-polymeric compounds of formula (II): L(OH)q (II) in which formula (II): q represents an integer greater than or equal to 2, preferably ranging from 2 to 10, more preferentially ranging from 2 to 5;

L denotes a saturated or unsaturated linear or branched, or a saturated or unsaturated (hetero)cyclic, multivalent (at least divalent) group, in particular comprising from 1 to 500 carbon and/or silicon atoms, more particularly from 2 to 40 carbon and/or silicon atoms, even more particularly from 3 to 30 carbon and/or silicon atoms, preferably from 6 to 20 carbon atoms;

L being optionally interrupted and/or terminated with one or more heteroatoms or groups chosen from O, S, N, Si and C(X), and combinations thereof such as -O-, -O-C(X)-, -N(R)- C(X)- or -Si(R_c)(Rd)-O- with R representing a hydrogen atom or a (Ci-Ce)alkyl group such as methyl; and/or

L being optionally substituted with one or more halogen atoms, or a group chosen from Ra(R_b)N- and -(X’)_a-C(X)-(X”)_b-R_a;

■ X, X’ and X”, which may be identical or different, represent an oxygen or sulfur atom, or a group N(R_b);

- a and b being equal to 0 or 1 ; preferably, the sum a + b is equal to 1 ;

- R_a and R_b, which may be identical or different, represent a hydrogen atom or a (Ci-Ce)alkyl or aryl(Ci-C4)alkyl group such as benzyl; preferably, R_a and R_b represent a hydrogen atom;

- R_c and Rd, which may be identical or different, represent a (Ci-Ce)alkyl, aryl(Ci-C4)alkyl or (Ci-Ce)alkoxy group.

According to a particular embodiment of the invention, the hydroxylated compound(s) are of formula (II) in which: q represents an integer greater than or equal to 2, preferably ranging from 2 to 10, more preferentially ranging from 2 to 5;

L denotes a saturated or unsaturated linear or branched, or saturated or unsaturated (hetero)cyclic, multivalent (at least divalent) radical comprising from 8 to 30 carbon and/or silicon atoms, preferably from 10 to 20 carbon and/or silicon atoms, L also possibly being interrupted with one or more oxygen atoms, and/or comprises one or more functions chosen from amino, ether, thio ether, ester, thio ester, ketone, thio ketone, amide and thio amide functions.

According to this particular embodiment, the polyol compound is preferably a diol compound. According to this particular embodiment, L preferably denotes a multivalent, notably linear, C₈-Ci8 radical.

Preferentially, the polyol is a notably linear, in particular liposoluble Cs-C diol. Advantageously, the Cs-C chain is a hydrocarbon-based chain, i.e. formed from carbon and hydrogen.

In particular, the polyol is a linear Cs-C and notably C10-C14 diol.

As polyols according to this particular embodiment of the invention, mention may be made of 1 ,8-octanediol, 1 ,10-decanediol, 1 ,12-dodecanediol, 1 ,14-tetradecanediol, 1 ,16- hexadecanediol and 1 ,18-octadecanediol.

Use is preferably made of 1 ,10-decanediol, 1 ,12-dodecanediol or 1 ,14-tetradecanediol. 1 ,12-Dodecanediol is preferentially used.

Polymeric hydroxylated compounds

According to one embodiment of the invention, the hydroxylated compound(s) are polymeric. The polymeric hydroxylated compound(s) of the invention may be star, comb, brush and dendritic homopolymers or copolymers bearing hydroxyl units. The polymers may be of natural origin such as polysaccharides or polypeptides, or of synthetic origin such as (meth)acrylic polymers, polyesters or polyglycols. The hydroxyl units may be present as terminal and/or side groups.

The polymeric hydroxylated compound(s) are preferably organic or silicone polymers, more preferentially of formula (V):

(HO)pPOLY (V) in which formula (V): p represents an integer greater than or equal to 2;

POLY denotes a polymeric radical which is preferably carbon-based or silicone-based;

POLY being optionally interrupted with one or more heteroatoms or groups chosen from O, S, N, Si and C(X), and combinations thereof such as -O-, -O-C(X)-, -N(R)-C(X)- or -Si(R_c)(Rd)-O- with R representing a hydrogen atom or a (Ci-Ce)alkyl group such as methyl; and/or

POLY being optionally substituted with one or more halogen atoms, or a group chosen from Ra(R_b)N- and -(X’)_a-C(X)-(X”)_b-R_a;

- a and b being equal to 0 or 1 ; preferably, the sum a + b is equal to 1 ; - R_a and Rb, which may be identical or different, represent a hydrogen atom or a (Ci-C )alkyl or aryl(Ci-C4)alkyl group such as benzyl; preferably, R_a and Rb represent a hydrogen atom; and

- R_c and Rd, which may be identical or different, represent a (Ci-C )alkyl, aryl(Ci-C4)alkyl or (Ci-Cio)alkoxy group.

According to a particular embodiment of the invention, the polymeric hydroxylated compound(s) are of formula (V) in which: p represents an integer greater than or equal to 2;

POLY denotes a carbon-based or silicone-based polymeric radical, POLY also possibly containing one or more heteroatoms such as O, N or S, and/or one or more functions chosen from amino, (thio)-ester, (thio)-ketone, (thio)-amide, (thio)-urea and (thio)carbamate functions, and/or possibly being substituted with one or more linear or branched (Ci- Cw)alkyl or linear or branched (Ci-C )alkoxy groups, it being understood that when POLY is substituted, the hydroxyl groups may be borne by the substituent(s).

The weight-average molecular weight of the polyol polymer compounds, such as those of formula (V), is generally between 500 and 400 000, preferably between 500 and 150 000. Preferably, the polymeric hydroxylated compound(s) may be (poly)ol polymers, notably polyolefin (poly)ols, polydi(Ci-C6)alkylsiloxane (poly)ols or polyester (poly)ols. Preferably, the (poly)ols are diols.

The polyolefin (poly)ols may be polydienes bearing hydroxyl end groups, for instance those described in FR-A-2 782 723. They may be chosen from (poly)ols derived from homopolymers and copolymers of polybutadiene, of polyisoprene and of poly(1 ,3- pentadiene). They preferably have a number-average molecular mass (Mn) of less than 7000, preferably between 1000 and 5000. Mention will be made in particular of the hydroxylated polybutadienes sold by the company Cray Valley under the brand names Poly BD R45HTLO, Poly BD R45V and Poly BD R-20 LM, which will preferably be used hydrogenated; and also (poly)hydroxylated hydrogenated (1 ,2-polybutadienes), such as GI3000 of Mn = 3100, GI2000 (Mn = 2100) and GI1000 (Mn = 1500) sold by the company Nisso.

According to one embodiment of the invention, the polymeric hydroxylated compound(s) are polyolefin (poly)ols of formula (VI):

in which formula (VI):

ALK⁴ and ALK⁵, which may be identical or different, preferably different, represent a linear or branched (Ci-Ce)alkylene group, optionally substituted with one or more hydroxyl, thiol or amino groups; preferably, ALK⁴ represents a linear (Ci-Ce)alkylene group such as n- butylene, and ALK⁵ represents a branched (C3-Ce)alkylene group such as /-butylene;

X represents an oxygen or sulfur atom or a group N(Ra) with Ra representing a hydrogen atom or a (Ci-C4)alkyl group; preferably, X represents an oxygen or sulfur atom, more preferentially an oxygen atom; and n and m, which may be identical or different, represent an integer, with n + m representing an integer greater than or equal to 1.

Among the polyolefins bearing hydroxyl end groups of formula (VI), mention may be made preferentially of polyolefin homopolymers or copolymers bearing a,w-hydroxy end groups, such as polyisobutylenes bearing a,w-hydroxy end groups and the copolymers of formula (VP):

(vrj notably those sold by Mitsubishi under the brand name Polytail. Hydrogenated polybutadiene diols are preferably used.

The polydi(Ci-C6)alkylsiloxane (poly)ols are particularly chosen from those of formula (VII):

in which formula (VII): R^a and R^b, which may be identical or different, preferably identical, represent a group from among: (Ci-Ce)alkyl optionally substituted with one or more hydroxyl, amino or thiol groups; (Ci-Ce)alkoxy such as methoxy; aryl such as phenyl; aryloxy such as phenoxy; aryl(Ci- C4)alkyl such as benzyl; or aryl(Ci-C4)alkoxy such as benzoxy; preferably (Ci-C4)alkyl such as methyl; n represents an integer greater than or equal to 1 and more particularly the value of n is such that the weight-average molecular weight of the silicone ranges from 500 to 55 000; in particular, n is an integer ranging from 1 to 100, preferably ranging from 5 to 50 and preferentially ranging from 10 to 30; and

L⁴ and L⁵, which may be identical or different, represent a covalent bond or a saturated or unsaturated, linear or branched, optionally cyclic hydrocarbon-based chain comprising from 1 to 100 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen, more preferentially a (Ci-Ce)alkylene, (C1- Ce)alkylenoxy, oxy(Ci-Ce)alkylene, (Ci-C6)alkylenoxy(Ci-C6)alkylene, (C1- C6)alkylenoxy(Ci-C6)alkylenoxy or oxy(Ci-C6)alkylenoxy(Ci-C6)alkylene group;

X represents an oxygen or sulfur atom, preferably an oxygen atom.

Preferably, the polydimethylsiloxane (poly)ols are chosen from those of formula (VII’):

in which formula (VII’):

L⁴ and L⁵ are as defined previously, and preferably represent a divalent group chosen from -R2-, -O-R2-, -R2-O- and -R2-O-R’2-, preferably -R2-O-R’2-, with R2 and R’2, which may be identical or different, representing a linear or branched (C2-Ce)alkylene group, such as ethylene or propylene; and n represents an integer ranging from 1 to 100, preferably ranging from 5 to 50 and preferentially ranging from 10 to 30.

Polydimethylsiloxanes diols that may be used include those sold under the names KF-6000, KF-6001 , KF-6002 and KF-6003 by the company Shin-Etsu Chemicals.

Use is preferably made of the polydimethylsiloxane diol of formula (VII”):

Use may also be made of dimethiconols, which are polydimethylsiloxanes bearing OH terminal functions. Mention may be made, for example, of the product sold under the name Xiameter PMX-1502 Fluid by the company Dow Corning.

According to a particular form of the invention, the polymeric hydroxylated compound(s) denote compounds of formula (Illa) below:

in which formula (Illa):

Ri, which may be identical or different, independently represents a hydroxyl group; an alkyl group containing from 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, notably 1 to 2 carbon atoms such as a methyl; an alkoxy group containing from 1 to 2 carbon atoms; or a group -(CH2)_s-Si(R4)3 in which s denotes an integer ranging from 1 to 4 such as 2 and R4 independently denotes an alkoxy group containing from 1 to 2 carbon atoms;

R’a and R”2 independently represent an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, notably 1 to 2 carbon atoms such as a methyl; a denotes an integer ranging from 0 to 10, b denotes an integer ranging from 0 to 500 with a+b > 4.

Among the silicones of formula (Illa), mention may be made of polydimethylsiloxanes (PDMS) bearing hydroxyl terminal functions, such as the compounds sold by the company Shin-Etsu under the name KF-9701 or X-21-5841 , or those sold by the company Sigma- Aldrich under the reference 481939 (Mn -550, -25 cSt), 481955 (-65 cSt), or 481963 (-750 cSt). Mention may also be made of the compounds sold by the company Gelest under the name DMS-S12 (16-32 cSt), DMS-S15 (45-85 cSt), DMS-S21 (90-120 cSt), DMS-S27 (700-800 cSt) or DMS-S31 (-1000 cSt).

According to a preferred embodiment, the silicone(s) of formula (Illa) used in the context of the invention are chosen from the compounds of formula (Illa) in which:

Ri independently represents an alkyl group containing from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and more particularly from 1 to 2 carbon atoms, such as a methyl;

R’a and R”2 independently represent an alkyl group containing from 1 to 10 carbon atoms, preferably an alkyl group containing from 1 to 4 carbon atoms and more particularly from 1 to 2 carbon atoms such as a methyl; b denotes an integer ranging from 0 to 10, a denotes an integer ranging from 0 to 5 with a+b > 4.

According to a particular embodiment of the invention, the hydroxylated compound(s) are chosen from polymeric compounds such as hyperbranched polymers and dendrimers.

“Hyperbranched polymers” are molecular constructions having a branched structure, generally around a core. Their structure is generally free of symmetry. Specifically, the base units or monomers which served for the construction of the hyperbranched polymer may be of different nature and their distribution is irregular. The branches of the polymer may be of different nature and lengths. The number of base units, or monomers, may be different according to the different branchings. While being asymmetric, hyperbranched polymers may have an extremely branched structure, around a core; successive generations or layers of branching; a layer of terminal chains.

Hyperbranched polymers are generally derived from the polycondensation of one or more monomers ABx, A and B being reactive groups that are capable of reacting together, x being an integer greater than or equal to 2, but other preparation processes may be envisaged.

Hyperbranched polymers are characterized by their degree of polymerization DP = 1-b, b being the percentage of non-terminal functions of B which have not reacted with a group A. Since the condensation is not systematic, unlike for the synthesis of dendrimers (see hereinbelow), the degree of polymerization is less than 100%. A terminal group T on the hyperbranched polymer can be made to react to obtain a particular function at the end of chains.

Several hyperbranched polymers can be combined together, by covalent bonding or another type of bonding, by means of their terminal groups. Such polymers, which are said to be bridged, are included in the definition of the hyperbranched polymers according to the present invention.

Numerous hyperbranched polymers and dendrimers have already been described. Reference may be made, for example, to: D.A. Tomalia et al., Angew. Chem. Int. Ed. Engl. 29 138-175 (1990); N. Ardoin and D. Astruc, Bull. Soc. Chim. Fr. 132, 875-909 (1995); B.l. Voit, Acta Polymer, 46, 87-99 (1995).

Such polymers are described in particular in B.l. Voit, Acta Polymer, 46, 87-99 (1995); EP- 682 059; WO-96/14346; WO-96/14345; WO-96/12754. Several hyperbranched polymers can be combined together, by covalent bonding or another type of bonding, by means of their terminal groups.

Such polymers, which are said to be bridged, are included in the definition of the hyperbranched polymers according to the present invention.

“Dendrimers” are macromolecules consisting of monomers which associate by means of an arborescent process around a multifunctional central core.

Dendrimers thus have a fractal (or fractal molecule) structure, consisting of a core, a given number of generations of branches (or wedges), of internal cavities originating from said branches of the molecule, and of terminal functions.

Dendrimers are, structurally, highly branched polymers and oligomers having a well-defined chemical structure.

Dendrimers may be in the form of an assembly of molecules of the same generation, the assembly being referred to as “monodisperse”; they may also be in the form of assemblies of different generations, which are referred to as being “polydisperse”. The definition of dendrimers according to the present invention includes monodisperse dendrimer assemblies as well as polydisperse dendrimer assemblies.

The generations of branches consist of structural units, which are identical for the same generation of branches and which may be identical or different for branches of different generations. All of the junction points of branches of the same generation are located an equal distance from the core; this corresponds to a generation.

The generations of branches extend radially in a geometrical progression from the core. The terminal groups of an n^th generation dendrimer are the terminal functional groups of the branches of the n^th generation, referred to as the terminal generation.

The definition of dendrimers given above includes molecules bearing symmetrical branching; it also includes molecules bearing non-symmetrical branching, for instance dendrimers in which the branches are lysine groups, in which the branching of one generation of wedges on the preceding generation takes place on the a and E amines of lysine, which leads to a difference in the length of the wedges of the various branches. Dendrimers also known as “dense star polymers” or “starburst polymers” or “rod-shaped dendrimers” are included in the present definition of dendrimers. The molecules known as “arborols” and “cascade molecules” are also included in the definition of dendrimers according to the present invention.

Moreover, several dendrimers may be combined together, via a covalent bond or another type of bonding, by means of their terminal groups to give species known as “bridged dendrimers” or “dendrimer aggregates”. Such species are included in the definition of dendrimers according to the present invention.

In the case where composition (B) comprises as compound(s) B: v) the hydroxylated compound(s) as defined previously, the process according to the invention may advantageously use one or more amine catalysts, the amine catalyst(s) preferably being present in composition (B).

The amine catalyst(s) may be chosen from catalysts bearing a tertiary amine function or bearing an aminidine function or bearing a guanidine function.

The catalysts bearing a tertiary amine function may be chosen from triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, methyldibutylamine, N- methyldicyclohexylamine, N,N-dimethylcyclohexylamine, ethyldiisopropylamine, N,N- diethylcyclohexylamine, pyridine, 4-dimethylaminopyridine, N-methylpiperidine, N- ethylpiperidine, N-n-butylpiperidine, 1 ,2-dimethylpiperidine, N-methylpyrrolidine, 1 ,2- dimethylpyrrolidine, dimethylaniline, picoline, N,N-dimethylbenzylamine, bis(2- dimethylaminoethyl) ether, N,N,N’,N’,N”-pentamethyldiethylenetriamine, N,N,N’,N’- tetramethylethylenediamine, N-methylmorpholine, N-ethylmorpholine and 1 ,4- diazabicyclo[2.2.2]octane, and mixtures thereof.

Diisopropylethylamine is preferably used.

The catalysts bearing an aminidine function are, for example, 1 ,5-diazabicyclo[4.3.0]non-5- ene (or DBN) and 1 ,8-diazabicyclo[5.4.0]undec-7-ene (or DBU). The catalysts bearing a guanidine function may be chosen from the compounds of formula (la) below:

in which R1, R2, R3, R4 and R5 independently represent a hydrogen atom or a linear or branched C1-C4 lower alkyl or alkenyl radical, when R1, R2 and R3 and R4 represent a hydrogen atom, R5 may also denote a radical from among: acetyl; carboxamide; methoxy; ethoxy; 1 ,2,4-triazolyl; cyclopentyl; methoxycarbonyl; ethoxycarbonyl; phenyl; benzyl; thiazolidone; benzimidazole; benzoxazole; benzothiazole; or C(=NH)-NR6R7 in which R6 and R7 denote, independently of each other, a hydrogen atom or a linear or branched C1-C4 lower alkyl radical; or else a phenyl radical, when R1=R2=R3=H, R4 and R5 may also form, with the nitrogen atom that bears them, a pyrrolidine, piperidine, pyrazole or 1 ,2,4-triazole ring, when R1=R2=H, and R4=H or methyl, R3 and R5 may also together form a 5-membered ring optionally containing an oxo group, and the organic or mineral salts thereof.

Salts that may be mentioned include the hydrochloride, sulfate, sulfamate, carbonate, bicarbonate, phosphate and acetate salts.

As compounds of formula (la), mention may notably be made of the following compounds: guanidine, aminoguanidine, 1 -acetylguanidine, guanylurea, phenylguanidine, 1,1- dimethylguanidine, 1-ethylguanidine, 1 , 1 -diethylguanidine, creatine, agmatine, biguanide, N-methyl biguanide, N-ethyl biguanide, N-propyl biguanide, N-butylbiguanide, 1,1- dimethylbiguanide, 1-phenylbiguanide, 1,1,3,3-tetramethylguanidine, 2-tert-butyl-1 , 1 ,3,3- tetramethylguanidine, 1 H-pyrazole-1-carboxamidine, 5-hydroxy-3-methyl-1 H-pyrazole-1- carboximidamide, 3,5-diamino-1 H-1,2,4-triazole-1-carboximidamide, 2-guanidone-4- thiazolidone, 2-guanidinobenzimidazole, 2-guanidinobenzoxazole, 2- guanidinobenzothiazole, 1,1,3,3-tetramethylguanidine (or TMG), 1,5,7- triazabicyclo[4.4.0]dec-5-ene (or TBD), 7-methyl-1 ,5,7-triazabicyclo[4.4.0]dec-5-ene (or MTBD). The amine catalyst(s) may be present in composition (B) in a content ranging from 0.1% to 0.5% by weight and preferably ranging from 0.1% to 0.2% by weight relative to the total weight of composition (B). vi) thiol compound(s)

According to one embodiment, composition (B) comprises as compound(s) B: vi) one or more organic or mineral, polymeric or non-polymeric, preferably organic or silicone, thiol compounds chosen from polythiol compounds containing at least two thiol groups.

The thiol compound(s) of the invention may be organic or mineral, preferably organic.

According to an advantageous variant, the thiol compound(s) are silicone compounds, i.e. they include at least two thiol groups, and at least one siloxane chain.

According to a particular embodiment of the invention, the thiol compound(s) are mineral. Mention may be made, for example, of polythiol silicones and polythiol silicas.

The thiol compounds of the invention may or may not be liposoluble.

The term “liposoluble compound” means a compound that is soluble or miscible to at least 1% by weight in isododecane at 25°C.

Non-polymeric thiol compounds

According to one embodiment of the invention, the thiol compound(s) are non-polymeric compounds of formula (HA):

L(SH)q (HA) in which formula (HA): q represents an integer greater than or equal to 2, preferably ranging from 2 to 10, more preferentially ranging from 2 to 5;

- X, X’ and X”, which may be identical or different, represent an oxygen or sulfur atom, or a group N(Rb);

- a and b being equal to 0 or 1 ; preferably, the sum a + b is equal to 1 ;

According to this embodiment, the polythiol compound is preferably a dithiol compound.

According to this embodiment, L preferably denotes a multivalent, notably linear, Cs-C radical. Preferentially, the polythiol is a notably linear Cs-C dithiol. Advantageously, the C₈-Ci8 chain is a hydrocarbon-based chain, i.e. formed from carbon and hydrogen. In particular, the liposoluble polythiol is a linear Cs-C and notably C10-C14 dithiol.

As polythiol of formula (HA), mention may be made of 1 ,8-octanedithiol, 1 ,10-decanedithiol, 1 ,12-dodecanedithiol, 1 ,14-tetradecanedithiol, 1 ,16-hexadecanedithiol and 1 ,18- octadecanedithiol.

Use is preferably made of 1 ,10-decanedithiol, 1 ,12-dodecanedithiol or 1 ,14- tetradecanedithiol. 1 ,12-Dodecanedithiol is preferentially used.

According to a particular embodiment of the invention, the thiol compound(s) are non- polymeric compounds of formula (IB):

W(SH)_n (IB) in which formula (IB): n denotes an integer greater than or equal to 2, preferably ranging from 2 to 10, preferably ranging from 2 to 5, and W denotes a linear or branched or (hetero)cyclic, saturated C2-C80 multivalent (at least divalent) radical, an aromatic radical, or a heteroaromatic cyclic radical, W also possibly containing one or more heteroatoms such as O, N or S and/or one or more functions chosen from ester, ketone, amide and urea functions, preferably ester and ketone functions, and/or possibly being substituted with one or more linear or branched C1-C10 alkyl or linear or branched C1-C10 alkoxy groups, it being understood that when the radical W is substituted, the thiol functions may be borne by the substituent(s).

The term “cyclic radical” means a hydrocarbon-based or heterocyclic saturated monocyclic radical, a saturated or aromatic polycyclic radical, for example biphenyl, or fused rings, for instance a naphthyl radical.

The molar mass of the compounds of formula (IB) generally ranges from 90 to 1500.

According to a more particular first embodiment, the thiol compound(s) of formula (IB) are such that n = 2 and W denotes a linear or branched C2-C20, preferably linear or branched C2-C12 saturated divalent hydrocarbon-based radical.

According to this more particular first embodiment, the thiol compound(s) may be chosen from: 1 ,2-ethanedithiol, 1 ,2-propanedithiol, 1 ,3-propanedithiol, 1 ,4-butanedithiol, 1 ,6- hexanedithiol, 1 ,7-heptanedithiol, 1 ,8-octanedithiol, 1 ,9-nonanedithiol, 1 ,10-decanedithiol, 1 ,12-dodecanedithiol, 2,2-dimethyl-1 ,3-propanedithiol, 3-methyl-1 ,5-pentanedithiol, 2- methyl-1 ,8-octanedithiol.

According to a more particular second embodiment, the thiol compound(s) of formula (IB) are such that n = 3 and W denotes a linear or branched C3-C20, preferably linear or branched C2-C12 saturated trivalent hydrocarbon-based radical.

According to this more particular second embodiment, the thiol compound(s) may be chosen from 1 ,1 ,1-tris(mercaptomethyl)ethane, 2-ethyl-2-mercaptomethyl-1 ,3- propanedithiol and 1 ,2,3-propanetrithiol.

According to a more particular third embodiment, the thiol compound(s) of formula (IB) are such that n = 2 or 3 and W denotes a linear or branched C3-C20, preferably linear or branched C2-C12 saturated divalent or trivalent hydrocarbon-based radical, said radical containing one or more non-adjacent heteroatoms chosen from O and S.

According to this more particular third embodiment, the thiol compound(s) may be chosen from:

C2-C12 bis-mercaptoalkyl ethers and sulfides such as bis(2-mercaptoethyl) ether, bis(2- mercaptoethyl) sulfide and bis(2-mercaptoethylthio-3-mercaptopropane) sulfide; bis(2-mercapto((Ci-C3)alkyl)thio) (Ci-Cs)alkanes or bis(2-mercapto((Ci-C3)alkyl)thio) (C1- C5)mecaptoalkanes, for instance bis(2-mercaptoethylthio)methane, 1 ,2-bis(2- mercaptoethylthio)ethane, 1 ,3-bis(2-mercaptoethylthio)propane, 1 ,2-bis(2- mercaptoethylthio)propanethiol, 1 ,2-bis(2-mercaptoethyl)thio-3-mercaptopropane, or 1 ,2,3- tris(2-mercaptoethylthio)propane. Preferably, according to this more particular third embodiment, the thiol compound(s) are chosen from 1 ,2-bis(2-mercaptoethylthio)propanethiol, 1 ,2,3-tris(2- mercaptoethylthio)propane and tetrakis(2-mercaptoethylthiomethyl)methane.

According to a more particular fourth embodiment, the thiol compound(s) of formula (IB) are such that n denotes an integer greater than or equal to 2 and W denotes a linear or branched C3-C20, preferably linear or branched C2-C12, hydrocarbon-based saturated multivalent (at least divalent) radical, said radical containing at least one ester function.

According to this more particular fourth embodiment, the thiol compound(s) may be chosen from: esters of polyols (glycols, triols, tetraols, pentaols, hexaols) and of C1-C6 mercaptocarboxylic acid, such as ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(thioglycolate), trimethylolpropane tris(thioglycolate), trimethylolpropane tris(P-mercaptopropionate), pentaerythrityl tetrakis(thioglycolate), pentaerythrityl tetrakis(P-mercaptopropionate), dipentaerylthrityl hexakis(P-mercaptoproprionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythrityl tetrakis(2-mercaptoacetate), pentaerythrityl tetrakis(3-mercaptopropionate), pentaerythrityl tetrakis(3- mercaptobutanate), and dipentaerythrityl hex-3-mercaptopropionate.

Preferably, according to this more particular fourth embodiment, the thiol compound(s) are chosen from trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3- mercaptopropionate), pentaerythrityl tetrakis(2-mercaptoacetate), pentaerythrityl tetrakis(3- mercaptopropionate), pentaerythrityl tetrakis(3-mercaptobutanate) and dipentaerythrityl hex-3-mercaptopropionate.

Particularly preferably, the thiol compound is pentaerythrityl tetrakis(3- mercaptopropionate).

According to a more particular fifth embodiment, the thiol compound(s) of formula (IB) are such that n = 4 and W denotes a branched C4-C20, preferably Cs-Cu saturated tetravalent hydrocarbon-based radical interrupted with one or more non-adjacent sulfur atoms.

According to this more particular fifth embodiment, the thiol compound(s) may be chosen from tetrakis(2-mercaptoethylthiomethyl)methane and bis(2-mercaptoethylthio-3- mercaptopropane) sulfide.

According to a more particular sixth embodiment, the thiol compound(s) of formula (IB) are such that n = 2 and W denotes a hydrocarbon-based cyclic divalent radical optionally containing one or more non-adjacent sulfur atoms, optionally substituted with one or more linear or branched C1-C10 alkyl radicals.

According to this more particular sixth embodiment, the thiol compound(s) may be chosen, for example, from 1 ,4-cyclohexanedithiol, 1 ,4-bis(mercaptomethyl)cyclohexane, 1 ,1- cyclohexanedithiol, 1 ,2-cyclohexanedithiol, 1 ,1-bis(mercaptomethyl)cyclohexane and 2,5- dimercapto-1 ,4-dithiane.

According to a more particular seventh embodiment, the thiol compound(s) of formula (IB) are such that n = 3 and W denotes a substituted isocyanurate-type cyclic radical.

According to this more particular seventh embodiment, the thiol compound(s) may be chosen from polythiols of the isocyanurate class, described in patents US 3 676 440 and US 2011/0 230 585, such as tris((mercaptopropionyloxy)ethyl) isocyanurate.

According to a more particular eighth embodiment, the thiol compound(s) of formula (IB) are such that n = 2 or 3 or 4 and W denotes an aromatic radical optionally substituted with one or more identical or different radicals of (Ci-C )alkyl or (Ci-C )alkoxy type, it being understood that when the radical W is substituted, the thiol functions may be borne by the substituent(s).

According to this more particular eighth embodiment, the thiol compound(s) may be chosen from:

1 .2-dimercaptobenzene, 1 ,3-dimercaptobenzene,

1 ,4-dimercaptobenzene, 1 ,2-bis(mercaptomethyl)benzene,

1 .3-bis(mercaptomethyl)benzene,

1 .4-bis(mercaptomethyl)benzene,

1.2-bis(2-mercaptoethyl)benzene,

1.3-bis(2-mercaptoethyl)benzene,

1.4-bis(2-mercaptoethyl)benzene,

1.2-bis(2-mercaptoethyleneoxy)benzene,

1.3-bis(2-mercaptoethyleneoxy)benzene,

1.4-bis(2-mercaptoethyleneoxy)benzene,

1 .2.3-trimercaptobenzene,

1 .2.4-trimercaptobenzene,

1 .3.5-trimercaptobenzene,

1.2.3-tris(mercaptomethyl)benzene,

1.2.4-tris(mercaptomethyl)benzene,

1.3.5-tris(mercaptomethyl)benzene, 1.2.3-tris(2-mercaptoethyl)benzene,

1.2.4-tris(2-mercaptoethyl)benzene,

1.3.5-tris(2-mercaptoethyl)benzene,

1.2.3-tris(2-mercaptoethyleneoxy)benzene,

1.2.4-tris(2-mercaptoethyleneoxy)benzene,

1.3.5-tris(2-mercaptoethyleneoxy)benzene,

1 .2.3.4-tetramercaptobenzene,

1 .2.3.5-tetramercaptobenzene,

1 .2.4.5-tetramercaptobenzene,

1.2.3.4-tetrakis(mercaptomethyl)benzene,

1.2.3.5-tetrakis(mercaptomethyl)benzene,

1.2.4.5-tetrakis(mercaptomethyl)benzene,

1.2.3.4-tetrakis(2-mercaptoethyl)benzene,

1.2.3.5-tetrakis(2-mercaptoethyl)benzene,

1.2.4.5-tetrakis(2-mercaptoethyl)benzene,

1.2.3.4-tetrakis(2-mercaptoethyleneoxy)benzene,

1.2.3.5-tetrakis(2-mercaptoethyleneoxy)benzene,

1.2.4.5-tetrakis(2-mercaptoethyleneoxy)benzene,

2,2’-dimercaptobiphenyl,

4,4’-dimercaptobiphenyl,

4,4’-dimercaptobibenzyl,

2.5-toluenedithiol,

3.4-toluenedithiol,

1 .4-naphthalenedithiol,

1 .5-naphthalenedithiol,

2.6-naphthalenedithiol,

2.7-naphthalenedithiol,

2.4-dimethylbenzene-1 ,3-dithiol,

4.5-dimethylbenzene-1 ,3-dithiol,

9,10-anthracenedimethanethiol,

1.3-bis(2-mercaptoethylthio)benzene,

1.4-bis(2-mercaptoethylthio)benzene,

1.2-bis(2-mercaptoethylthiomethyl)benzene,

1.3-bis(2-mercaptoethylthiomethyl)benzene,

1.4-bis(2-mercaptoethylthiomethyl)benzene, 1.2.3-tris(2-mercaptoethylthio)benzene,

1.2.4-tris(2-mercaptoethylthio)benzene,

1.3.5-tris(2-mercaptoethylthio)benzene,

1.2.3.4-tetrakis(2-mercaptoethylthio)benzene,

1.2.3.5-tetrakis(2-mercaptoethylthio)benzene,

1.2.4.5-tetrakis(2-mercaptoethylthio)benzene,

3,4-thiophenedithiol.

According to this more particular eighth embodiment, the thiol compound(s) may be chosen from 1 ,2,3-trimercaptobenzene, 1 ,2,4-trimercaptobenzene, 1 ,3,5-trimercaptobenzene,

1 ,2,3-tris(mercaptomethyl)benzene, 1.2.4-tris(mercaptomethyl)benzene, 1 ,3,5- tris(mercaptomethyl)benzene, 1 ,2,3-tris(2-mercaptoethyl)benzene, 1.2.4-tris(2- mercaptoethyl)benzene, 1 ,3,5-tris(2-mercaptoethyl)benzene, 1 ,2,3-tris(2- mercaptoethyleneoxy)benzene, 1 ,2,4-tris(2-mercaptoethyleneoxy)benzene, 1.3.5-tris(2- mercaptoethyleneoxy)benzene, 1 .2.3.4-tetramercaptobenzene, 1 ,2,3,5- tetramercaptobenzene, 1 .2.4.5-tetramercaptobenzene, 1.2.3.4- tetrakis(mercaptomethyl)benzene, 1.2.3.5-tetrakis(mercaptomethyl)benzene, 1.2.4.5- tetrakis(mercaptomethyl)benzene, 1.2.3.4-tetrakis(2-mercaptoethyl)benzene, 1.2.3.5- tetrakis(2-mercaptoethyl)benzene, 1.2.4.5-tetrakis(2-mercaptoethyl)benzene, 1 , 2,3,4- tetrakis(2-mercaptoethyleneoxy)benzene, 1 ,2,3,5-tetrakis(2- mercaptoethyleneoxy)benzene, 1 ,2,4,5-tetrakis(2-mercaptoethyleneoxy)benzene, 1 ,2,3- tris(2-mercaptoethylthio)benzene, 1 ,2,4-tris(2-mercaptoethylthio)benzene, 1 , 3, 5-tris(2- mercaptoethylthio)benzene, 1 ,2,3,4-tetrakis(2-mercaptoethylthio)benzene, 1 ,2,3,5- tetrakis(2-mercaptoethylthio)benzene, 1 ,2,4,5-tetrakis(2-mercaptoethylthio)benzene and

3,4-thiophenedithiol.

According to a more particular ninth embodiment, the thiol compound(s) of formula (IB) are such that n = 2 or 3 or 4 and W denotes a fatty acid triglyceride or a plant oil, which are optionally substituted, it being understood that when the radical W is substituted, the thiol functions may be borne by the substituent(s).

According to another particular embodiment of the invention, the thiol compound(s) are chosen from thiol-based fatty acid triglyceride derivatives, such as those of formula (IV) below:

in which formula (IV):

R¹, R² and R³, which may be identical or different, represent a hydrogen atom or a thiol group;

ALK¹, ALK² and ALK³, which may be identical or different, represent a (Ci-C3o)alkylene group optionally substituted with one or more thiol groups;

X¹, X² and X³, which may be identical or different, preferably identical, represent a group -C(Y)-Y’- or -Y’-C(Y)- with Y and Y’, which may be identical or different, preferably identical, representing a heteroatom such as O, S and N, preferably O.

Preferably, the compounds of formula (IV) are such that:

R¹, R² and R³ represent a hydrogen atom;

ALK¹ represents a (C -C24)alkylene and particularly (Ci4-C2o)alkylene group, which is preferably linear;

ALK² represents a (C -C24)alkylene and particularly (Ci4-C2o)alkylene group, which is preferably linear, substituted with one or more thiol groups;

ALK³ represents a (C -C24)alkylene and particularly (Ci4-C2o)alkylene group, which is preferably linear, substituted with one or more thiol groups, preferably two thiol groups;

X¹, X² and X³, which are identical, represent a -C(O)-O- or -O-C(O)- group.

More preferentially, the thiol-based fatty acid triglyceride derivatives are those of formula (IV’) below:

According to this other particular embodiment, the thiol compound(s) may be chosen from: fatty acid triglycerides or plant oils modified with thiol groups by chemical reaction, for instance thiolated soybean oils and hydroxylated and thiolated soybean oils, notably the polymercaptan® products from the company Chevron Phillips, such as Polymercaptan 358 (mercaptanized soybean oil) and Polymercaptan 407 (mercapto hydroxy soybean oil).

According to a particular embodiment of the invention, the thiol compound(s) are chosen from polythiol compounds containing several thiol groups, and having a weight-average molecular weight ranging from 500 to 1 000 000, preferably ranging from 500 to 500 000 and preferentially ranging from 500 to 100 000.

According to this variant, preference will be given to the compounds of formula (IB) for which n denotes an integer greater than or equal to 3, preferably ranging from 3 to 10 and more preferentially ranging from 3 to 5.

Preferably, according to this variant, the thiol compound(s) are chosen from compounds of the more particular second embodiment; or from compounds of the more particular third embodiment; or from compounds of the more particular fourth embodiment, in particular such as trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3- mercaptopropionate), pentaerythrityl tetrakis(2-mercaptoacetate), pentaerythrityl tetrakis(3- mercaptopropionate), pentaerythrityl tetrakis(3-mercaptobutanate) or dipentaerythrityl hex- 3-mercaptopropionate; or from compounds of the more particular fifth embodiment; or from compounds of the more particular seventh embodiment, in particular such as tris((mercaptopropionyloxy)ethyl) isocyanurate.

Particularly preferably, according to this variant, the thiol compound(s) denote trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythrityl tetrakis(2-mercaptoacetate), pentaerythrityl tetrakis(3-mercaptopropionate), pentaerythrityl tetrakis(3-mercaptobutanate), dipentaerythrityl hex-3-mercaptopropionate or tris((mercaptopropionyloxy)ethyl) isocyanurate.

Polymeric thiol compounds

According to one embodiment of the invention, the thiol compound(s) are polymeric compounds. The polymeric hydroxylated compound(s) of the invention may be star, comb, brush and dendritic homopolymers or copolymers bearing thiol units. The polymers may be of natural origin such as polysaccharides or peptides, or of synthetic origin such as acrylic polymers or polyesters. The thiol units may be present as terminal and/or side groups. The polymeric thiol compound(s) are preferably organic or silicone compounds, more preferentially of formula (VB):

POLY(SH)q (VB) in which formula (VB): q is an integer greater than or equal to 2;

- a and b being equal to 0 or 1 ; preferably, the sum a + b is equal to 1 ;

- R_a and R_b, which may be identical or different, represent a hydrogen atom or a (Ci-C )alkyl or aryl(Ci-C4)alkyl group such as benzyl; preferably, R_a and R_b represent a hydrogen atom; and

The methods for preparing the thiol-based polymers according to the invention are known to those skilled in the art; several methods are reported hereinbelow in a non-limiting manner.

The thiol-based polymers according to the invention may be obtained by polymerization or polycondensation of monomer units bearing thiol or protected thiol functions, optionally as a copolymerization or co-polycondensation of monomer units free of thiol or protected thiol functions.

Alternatively, the thiol-based polymers according to the invention may be obtained by addition of hydrogen sulfide, of salts thereof such as sodium hydrogen sulfide or potassium sulfide or alternatively a group that is capable of forming a carbon-sulfur bond such as thiourea derivatives or thiosulfate, on a polymer bearing at least one double bond.

The thiol-based polymers according to the invention may also be obtained by nucleophilic substitution of a leaving group present on a polymer chain (for example a halogen such as chlorine or bromine, or a sulfonic ester such as mesylate or tosylate) with a compound including at least one sulfur atom such as those mentioned previously.

The thiol-based polymers according to the invention may also be obtained by reaction of polymers including nucleophilic groups such as amines on electrophilic compounds including a sulfur atom, such as 2-oxo-4-thiazolidinecarboxylic acid, also known as procysteine:

- N-acetyl homocysteine thiolactone:

- y-thiobutyrolactone:

- iminothiolane:

According to one embodiment of the invention, the polymeric thiol compound(s) are of formula (VIIIB):

POLY(SH)q (VIIIB) in which formula (VIIIB): q denotes an integer greater than or equal to 2, and

POLY denotes a carbon-based and/or silicone-based, preferably silicone-based, polymeric radical, POLY also possibly containing one or more heteroatoms such as O, N or S, and/or one or more functions chosen from (thio)-ester, (thio)-ketone, (thio)-amide, (thio)urea and (thio)carbamate functions, and/or possibly being substituted with one or more linear or branched (Ci-C )alkyl or linear or branched (Ci-Cio)alkoxy groups, it being understood that when POLY is substituted, the thiol functions may be borne by the substituent(s).

The weight-average molecular weight of the polythiol polymer compounds, such as those of formula (VIIIB), generally ranges from 500 to 400 000, preferably from 500 to 150 000. According to a particular embodiment of the invention, the polymeric thiol compound(s) are chosen from the polyorganosiloxanes of formula (VIIIB’):

(VIIIB’) in which formula (VIIIB’):

R^a and R^b, which may be identical or different, preferably identical, represent a group from among: (Ci-C4)alkyl such as methyl, (Ci-C4)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(Ci-C4)alkyl such as benzyl, or aryl(Ci-C4)alkoxy such as benzoxy, preferably (Ci-C4)alkyl such as methyl; n represents an integer greater than or equal to 1 and more particularly the value of n is such that the weight-average molecular weight of the silicone ranges from 500 to 55 000; in particular, n is an integer ranging from 1 to 100, preferably ranging from 5 to 50 and preferentially ranging from 10 to 30; and

L⁴ and L⁵, which may be identical or different, represent a covalent bond, or a linear or branched, saturated or unsaturated, optionally cyclic hydrocarbon-based chain comprising from 1 to 100 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen; preferably, L⁴ and L⁵, which may be identical or different, represent a covalent bond or a (Ci-Ce)alkylene, (Ci-Ce)alkylenoxy, oxy(Ci- Ce)alkylene, (Ci-C6)alkylenoxy(Ci-C6)alkylene, (Ci-C6)alkylenoxy(Ci-C6)alkylenoxy or oxy(Ci-C6)alkylenoxy(Ci-C6)alkylene group, preferably a (Ci-Ce)alkylene, (Ci- Ce)alkylenoxy, oxy(Ci-Ce)alkylene or (Ci-C6)alkylenoxy(Ci-C6)alkylene group.

Preferentially, the polydimethylsiloxane thiols are chosen from those of formula (VIIIB”):

(VIIIB”) in which formula (VIIIB”):

L⁴ and L⁵ represent a linear or branched, optionally cyclic, saturated or unsaturated hydrocarbon-based chain comprising from 1 to 100 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen; preferably L⁴ a L⁵ represent a (Ci-Ce)alkylene, (Ci-Ce)alkylenoxy, oxy(Ci-Ce)alkylene or (Ci-C6)alkylenoxy(Ci-C6)alkylene group, more preferentially a divalent group chosen from -R2-, -O-R2-, -R2-O- and -R2-O-R2-, preferably -R2-O-R2-, with R2 representing a linear or branched, preferably linear, (C2-Ce)alkylene group, such as ethylene or n-propylene; n represents an integer ranging from 1 to 100, preferably ranging from 5 to 50 and preferentially ranging from 10 to 30.

As thiol-based poly(Ci-C4)alkylsiloxanes, mention may be made of mercaptosiloxanes or thiol-based siloxanes in which the thiol functions are at the chain ends, sold by the company Shin-Etsu under the reference X-22-167B, and mercaptosiloxane in which the mercapto functions are pendent, sold by the company Shin-Etsu under the reference KF-2001 , or polydimethylsiloxanes in which the thiol functions are at the chain ends, sold by the company Gelest under the name DMS-SM 21 , of formula (VIII’”):

(viir”)

Preferably, the polymeric thiol compound(s) are chosen from those of formula (IX):

in which formula (IX):

R^a, R^b and R^d, which may be identical or different, preferably identical, represent a group from among: (Ci-Ce)alkyl group optionally substituted with a hydroxyl or amino group, preferably (Ci-C4)alkyl such as methyl; (Ci-C4)alkoxy such as methoxy; aryl such as phenyl; aryloxy such as phenoxy; aryl(Ci-C4)alkyl such as benzyl; or aryl(Ci-C4)alkoxy such as benzoxy; preferably (Ci-C4)alkyl such as methyl;

R^d may also represent a (Ci-Ce)alkyl group substituted with a (Ci-C4)alkylamino or amino or thiol group, preferably (Ci-C4)alkyl such as methyl; ALK represents a linear or branched, optionally cyclic, saturated or unsaturated hydrocarbon-based chain comprising from 1 to 100 carbon atoms, optionally interrupted with one or more heteroatoms such as oxygen, sulfur or nitrogen (in particular O), a (thio)carbonyl group C(X) with X representing O or S, or combinations thereof such as -O- , -O-C(O)- or -C(O)-O-; preferably, ALK represents a (Ci-Ce)alkylene and more preferentially (Ci-C4)alkylene group such as propylene; n and m, which may be identical or different, representing an integer greater than 2, and more particularly the values of m and n are such that the weight-average molecular weight of the silicone ranges from 1000 to 55 000;

Preferentially, the polydi(Ci-C4)alkylsiloxanes of formula (IX) have the formula (IX’) below:

in which formula (IX’) the values of n and m, are such that the weight-average molecular weight of the silicone ranges from 1000 to 55 000. As examples of silicones (IX’), mention may be made of the products GP-367 and others sold by Genesee Polymers. The polythiol silicones are notably polydimethylsiloxanes including two or more than two thiol groups, for instance the products SMS-022, SMS 042 and SMS 992 sold by the company Gelest In https://www.gpcsilicones.com/products/silicone-fluids/mercapto- functional,https://www.shinetsusilicone- global.com/products/type/oil/detail/search/deg07.shtml, and 1053_Reactive Silicones_Silanes/Silicones - Gelest.

According to a particular embodiment of the invention, the thiol compound(s) are chosen from polymeric compounds such as hyperbranched polymers and dendrimers.

The definition of dendrimers given above includes molecules bearing symmetrical branching; it also includes molecules bearing non-symmetrical branching, for instance dendrimers in which the branches are lysine groups, in which the branching of one generation of wedges on the preceding generation takes place on the a and E amines of lysine, which leads to a difference in the length of the wedges of the various branches.

Dendrimers also known as “dense star polymers” or “starburst polymers” or “rod-shaped dendrimers” are included in the present definition of dendrimers. The molecules known as “arborols” and “cascade molecules” are also included in the definition of dendrimers according to the present invention.

According to one embodiment, the polymeric thiol compound(s) are of formula (ll’B):

POL(SH)n (ll’B) in which formula (ll’B) n represents an integer greater than or equal to 5, preferably ranging from 5 to 5000, more preferentially ranging from 5 to 1000; and POL denotes a carbon-based or silicone-based multivalent (at least pentavalent) polymeric radical, POL also possibly containing one or more heteroatoms such as O, N or S, and/or one or more functions chosen from ester, ketone, amide, urea and carbamate functions, and/or possibly being substituted with one or more linear or branched C1-C10 alkyl or linear or branched C1-C10 alkoxy groups, it being understood that when POL is substituted, the thiol functions may be borne by the substituent(s).

The molar mass of the compounds of formula (ll’B) generally ranges from 500 to 400 000 and preferably from 500 to 150 000.

POL may denote a multivalent radical of homopolymer or copolymer type;

POL may denote a polymeric radical of star, comb, brush or dendritic type. The radical POL may be of natural origin (such as polysaccharides or peptides) or of synthetic origin (such as acrylic polymers, polyesters or polyglycols).

The thiol functions (-SH) may be terminal and/or side groups.

According to a first embodiment, the polymeric thiol compound(s) of formula (ll’B) are such that POL denotes a hydrocarbon-based polymeric radical.

Examples that may be mentioned include the polymers described in the following articles: Polymers containing groups of biological activity, C.G. Overberger et al., Polytechnic Institute of Brooklyn, http://pac.iupac.org/publications/pac/pdf/1962/pdf/0402x0521.pdf and Mercaptan-containing polymers, Advances in Polymer Science, volume 15, 1974, pages 61-90.

In particular, mention may be made of the polymeric thiol compound(s) of formula (ll’B), such as poly(vinyl mercaptan), poly(4-mercaptostyrene), poly(vinylbenzyl mercaptan), poly(4-mercaptostyrene)-co-poly(methyl methacrylate), and also polymers containing amide functions in the polymer, such as poly(thiolated hexamethylene adipamide).

The polymeric thiol compound(s) of formula (ll’B) also denote proteins and peptides with thiol units, for instance the structures represented in the following table:

The polymeric thiol compound(s) of formula (ll’B) also denote the compounds of formula (ll’B) such that POL denotes a radical termed a dendrimer or a branched or hyperbranched polymer, and the thiol groups are terminal groups. As examples, mention may be made of the polymers described in the article Progress in Organic Coatings, volume 63, issue 1 , July 2008, pages 100-109. As an example of a synthesis of such polymers, mention may be made of the synthesis described in said article in which the polymer Boltorn H40 is transformed into a thiol polymer of formula (ll’B) according to the scheme below:

The structure of the thiol polymer (ll’B) obtained is given below:

The polymeric thiol compound(s) of formula (ll’B) may also denote a hyperbranched or dendritic polymer modified with thiol functions, as described in patent application FR 2 761 691. As examples of hyperbranched polymers and dendrimers including thiol functional groups, mention may be made of the hyperbranched polymers and dendrimers including functional groups of formula (X) below:

HS-A-C(Y)-X-

(X) in which formula (X):

Y represents an oxygen or sulfur atom or a group NR’;

X represents i) an oxygen atom or ii) a group -N(R’)- in which R’ is chosen from a) a hydrogen atom, b) a linear or branched, saturated or unsaturated Ci-Ce alkyl group, c) a linear or branched, saturated or unsaturated Ci-Ce monohydroxyalkyl or polyhydroxyalkyl group, d) a Ci-Ce aminoalkyl group or a polyalkyleneimine group; preferably, X represents -N(R’)- with R’ representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl; and A represents a linear, branched or cyclic, saturated or unsaturated (Ci-Ci2)alkylene group; this group being optionally interrupted with one or more heteroatoms such as O, S or N and/or optionally substituted with one or more groups chosen from amino (-NH2), acylamino (-N(H)-C(O)-R) or aminoacyl (RN(H)-C(O)-) in which R represents a linear, branched or cyclic, saturated or unsaturated C1-C10 alkyl, carboxyl (-C(O)OH) or ester (-C(O)-OR) group in which R represents a linear, branched or cyclic, saturated or unsaturated C1-C10 alkyl group.

Preferably, the polymeric thiol compound(s) according to the invention are chosen from hyperbranched polymers, and notably polyethyleneimine including at least one group chosen from the groups of formula (X) as defined previously.

Preferably, Y represents an oxygen atom. Preferably, the heteroatoms are chosen from oxygen and nitrogen (O and N).

Preferably, A is a methylene, ethylene, propylene, methylpropylene, ethylpropylene, tetramethylene, pentamethylene, hexamethylene or phenylene group.

Advantageously, A represents a radical corresponding to one of the formulae (a) to (d) below:

in which formulae (a), (b), (c) and (d):

R¹, R², R³, R’¹, R’², R’³ and R’⁴, R’”¹ and R’”², which may be identical or different, represent: a hydrogen atom; a linear, branched or cyclic, saturated or unsaturated Ci-Ce alkyl group; an amino group (-NH2); a carboxylic acid group (-COOH); a C1-C10 alkylamino group; a C1- C10 acylamino group;

R”¹, R”², R”³ and R”⁴, which may be identical or different, represent a hydrogen atom or a linear or branched, saturated or unsaturated C1-C4 alkyl group; the arrows indicating the positions of the substitutions; and k is an integer, preferentially 0 or 1 ; represents the point of attachment to the rest of the molecule on the phenylene group in position 1-2, or 1-3, or 1-4; it being understood that the radicals R”i, R”2, R”s and R”4 are then positioned on the carbon atoms 3, 4, 5, 6, or 2, 4, 5 or 6 or 2, 3, 5, 6, respectively.

According to a preferred embodiment of the invention, the polymeric thiol compound(s) are hyperbranched polymers and dendrimers including functional groups of formula (X) such that A is chosen from:

-CH2-CH(CC>2H)-NH- and Y represents an oxygen atom;

-(CH₂)2-(CH₃CONH)CH- and Y represents an oxygen atom;

-(CH₂)₃- and Y represents an oxygen atom or an NH group.

In particular, A is the propylene group -CH2-CH2-CH2- and Y represents an oxygen atom, the compound according to the invention then corresponding to formula (XI) below: HS-CH₂-CH₂-CH₂-C(O)-X- (XI) in which formula (XI) X is as defined previously; preferably, X represents -N(R’)- with R’ representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl. Preferentially, according to the invention, X of formulae (X) and (XI) is chosen from an oxygen atom and an NH group.

According to one of the preferred embodiments of the invention, the thiol polymers are as described in FR 2 853 533, that is to say poly-N-a- and N-E- lysine and ornithine of formula I, bearing a thiol function, which may be obtained from poly-N-a- and N-E- lysine and ornithine by reaction with a thiolactone, for instance thiobutyrolactone (dihydrothiophen- 2(3H)-one).

According to a preferred embodiment of the invention, the hyperbranched polymers and dendrimers that are useful in the invention include functional groups corresponding to formula (XII):

in which formula (XII): p is different from p’ and p and p’ are equal to 0 or 1 ; n is 3 or 4; if p’ is equal to 0, then the neighbouring NH is engaged in an N-E polymerization; if p is equal to 0, then the neighbouring NH is engaged in an N-a polymerization; if p or p’ is equal to 1 , then R or R’ represents -B-SH, with B representing a saturated or unsaturated, linear or branched C1-C30 hydrocarbon-based chain which may be interrupted with one or more heteroatoms or groups, alone or in combination, such as: -N(R¹)-, -O-, -S(O)_r-, -C(O)-, -C(S)- or -C(NR¹)-, with r being equal to 0, 1 or 2, and/or with one or more 5-, 6- or 7-membered aryl, heteroaryl, cycloalkyl or heterocycloalkyl which may be substituted with one or more halogen atoms or groups from among: hydroxyl, amino, carboxyl, (di)(Ci-Cs)alkylamino, (Ci-Cs)acylamino, (Ci-Cs)acyloxy, (C1- C8)alkyloxycarbonylamino, (Ci-C8)alkylaminocarbonyloxy or (Ci-C8)alkylaminocarbonyl; given that R or R’ may also, in part only, represent a hydrogen atom, and/or -C(NH)- and salts thereof and/or -C(NH)-N(H)-C(NH)-NH₂ and salts thereof

R1 represents a hydrogen atom or a (Ci-Cs)alkyl, (Ci-Cs)acyl, (Ci-C8)alkyloxycarbonyl, (C1- C8)alkylaminocarbonyl or halo group; B may also represent an optionally substituted 5-, 6- or 7-membered aryl, heteroaryl, cycloalkyl or heterocycloalkyl group; m represents an integer ranging from 3 to 10 000.

Preferably, the degree of thiol function grafting will be greater than or equal to 1 %.

Advantageously, the poly N-a- and N-E- lysine and ornithine corresponding to formula (XII) have: 5 < m < 1000.

The term “theoretical degree of thiol function grafting” represents the theoretical percentage of lysine or ornithine units bearing the thiol function in the compound of formula (XII).

Examples of hyperbranched polymers that may be mentioned most particularly include hyperbranched thiolated polyethyleneimines, such as those described in patent application EP 103 759 with a molecular molar mass ranging from 30x10⁴ to 50x10⁴.

These polymers are prepared according to methods that are conventional to those skilled in the art, such as the methods described in French patent application FR 2 761 691 and EP 1 037 938.

According to a particular embodiment of the invention, the dendrimers and branched or hyperbranched polymers bear thiol terminal groups, such as the Boltorn™ dendritic polythiols from the company BASF esterified with compounds such as thioglycolic acid and described in the literature.

Polymers such as polypropylene ether glycol bis(P-mercaptopropionate) may also be used in the invention. They are prepared via the methods known to those skilled in the art. Mention may be made, for example, of the preparation method by esterification reaction of polypropylene ether glycol (e.g., Pluracol P201 , Wyandotte Chemical Corp.) and p- mercaptopropionic acid.

According to a particular embodiment of the invention, the thiol polymers are polyethoxylated polymers of formula (XIII):

in which formula (XIII):

Ri, R2 and R3, which may be identical or different, represent a thio(Ci-Ce)alkyl group;

R4 represents a hydrogen atom or a group from among: hydroxyl, thiol, amino or (C1- Ce)alkyl, preferably (Ci-C4)alkyl such as ethyl;

Xi and X2, which may be identical or different, preferably identical, represent an oxygen or sulfur atom, or amino, preferably oxygen; m, n and I, which may be identical or different, represent an integer greater than or equal to 1.

The thiol polymer compounds of formula (XIII) are commercially available. Mention may be made, for example, of the products Thiocure® from the company Bruno Brock, Thiocure® ETTMP 1300 (Ethoxylated-Trimethylolpropane Tri-3-Mercaptopropionate (CAS# 345352- 19-4) and Thiocure® ETTMP 700 (Ethoxylated-Trimethylolpropane Tri-3- Mercaptopropionate (CAS# 345352-19-4).

According to a particular embodiment of the invention, the polythiol polymer(s) are mineral polymers. Mention may be made of polythiol silicones and polythiol silicas.

Compound(s) E

The process according to the invention uses a) one or more compounds E chosen from metal salts, salts of a metal belonging to the rare-earth metal group, organometallic compounds, and mixtures thereof, the compound(s) E being included in composition (A) and/or in composition (B) and/or in a different composition (C), composition (C) also being applied to the keratin fibres. According to a particular embodiment of the invention, composition (A) comprises the compound(s) E as defined previously.

According to a particular embodiment of the invention, composition (B) comprises the compound(s) E as defined previously.

According to a particular embodiment of the invention, composition (C) comprises the compound(s) E as defined previously.

According to a particular embodiment of the invention, compositions (A) and (B) comprise the compound(s) E as defined previously.

According to another embodiment, compositions (A) and (C) comprise the compound(s) E as defined previously.

According to another embodiment, compositions (B) and (C) comprise the compound(s) E as defined previously.

According to another particular embodiment, compositions (A), (B) and (C) comprise the compound(s) E as defined previously.

When several compositions chosen from (A), (B) and (C) comprise the compound(s) E as defined previously, the compound(s) E included in each of the compositions may be identical or different.

The compound(s) E are preferably included in composition (A) or in composition (C), more preferentially in composition (C).

According to a preferred embodiment of the invention, the compound(s) E are present in a total content ranging from 0.1% to 30% by weight, preferably ranging from 0.5% to 20% by weight, relative to the weight of the composition comprising them. Metal salts

The metal salts are chosen from the salts of transition metals, alkali metal salts, alkaline- earth metal salts, aluminium salts, boron salts, tin salts, magnesium salts, hydrates thereof and mixtures thereof.

Preferably, the metal salts are chosen from aluminium salts, hydrates thereof, and mixtures thereof.

The term “metal salt” means a salt notably obtained from the action of an acid on a metal.

The metal salts may be in the form of hydrates.

The metal salts may be mineral or organic salts.

The term “organic metal salt” means a salt notably obtained from the action of an organic acid on a metal.

The term “mineral metal salt” means a salt notably obtained from the action of a mineral acid on a metal.

The term “mineral acid” means an acid which does not include any carbon atoms, apart from carbonic acid.

According to a particular embodiment of the invention, the mineral metal salts may be chosen from halides such as chlorides, fluorides, iodides and bromides, carbonates, sulfates, phosphates, nitrates and perchlorates, hydrates thereof, and mixtures thereof.

According to a preferred embodiment of the invention, the metal salts are organic, preferably chosen from citrates, lactates, glycolates, gluconates, acetates, propionates, fumarates, oxalates, glycinates and tartrates, hydrates thereof, and mixtures thereof.

According to a more preferred embodiment, the metal salts are chosen from basic aluminium acetate, aluminium oxalate, hydrated or non-hydrated aluminium citrate, aluminium lactate and aluminium glycinate, and mixtures thereof. According to an even more preferred embodiment, the metal salt is basic aluminium acetate.

According to a particular embodiment of the invention, composition (A) comprises one or more metal salts as defined previously.

According to a particular embodiment of the invention, composition (B) comprises one or more metal salts as defined previously.

According to a particular embodiment of the invention, composition (C) comprises one or more metal salts as defined previously.

According to a particular embodiment of the invention, compositions (A) and (B) comprise one or more metal salts as defined previously.

According to another embodiment, compositions (A) and (C) comprise one or more metal salts as defined previously.

According to another embodiment, compositions (B) and (C) comprise one or more metal salts as defined previously.

According to another embodiment, compositions (A), (B) and (C) comprise one or more metal salts as defined previously.

When several compositions chosen from (A), (B) and (C) comprise one or more metal salts as defined previously, the metal salt(s) included in each of the compositions may be identical or different.

The metal salt(s) are preferably included in composition (A) or in composition (C), more preferentially in composition (C).

According to a preferred embodiment of the invention, the metal salt(s) as defined previously are present in a total content ranging from 0.1% to 20% by weight, preferably ranging from 0.5% to 15% by weight, relative to the weight of the composition comprising them. Salts of a metal belonging to the rare-earth metal group

As examples of metals belonging to the rare-earth metal group, mention may be made of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.

Preferably, the metal belonging to the rare-earth metal group is chosen from cerium, yttrium, ytterbium, lanthanum and europium, and mixtures thereof. More preferentially, the metal belonging to the rare-earth metal group is chosen from cerium and yttrium, and mixtures thereof.

Preferably, the metal is in the oxidation state +III.

The term “salt of a metal belonging to the rare-earth metal group” means a salt notably derived from the action of an acid on a metal belonging to the rare-earth metal group.

The salts of a metal belonging to the rare-earth metal group may be in the form of hydrates.

The salts of a metal belonging to the rare-earth metal group may be organic or mineral salts.

The term “organic salt of a metal belonging to the rare-earth metal group” means a salt notably derived from the action of an organic acid on a metal belonging to the rare-earth metal group.

The term “mineral salt of a metal belonging to the rare-earth metal group” means a salt notably derived from the action of a mineral acid on a metal belonging to the rare-earth metal group.

According to a particular embodiment of the invention, the organic salts of a metal belonging to the rare-earth metal group may be chosen from the salts of organic acids such as citrates, lactates, glycolates, gluconates, acetates, propionates, fumarates, oxalates, tartrates, mesylates and methosulfates, notably gluconates, hydrates thereof, and mixtures thereof. According to a preferred embodiment, the salts of a metal belonging to the rare-earth metal group are mineral salts.

Preferably, the mineral salts of a metal belonging to the rare-earth metal group are chosen from halides such as chlorides, fluorides, iodides and bromides, carbonates, sulfates, phosphates, nitrates and perchlorates, hydrates thereof, and mixtures thereof.

More preferentially, the mineral salts of a metal belonging to the rare-earth metal group are chosen from halides such as chlorides, fluorides, iodides and bromides, and nitrates, hydrates thereof, and mixtures thereof.

Even more preferentially, the mineral salts of a metal belonging to the rare-earth metal group are chosen from chlorides and nitrates, hydrates thereof, and mixtures thereof.

According to a particularly preferred embodiment, the salt(s) of a metal belonging to the rare-earth metal group are chosen from Ce(NOs)3, Y(NOs)3, La(NOs)3, CeCh, YCh and LaCh, and mixtures thereof.

According to an even more preferred embodiment, the salts of a metal belonging to the rare-earth metal group are chosen from CeCh and YC , and mixtures thereof.

According to a particular embodiment of the invention, composition (A) comprises one or more salts of a metal belonging to the rare-earth metal group as defined previously.

According to a particular embodiment of the invention, composition (B) comprises one or more salts of a metal belonging to the rare-earth metal group as defined previously.

According to a particular embodiment of the invention, composition (C) comprises one or more salts of a metal belonging to the rare-earth metal group as defined previously.

According to a particular embodiment of the invention, compositions (A) and (B) comprise one or more salts of a metal belonging to the rare-earth metal group as defined previously.

According to another embodiment, compositions (A) and (C) comprise one or more salts of a metal belonging to the rare-earth metal group as defined previously.

According to another embodiment, compositions (B) and (C) comprise one or more salts of a metal belonging to the rare-earth metal group as defined previously. According to another embodiment, compositions (A), (B) and (C) comprise one or more salts of a metal belonging to the rare-earth metal group as defined previously.

When several compositions chosen from (A), (B) and (C) comprise one or more salts of a metal belonging to the rare-earth metal group as defined previously, the salt(s) of a metal belonging to the rare-earth metal group included in each of the compositions may be identical or different.

The salt(s) of a metal belonging to the rare-earth metal group are preferably included in composition (A) or in composition (C), more preferentially in composition (C).

According to a preferred embodiment of the invention, the salt(s) of a metal belonging to the rare-earth metal group are present in a total content ranging from 0.1 % to 20% by weight, preferably ranging from 0.5% to 15% by weight, relative to the weight of the composition comprising them.

Organometallic compounds

The organometallic compounds are chosen from the alkoxides of formulae (la), (lb), (Ic) and (Id) below and mixtures thereof:

M-(ORi)_n (la)

R-M-(ORi)_n-i (lb)

(RlO)n-1-M-R”-M’-(ORl)n-1 (Ic)

RR’-M-(ORi)_n-2 (Id) in which formulae (la), (lb), (Ic) and (Id):

- n represents the valency of the atom;

- R and R’, independently of each other, represent a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, optionally interrupted with 1 to 20 heteroatoms chosen from O, N, S and/or P; - R” represents -O-, -NR²-, -S- or a linear, cyclic or branched, saturated or unsaturated divalent hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, optionally interrupted with 1 to 20 heteroatoms chosen from O, N, S and/or P, with R² representing a linear, cyclic or branched, saturated or unsaturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms.

Preferably, M and M’, independently of each other, represent an atom chosen from titanium, zirconium and magnesium, more preferentially chosen from titanium and zirconium.

Preferably, the organometallic compounds are chosen from the alkoxides of formula (la) as defined previously.

According to a preferred embodiment, the organometallic compounds are chosen from the alkoxides of formula (la) in which:

- M represents an atom chosen from transition metals, metals of the lanthanide family, aluminium, boron, tin or alkaline-earth metals;

- n represents the valency of the atom;

- Ri, which my be identical or different, represent a linear or branched saturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 1 to 6 carbon atoms.

According to a more preferred embodiment, the organometallic compounds are chosen from the alkoxides of formula (la) in which:

- n represents the valency of the atom;

- Ri represents a methyl, ethyl, 2-ethylhexyl, propyl, isopropyl, n-butyl, isobutyl or t-butyl group.

According to an even more preferred embodiment, the organometallic compounds are chosen from zirconium ethoxide (Zr(OC2Hs)4), zirconium propoxide (Zr(OCH2CH2CHs)4), zirconium isopropoxide (Zr(OCH(CHs)2)4), zirconium butoxide Zr(OCH2CH2CH2CH3)4, zirconium tert-butoxide (Zr(OC(CHs)3)4), titanium ethoxide (Ti(OC2Hs)4), titanium propoxide (Ti(OCH2CH2CH3)4), titanium isopropoxide (Ti(OCH(CH3)2)4), titanium butoxide (Ti(OCH2CH2CH2CH3)4), titanium tert-butoxide (Ti(OC(CHs)3)4), titanium 2-ethylhexyloxide (Ti(OCH2CH(C2H5)(CH2)3CH3)4), and mixtures thereof.

Particularly preferably, the organometallic compounds are chosen from zirconium propoxide (Zr(OCH2CH2CH3)4), titanium propoxide (Ti(OCH2CH2CH3)4), titanium butoxide (Ti(OCH2CH2CH2CH3)4) and mixtures thereof.

According to a particular embodiment of the invention, composition (A) comprises one or more organometallic compounds as defined previously.

According to a particular embodiment of the invention, composition (B) comprises one or more organometallic compounds as defined previously.

According to a particular embodiment of the invention, composition (C) comprises one or more organometallic compounds as defined previously.

According to a particular embodiment of the invention, compositions (A) and (B) comprise one or more organometallic compounds as defined previously.

According to another embodiment, compositions (A) and (C) comprise one or more organometallic compounds as defined previously.

According to another embodiment, compositions (B) and (C) comprise one or more organometallic compounds as defined previously.

According to another embodiment, compositions (A), (B) and (C) comprise one or more organometallic compounds as defined previously.

When several compositions chosen from (A), (B) and (C) comprise one or more organometallic compounds as defined previously, the organometallic compound(s) in each of the compositions may be identical or different.

The organometallic compound(s) are preferably included in composition (A) or in composition (C), more preferentially in composition (C). According to a preferred embodiment of the invention, the organometallic compound(s) are present in a total content ranging from 0.1% to 30% by weight, preferably ranging from 0.5% to 20% by weight, relative to the weight of the composition comprising them.

Colouring aqent(s) 3)

The process according to the invention uses P) one or more colouring agents chosen from direct dyes, oxidation dyes, pigments and mixtures thereof, the colouring agent(s) being included in composition (A) and/or in composition (B) and/or in composition (C) and/or in a different composition (D), composition (D) also being applied to the keratin fibres.

According to a particular embodiment of the invention, composition (A) comprises the colouring agent(s).

According to a particular embodiment of the invention, composition (B) comprises the colouring agent(s).

According to a particular embodiment of the invention, composition (C) comprises the colouring agent(s).

According to a particular embodiment of the invention, composition (D) comprises the colouring agent(s).

According to another particular embodiment of the invention, compositions (A) and (C) comprise the colouring agent(s). When compositions (A) and (C) comprise the colouring agent(s), the colouring agent(s) included in each of the compositions may be identical or different.

According to a preferred embodiment of the invention, the colouring agent(s) are included in composition (A).

Preferably, composition B does not comprise any colouring agent(s).

The term “colouring agent” means an oxidation dye, a direct dye or a pigment.

The term “oxidation dye” means an oxidation dye precursor chosen from oxidation bases and couplers. Oxidation bases and couplers are colourless or sparingly coloured compounds, which, via a condensation reaction in the presence of an oxidizing agent, give a coloured species.

The term “direct dye” means a natural and/or synthetic dye, including in the form of an extract or extracts, other than oxidation dyes. These are coloured compounds that will spread superficially on the fibre. They may be ionic or nonionic, i.e. anionic, cationic, neutral or nonionic.

Direct dyes and/or oxidation dyes

The colouring agent(s) used in the process according to the invention may be chosen from direct dyes, oxidation dyes and mixtures thereof, preferably from direct dyes.

The oxidation dyes are generally chosen from one or more oxidation bases, optionally combined with one or more coupling agents.

By way of example, the oxidation bases may be chosen from para-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases and the corresponding addition salts, optionally combined with coupling agents; they may in particular be chosen from meta-phenylenediamines, meta-aminophenols, metadiphenols, naphthalene-based coupling agents and heterocyclic coupling agents and also the corresponding addition salts.

By way of example, the direct dyes may notably be chosen from azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures. The direct dyes may be anionic, cationic or neutral;

The natural direct dyes may notably be chosen from hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin and orcein, and also extracts or decoctions containing these natural dyes.

The colouring agent(s) chosen from direct dyes, oxidation dyes and mixtures thereof more particularly represent from 0.001% to 10% and preferably from 0.005% to 5% by weight relative to the total weight of the composition comprising them. Pigments

The colouring agent(s) used in the process according to the invention are chosen from pigments.

According to a preferred embodiment of the invention, composition (A) comprises one or more colouring agents chosen from pigments.

According to a particular embodiment of the invention, composition (B) comprises one or more colouring agents chosen from pigments.

According to a particular embodiment of the invention, composition (C) comprises one or more colouring agents chosen from pigments.

According to a particular embodiment of the invention, composition (D) comprises one or more colouring agents chosen from pigments.

According to a particular embodiment of the invention, composition (A) and/or composition (C) comprise one or more colouring agents chosen from pigments.

According to a particular embodiment of the invention, compositions (A) and (C) comprise one or more colouring agents chosen from pigments, the pigment(s) contained in compositions (A) and (C) possibly being identical or different.

The term “pigment” refers to any pigment that gives colour to keratin fibres. The solubility of the pigments in water at 25°C and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

They are white or coloured solid particles which are naturally insoluble in the hydrophilic and lipophilic liquid phases usually employed in cosmetics or which are rendered insoluble by formulation in the form of a lake, where appropriate. More particularly, the pigments have little or no solubility in aqueous-alcoholic media.

The pigments that may be used are notably chosen from the organic and/or mineral pigments known in the art, notably those described in Kirk-Othmer’s Encyclopedia of Chemical Technology and in Ullmann’s Encyclopedia of Industrial Chemistry. Pigments that may notably be mentioned include organic and mineral pigments such as those defined and described in Ullmann’s Encyclopedia of Industrial Chemistry “Pigments, organic”, 2005 Wiley- VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a20 371 and ibid, “Pigments, Inorganic, 1. General” 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a20_243.pub3.

These pigments may be in pigment powder or paste form. They may be coated or uncoated. The pigments may be chosen, for example, from mineral pigments, organic pigments, lakes, pigments with special effects such as nacres or glitter flakes, and mixtures thereof.

The pigment may be a mineral pigment. The term “mineral pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopaedia in the chapter on inorganic pigments. Among the mineral pigments that are useful in the present invention, mention may be made of iron oxides, chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

The pigment may be an organic pigment. The term “organic pigment” refers to any pigment that satisfies the definition in Ullmann’s encyclopaedia in the chapter on organic pigments. The organic pigment may notably be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane and quinophthalone compounds.

In particular, the white or coloured organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Colour Index under the references Cl 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Colour Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Colour Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Colour Index under the references Cl 11725, 15510, 45370, 71105, the red pigments codified in the Colour Index under the references Cl 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole or phenolic derivatives as described in patent FR 2 679 771.

According to a particular embodiment of the invention, the pigment(s) used are pigment pastes of organic pigments such as the products sold by the company Hoechst under the name:

- Cosmenyl Yellow IOG: Yellow 3 pigment (Cl 11710);

- Cosmenyl Yellow G: Yellow 1 pigment (Cl 11680);

- Cosmenyl Orange GR: Orange 43 pigment (Cl 71105);

- Cosmenyl Red R: Red 4 pigment (Cl 12085); - Cosmenyl Carmine FB: Red 5 pigment (Cl 12490);

- Cosmenyl Violet RL: Violet 23 pigment (Cl 51319);

- Cosmenyl Blue A2R: Blue 15.1 pigment (Cl 74160);

- Cosmenyl Green GG: Green 7 pigment (Cl 74260);

- Cosmenyl Black R: Black 7 pigment (Cl 77266).

The pigments in accordance with the invention may also be in the form of composite pigments, as described in patent EP 1 184 426. These composite pigments may be composed notably of particles including:

- a mineral core,

- at least one binder for fixing the organic pigments to the core, and

- at least one organic pigment at least partially covering the core.

The term “lake” refers to dyes adsorbed onto insoluble particles, the assembly thus obtained remaining insoluble during use. The inorganic substrates onto which the dyes are adsorbed are, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate and aluminium. Among the organic dyes, mention may be made of cochineal carmine.

Examples of lakes that may be mentioned include the products known under the following names: D & C Red 21 (Cl 45 380), D & C Orange 5 (Cl 45 370), D & C Red 27 (Cl 45 410), D & C Orange 10 (Cl 45 425), D & C Red 3 (Cl 45 430), D & C Red 7 (Cl 15 850:1), D & C Red 4 (Cl 15 510), D & C Red 33 (Cl 17 200), D & C Yellow 5 (Cl 19 140), D & C Yellow 6 (Cl 15 985), D & C Green 5 (Cl 61 570), D & C Yellow 10 (Cl 77 002), D & C Green 3 (Cl 42 053), D & C Blue 1 (Cl 42 090).

The pigment(s) may also be pigments with special effects.

The term “pigments with special effects” means pigments that generally create a coloured appearance (characterized by a certain shade, a certain vivacity and a certain level of luminance) that is non-uniform and that changes as a function of the conditions of observation (light, temperature, angles of observation, etc.). They thereby differ from coloured pigments, which afford a standard uniform opaque, semi-transparent or transparent shade.

Several types of pigments with special effects exist: those with a low refractive index, such as fluorescent, photochromic or thermochromic pigments, and those with a higher refractive index, such as nacres or glitter flakes.

Examples of pigments with special effects that may be mentioned include nacreous pigments such as titanium mica coated with an iron oxide, mica coated with an iron oxide, mica coated with bismuth oxychloride, titanium mica coated with chromium oxide, titanium mica coated with an organic dye notably of the abovementioned type, and also nacreous pigments based on bismuth oxychloride. They may also be mica particles, at the surface of which are superposed at least two successive layers of metal oxides and/or of organic dyestuffs.

The nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or coppery colour or tint.

As illustrations of nacres that may be used in the context of the present invention, mention may notably be made of the gold-coloured nacres sold notably by the company Engelhard under the name Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); the bronze nacres sold notably by the company Merck under the names Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona), by the company Eckart under the name Prestige Bronze and by the company Engelhard under the name Super bronze (Cloisonne); the orange nacres sold notably by the company Engelhard under the names Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company Merck under the names Passion orange (Colorona) and Matte orange (17449) (Microna); the brown-tinted nacres sold notably by the company Engelhard under the names Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); the nacres with a copper tint sold notably by the company Engelhard under the name Copper 340A (Timica) and by the company Eckart under the name Prestige Copper; the nacres with a red tint sold notably by the company Merck under the name Sienna fine (17386) (Colorona); the nacres with a yellow tint sold notably by the company Engelhard under the name Yellow (4502) (Chromalite); the red-coloured nacres with a golden tint sold notably by the company Engelhard under the name Sunstone G012 (Gemtone); the black nacres with a golden tint sold notably by the company Engelhard under the name Nu-antique bronze 240 AB (Timica); the blue nacres sold notably by the company Merck under the names Matte blue (17433) (Microna), Dark Blue (117324) (Colorona); the white nacres with a silvery tint sold notably by the company Merck under the name Xirona Silver; and the golden-green pinkishorange nacres sold notably by the company Merck under the name Indian summer (Xirona), and mixtures thereof.

In addition to nacres on a mica support, multilayer pigments based on synthetic substrates such as alumina, silica, sodium calcium borosilicate or calcium aluminium borosilicate, and aluminium, may be envisaged.

Mention may also be made of pigments with an interference effect which are not attached to a substrate, such as liquid crystals (Helicones HC from Wacker) or interference holographic glitter flakes (Geometric Pigments or Spectra f/x from Spectratek). Pigments with special effects also comprise fluorescent pigments, whether these are substances that are fluorescent in daylight or that produce an ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, sold, for example, by the company Quantum Dots Corporation.

The variety of pigments that may be used in the present invention makes it possible to obtain a wide range of colours, and also particular optical effects such as metallic effects or interference effects.

The size of the pigment(s) used in the process according to the present invention generally ranges from 10 nm to 200 pm, preferably from 20 nm to 80 pm and more preferentially from 30 nm to 50 pm.

The pigments may be dispersed in the composition comprising them by means of a dispersant.

The term “dispersant” refers to a compound which can protect the dispersed particles from agglomerating or flocculating. This dispersant may be a surfactant, an oligomer, a polymer or a mixture of several thereof, bearing one or more functionalities with strong affinity for the surface of the particles to be dispersed. In particular, they may become physically or chemically attached to the surface of the pigments. These dispersants also contain at least one functional group that is compatible with or soluble in the continuous medium. Said agent may be charged: it may be anionic, cationic, zwitterionic or neutral.

According to a particular embodiment of the invention, the dispersants used are chosen from esters of 12-hydroxystearic acid, more particularly, and of Cs to C20 fatty acid and of polyols such as glycerol or diglycerol, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol, such as the product sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel, or polyhydroxystearic acid such as the product sold under the reference Arlacel P100 by the company Uniqema, and mixtures thereof.

As other dispersants that may be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids, for instance Solsperse 17 000 sold by the company Avecia, and polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185 and DC2-5225 C. The pigments used in the process according to the invention may be surface-treated with an organic agent.

Thus, the pigments that have been surface-treated beforehand, which are useful in the context of the invention, are pigments that have totally or partially undergone a surface treatment of chemical, electronic, electrochemical, mechanochemical or mechanical nature, with an organic agent such as those described notably in Cosmetics and Toiletries, February 1990, volume 105, pages 53-64, before being dispersed in the composition in accordance with the invention. These organic agents may be chosen, for example, from amino acids; waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and derivatives thereof, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol and lauric acid and derivatives thereof; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminium salts of fatty acids, for example aluminium stearate or laurate; metal alkoxides; polysaccharides, for example chitosan, cellulose and derivatives thereof; polyethylene; (meth)acrylic polymers, for example polymethyl methacrylates; polymers and copolymers containing acrylate units; proteins; alkanolamines; silicone compounds, for example silicones, polydimethylsiloxanes, alkoxysilanes, alkylsilanes and siloxysilicates; organofluorine compounds, for example perfluoroalkyl ethers; fluorosilicone compounds.

The surface-treated pigments used in the process according to the invention may also have been treated with a mixture of these compounds and/or may have undergone several surface treatments.

The surface-treated pigments that are useful in the context of the present invention may be prepared according to surface-treatment techniques that are well known to those skilled in the art, or may be commercially available as is.

Preferably, the surface-treated pigments are coated with an organic layer.

The organic agent with which the pigments are treated may be deposited on the pigments by evaporation of solvent, chemical reaction between the molecules of the surface agent or creation of a covalent bond between the surface agent and the pigments.

The surface treatment may thus be performed, for example, by chemical reaction of a surface agent with the surface of the pigments and creation of a covalent bond between the surface agent and the pigments or the fillers. This method is notably described in patent US 4 578 266.

An organic agent covalently bonded to the pigments will preferably be used.

The agent for the surface treatment may represent from 0.1% to 50% by weight, preferably from 0.5% to 30% by weight and even more preferentially from 1% to 10% by weight relative to the total weight of the surface-treated pigments.

Preferably, the surface treatments of the pigments are chosen from the following treatments:

- a PEG-silicone treatment, for instance the AQ surface treatment sold by LCW;

- a chitosan treatment, for instance the CTS surface treatment sold by LCW;

- a triethoxycaprylylsilane treatment, for instance the AS surface treatment sold by LCW;

- a methicone treatment, for instance the SI surface treatment sold by LCW;

- a dimethicone treatment, for instance the Covasil 3.05 surface treatment sold by LCW;

- a dimethicone/trimethyl siloxysilicate treatment, for instance the Covasil 4.05 surface treatment sold by LCW;

- a lauroyllysine treatment, for instance the LL surface treatment sold by LCW;

- a lauroyllysine dimethicone treatment, for instance the LL/SI surface treatment sold by LCW;

- a magnesium myristate treatment, for instance the MM surface treatment sold by LCW;

- an aluminium dimyristate treatment, such as the Ml surface treatment sold by Miyoshi;

- a perfluoropolymethyl isopropyl ether treatment, for instance the FHC surface treatment sold by LCW;

- an isostearyl sebacate treatment, for instance the HS surface treatment sold by Miyoshi;

- a disodium stearoyl glutamate treatment, for instance the NAI surface treatment sold by Miyoshi;

- a dimethicone/disodium stearoyl glutamate treatment, for instance the SA/NAI surface treatment sold by Miyoshi;

- a perfluoroalkyl phosphate treatment, for instance the PF surface treatment sold by Daito;

- an acrylate/dimethicone copolymer and perfluoroalkyl phosphate treatment, for instance the FSA surface treatment sold by Daito;

- a polymethylhydrogenosiloxane/perfluoroalkyl phosphate treatment, for instance the FS01 surface treatment sold by Daito;

- a lauroyllysine/aluminium tristearate treatment, for instance the LL-StAI surface treatment sold by Daito;

- an octyltriethylsilane treatment, for instance the OTS surface treatment sold by Daito; - an octyltriethylsilane/perfluoroalkyl phosphate treatment, for instance the FOTS surface treatment sold by Daito;

- an acrylate/dimethicone copolymer treatment, for instance the ASC surface treatment sold by Daito;

- an isopropyl titanium tri isostearate treatment, for instance the ITT surface treatment sold by Daito;

- a microcrystalline cellulose and carboxymethylcellulose treatment, for instance the AC surface treatment sold by Daito;

- a cellulose treatment, for instance the C2 surface treatment sold by Daito;

- an acrylate copolymer treatment, for instance the APD surface treatment sold by Daito;

- a perfluoroalkyl phosphate/isopropyl titanium triisostearate treatment, for instance the PF + ITT surface treatment sold by Daito.

The pigments used in the process according to the invention may be surface-treated with an organic agent.

The compositions used in the process according to the present invention may also comprise one or more pigments that are not surface-treated.

According to a particular embodiment of the invention, the pigment(s) are mineral pigments. According to another particular embodiment of the invention, the pigment(s) are chosen from nacres.

According to a particular embodiment of the invention, the dispersant is present with organic or mineral pigments in submicron-sized particulate form in the composition comprising them.

The term “submicron” or “submicronic” refers to pigments having a particle size that has been micronized by a micronization method and having a mean particle size of less than a micrometre (pm), in particular ranging from 0.1 to 0.9 pm and preferably ranging from 0.2 to 0.6 pm.

According to one embodiment, the dispersant and the pigment(s) are present in an amount (dispersantpigment) ranging from 0.5:1 to 2:1 , particularly ranging from 0.75:1 to 1.5:1 or better still ranging from 0.8:1 to 1.2:1. According to a particular embodiment, the dispersant is suitable for dispersing the pigments and is compatible with a condensation-curable formulation.

The term “compatible” means, for example, that said dispersant is miscible in the oily phase of the composition containing the pigment(s), and it does not retard or reduce the curing. The dispersant is preferably cationic.

The dispersant(s) may therefore have a silicone backbone, such as silicone polyether and dispersants of amino silicone type. Among the suitable dispersants that may be mentioned are:

- amino silicones, i.e. silicones comprising one or more amino groups such as those sold under the names and references: BYK LPX 21879 by BYK, GP-4, GP-6, GP-344, GP-851 , GP-965, GP-967 and GP-988-1 , sold by Genesee Polymers,

- silicone acrylates such as Tego® RC 902, Tego® RC 922, Tego® RC 1041 and Tego® RC 1043, sold by Evonik,

- polydimethylsiloxane (PDMS) silicones bearing carboxyl groups such as X-22162 and X- 22370 by Shin-Etsu, epoxy silicones such as GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, and GP-695 by Genesee Polymers, or Tego® RC 1401 , Tego® RC 1403 and Tego® RC 1412 by Evonik.

According to a particular embodiment, the dispersant(s) are of amino silicone type and are positively charged.

Mention may also be made of dispersants bearing chemical groups that are capable of reacting with the reagents of the oily phase and are thus capable of improving the 3D network formed from the amino silicones. For example, dispersants of epoxy silicone pigments can react chemically with the amino silicone prepolymer amino group(s) to increase the cohesion of the aminosilicone film comprising the pigment(s).

Preferably, the pigment(s) used in the process of the invention are chosen from carbon black, such as Black 2, iron oxides, notably red, brown or black iron oxides, and micas coated with iron oxide, triarylmethane pigments, notably blue and violet triarylmethane pigments, such as Blue 1 Lake, azo pigments, notably red azo pigments, such as D&C Red 7, alkali metal or alkaline-earth metal salts of lithol red, such as the calcium salt of lithol red B, and mixtures thereof. According to a particular embodiment of the invention, the amount of pigments ranges from 0.5% to 40% by weight and preferably from 1 % to 20% by weight relative to the weight of the composition(s) comprising them.

Variants of the process according to the present invention

According to a preferred variant of the invention, the process involves:

■ applying to the keratin fibres a composition (C) comprising the compound(s) E as defined previously; followed by

■ applying to the keratin fibres a composition (A) as defined previously; followed by

■ applying to the keratin fibres a composition (B) as defined previously; it being understood that the colouring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) and/or in composition (C), preferably in composition (A) and/or in composition (B), more preferentially in composition (A).

According to a more preferred variant of the invention, the process involves:

■ applying to the keratin fibres a composition (A), composition (A) being or comprising an oily dispersion (A’), the oily dispersion (A’) comprising: i) the compound(s) A in the form of one or more particles consisting of one or more ethylenic copolymers a) and b) as defined previously; and ii) one or more stabilizers consisting of ethylenic polymers chosen from c) and d) as defined previously; and iii) one or more hydrocarbon-based oil(s); followed by

According to an even more preferred variant of the invention, the process involves:

■ applying to the keratin fibres a composition (B) comprising iv) one or more amine compounds chosen from polyamine compounds containing at least two primary amine and/or secondary amine groups as defined previously; it being understood that the colouring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) and/or in composition (C), preferably in composition (A) and/or in composition (B), more preferentially in composition (A).

According to a particular variant of the invention, the process involves:

■ applying to the keratin fibres a composition (B) as defined previously; followed by

■ applying to the keratin fibres a composition (A) as defined previously; it being understood that the colouring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) and/or in composition (C), preferably in composition (A) and/or in composition (B), more preferentially in composition (A).

According to a more particular variant of the invention, the process involves:

■ applying to the keratin fibres a composition (A), composition (A) being or comprising an oily dispersion (A’), the oily dispersion (A’) comprising: i) the compound(s) A in the form of one or more particles consisting of one or more ethylenic copolymers a) and b) as defined previously; and ii) one or more stabilizers consisting of ethylenic polymers chosen from c) and d) as defined previously; and iii) one or more hydrocarbon-based oils; it being understood that the colouring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) and/or in composition (C), preferably in composition (A) and/or in composition (B), more preferentially in composition (A). According to an even more particular variant of the invention, the process involves:

■ applying to the keratin fibres a composition (B) comprising iv) one or more amine compounds chosen from polyamine compounds containing at least two primary amine and/or secondary amine groups as defined previously; followed by

■ applying to the keratin fibres a composition (A), composition (A) being or comprising an oily dispersion (A’), the oily dispersion (A’) comprising: i) the compound(s) A in the form of one or more particles consisting of one or more ethylenic copolymers a) and b) as defined previously; and ii) one or more stabilizers consisting of ethylenic polymers chosen from c) and d) as defined previously; and iii) one or more hydrocarbon-based oils; it being understood that the colouring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) and/or in composition (C), preferably in composition (A) and/or in composition (B), more preferentially in composition (A).

According to another preferred variant of the invention, the process involves:

■ applying to the keratin fibres a composition (B) as defined previously; it being understood that:

- the compound(s) E as defined previously are included in composition (A) and/or in composition (B), preferably in composition (A);

- the colouring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B), preferably in composition (A).

According to another more preferred variant of the invention, the process involves:

- the compound(s) E as defined previously are included in composition (A) and/or in composition (B), preferably in composition (A); and

According to another even more preferred variant of the invention, the process involves:

■ applying to the keratin fibres a composition (B) comprising iv) one or more amine compounds chosen from polyamine compounds containing at least two primary amine and/or secondary amine groups as defined previously; it being understood that:

According to another particular variant of the invention, the process involves:

■ applying to the keratin fibres a composition (A) as defined previously; it being understood that:

According to another more particular variant of the invention, the process involves: ■ applying to the keratin fibres a composition (B) as defined previously; followed by

■ applying to the keratin fibres a composition (A), composition (A) being or comprising an oily dispersion (A’), the oily dispersion (A’) comprising: i) the compound(s) A in the form of one or more particles consisting of one or more ethylenic copolymers a) and b) as defined previously; and ii) one or more stabilizers consisting of ethylenic polymers chosen from c) and d) as defined previously; and iii) one or more hydrocarbon-based oils; it being understood that:

According to another even more particular variant of the invention, the process involves:

Additional characteristics concerning the compositions of the present invention Compositions (A), (B), (C) and (D) are cosmetic compositions, i.e. they comprise only cosmetically acceptable ingredients. Compositions (A), (B), (C) and (D) according to the invention may also comprise a cosmetic additive chosen from fragrances, preserving agents, fillers, UV-screening agents, waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, free-radical scavengers and thickeners.

Compositions (A), (B), (C) and (D) according to the invention may be in any presentation form conventionally used for hair application. In a non-limiting manner, compositions (A), (B), (C) and (D) may be in the form of a lotion, a cream, a foam, a gel, a spray or a lacquer.

According to one embodiment of the invention, compositions (B), (C) and (D) comprise water and optionally one or more organic solvents chosen from C2-C4 alcohols, polyols, polyol ethers and mixtures thereof, preferably chosen from ethanol, isopropanol, glycerol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, 2-butoxyethanol, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and mixtures thereof.

According to a particular embodiment of the invention, compositions (A), (B) and (C) are anhydrous.

According to another particular embodiment of the invention, compositions (A) and (B) are anhydrous.

According to a preferred embodiment of the invention, composition (B) also comprises one or more hydrocarbon-based oils iii) as defined previously. Advantageously, the hydrocarbon-based oils iii) included in the oily dispersion (A’) and composition (B) are identical.

According to a preferred embodiment of the invention, the hydrocarbon-based oil(s) iii) included in composition (B) are chosen from hydrocarbon-based oils containing from 8 to 14 carbon atoms, in particular the apolar oils described previously. Even more preferentially, the hydrocarbon-based oil included in composition (B) is isododecane.

According to yet another advantageous embodiment of the invention, composition (B) comprises water and comprises iv) one or more amine compounds chosen from polyamine compounds containing at least two primary amine and/or secondary amine groups as defined previously in emulsion of oil-in-water (O/W) type. Compositions (A), (B), (C) and (D) may be used on wet or dry keratin fibres, and also on any type of fair or dark, natural or dyed, permanent-waved, bleached or relaxed fibres.

The application to the fibres may be performed via any standard means, in particular using a comb, a fine brush, a coarse brush or with the fingers.

After applying each of the compositions (A), (B), (C) and (D), the fibres may be left to dry or may be dried, for example at a temperature of greater than or equal to 30°C. According to a particular embodiment, this temperature is greater than 40°C. According to a particular embodiment, this temperature is greater than 45°C and less than 220°C, for example with a hairdryer, a heating lamp and then optionally with a straightening iron.

Preferably, if the fibres are dried, they are dried, in addition to a supply of heat, with a flow of air.

During drying, a mechanical action may be exerted on the locks, such as combing, brushing or running the fingers through. This operation may similarly be performed once the fibres have dried, naturally or otherwise.

The drying step of the process of the invention may be performed with a drying device such as a hood, a hairdryer, a straightening iron or a Climazon.

When the drying step is performed with a hood ora hairdryer, the drying temperature ranges from 40°C to 110°C and preferably from 50°C to 90°C.

When the drying step is performed with a straightening iron, the drying temperature ranges from 110°C to 220°C and preferably from 140°C to 200°C.

Once the drying is complete, final rinsing or shampooing may optionally be performed.

According to an advantageous variant of the process of the invention, there is no rinsing, and drying of the keratin fibres is performed naturally or using a drying device such as a hairdryer between the step of applying composition (A) to the keratin fibres and the step of applying composition (B) to the keratin fibres. Preferably, there is a waiting time between the two steps of from 1 minute to 6 hours, in particular from 10 minutes to 5 hours, more particularly from 30 minutes to 4 hours, preferably about 3 hours.

According to another variant of the process of the invention, there is no rinsing or drying of the keratin fibres between the step of applying composition (A) to the keratin fibres and the step of applying composition (B) to the keratin fibres. Preferably, there is a waiting time between the two steps of from 1 minute to 6 hours, in particular from 10 minutes to 5 hours, more particularly from 30 minutes to 4 hours, preferably about 3 hours. Particular compositions

According to a second aspect, a subject of the present invention is a composition (AO) comprising:

- the oily dispersion (A’) as defined previously;

- one or more compound(s) E as defined previously;

- optionally one or more colouring agent(s) as defined previously.

Multi-compartment kit or device

■ in a first compartment: composition (A) as defined previously;

■ in a second separate compartment separate from the first: composition (B) as defined previously; and

The composition packaging assembly is, in a known manner, any packaging that is suitable for storing cosmetic compositions (notably a bottle, tube, spray bottle or aerosol can).

Examples

The examples that follow allow the invention to be understood more clearly, without, however, being limiting in nature.

Example 1 : Preparation of the oily dispersions (A’)

The oily dispersions (A’) are formed as a whole [particles i) + stabilizer ii)] containing:

- 70% by weight of ethyl acrylate;

- 10% by weight of maleic anhydride; and - 20% by weight of isobornyl acrylate.

The preparation of these oily dispersions was performed in a 1 litre pilot reactor. The synthesis is performed in two steps:

In a first step, isobornyl acrylate is polymerized in isododecane/ethyl acetate (60/40) in the presence of a small amount of ethyl acrylate and of a radical initiator (T21S). In the first step, the isobornyl acrylate/ethyl acrylate mass ratio is 92/8.

In the second step, the rest of the ethyl acrylate and the maleic anhydride are added in the presence of isododecane/ethyl acetate (60/40) and of the radical initiator T rigonox 21 S (T21S).

After stripping, the polymer is at a solids content of 52% in the isododecane. The ratios employed to obtain the stabilizer and the particulate core are summarized in the table below:

[Table 1]

Amount of reagents:

Step 1 :

[Table 2]

Isododecane I EtOAc (60/40) added between the two steps:

[Table 3]

Step 2: [Table 4]

Experimental protocol:

Isododecane/ethyl acetate (60/40), isobornyl acrylate, ethyl acrylate and T21S are introduced as feedstock into a reactor. The medium is heated to 90°C under argon and with stirring. The solids content during this first step is 35.9%.

After heating for 2 hours, NMR indicates an isobornyl acrylate consumption of 97% (ethyl acrylate consumption: 97%).

After 2 hours of reaction, isododecane/ethyl acetate (60/40) are introduced into the feedstock. The medium is heated to 90°C.

Once the medium is at 90°C, ethyl acrylate/maleic anhydride, isododecane/ethyl acetate (60/40) and T21S are introduced over 2 hours by pouring. At the end of the introduction by pouring, the medium is milky. The solids content is 40%.

After 7 hours of synthesis, traces of the starting monomers remain.

1 L of isododecane and of ethyl acetate is then stripped out (NMR indicates that there are no more monomers and that the ethyl acetate has been totally removed from the dispersion). The solids content is about 52%.

Examples 2A to 6A

Compositions tested

The following compositions were used in Examples 2A to 6A below. The amounts are given in g per 100 g of composition.

Composition (A1a)

[Table 5]

AM: Active Material

Composition (A2a)

[Table 6]

AM: Active Material

Composition (B1a)

[Table 7]

AM: Active Material

Composition (B2a)

[Table 8]

Composition (C1a)

[Table 9]

Composition (C2a)

[Table 10]

Application protocol

The application protocol followed in Examples 2A to 6A below involves applying either two different compositions or three different compositions.

Application protocol No. 1 (with two different compositions)

The application protocol with two different compositions involves the following steps:

- applying to a lock of dry hair composition (A1a) or (A2a) in a bath ratio of 0.5 g of composition (A1a) or (A2a)/g of hair; and then

- drying the lock with a hairdryer; and then

- applying to the lock composition (B1a) or (B2a) in a bath ratio of 0.5 g of composition (B1a) or (B2a)/g of hair; and then - drying the lock with a hairdryer.

Application protocol No. 2 (with three different compositions)

The application protocol with three different compositions involves the following steps:

- applying to a lock of dry hair composition (C1a) or (C2a) in a bath ratio of 0.5 g of composition (C1a) or (C2a)/g of hair; and then

- applying to the lock composition (A1a) or (A2a) in a bath ratio of 0.5 g of composition (A1a) or (A2a)/g of hair; and then

- drying the lock with a hairdryer; and then

- applying to the lock composition (B1a) or (B2a) in a bath ratio of 0.5 g of composition (B1a) or (B2a)/g of hair; and then

- drying the lock with a hairdryer.

Intensive shampoo washing protocol

The shampoo-washing resistance evaluations were conducted according to the following shampoo washing protocol, 24 hours after applying the compositions according to the application protocol described previously:

The dyed locks of hair are combed, moistened with water at 35°C and then passed between the fingers five times for 5 seconds. The locks of hair are then squeezed dry between two fingers.

A standard shampoo (Garnier Ultra Doux) is applied uniformly to the dyed locks in a proportion of 0.4 g of standard shampoo per gram of locks, the locks of hair being massaged gently along their length (six passes) for 15 seconds, from the root to the end.

The locks of hair are then placed on a watch glass and left to stand for 1 minute.

Next, the locks of hair are rinsed with water while passing the locks between the fingers (15 passes). The locks of hair are then squeezed dry between two fingers before the next shampoo wash.

Once the tests of several shampoo washes have been performed, the locks of hair are combed and dried with a hairdryer.

Evaluation of the persistence of the colour with respect to shampoo washing

The persistence of the colour of the locks was evaluated in the CIE L* a* b* system, using a Minolta CM-3610d spectrophotometer.

In this L*a*b* system, L* represents the intensity of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis. The persistence of the colouring is evaluated by the colour difference AE between the dyed locks before shampooing, then after having undergone eight shampoo washes according to the protocol described above. The lower the AE value, the more persistent the colour with respect to shampoo washing.

The AE value is calculated according to the following equation:

In this equation, L*a*b* represent the values measured after dyeing the hair and after performing the shampoo washes, and Lo*ao*bo* represent the values measured after dyeing the hair but before shampoo washing.

Example 2A (Comparative)

Composition (A1a) and composition (B1a) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 1 described previously.

The shampoo-washing resistance evaluations were conducted according to the intensive shampoo washing protocol described previously.

Colorimetric measurements:

[Table 11]

It is seen visually that the red colouring obtained after applying composition (A1a) and composition (B1a) has almost completely disappeared after eight shampoo washes.

Example 3A

Composition (C1a), composition (A1a) and composition (B1a) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 12]

Visually, the red colouring appears unchanged between the colouring obtained just after having performed the process of the invention and after 8 successive shampoo washes. In addition, the hair strands appear separated after treatment, and after 8 shampoo washes. The feel is pleasant.

Example 4A

Composition (C2a), composition (A1a) and composition (B1a) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 13]

Example 5A

Composition (A2a) and composition (B1a) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 1 described previously. The shampoo-washing resistance evaluations were conducted according to the intensive shampoo washing protocol described previously.

Colorimetric measurements:

[Table 14]

Visually, the red colouring appears to have slightly disappeared between the colouring obtained just after having performed the process of the invention and after 8 successive shampoo washes, but still remains quite visible. In addition, the hair strands appear separated after treatment, and after 8 shampoo washes. The feel is very pleasant.

Example 6A

Composition (A1a) and composition (B2a) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 1 described previously.

Colorimetric measurements:

[Table 15]

Visually, the red colouring appears to have slightly disappeared between the colouring obtained just after having performed the process of the invention and after 8 successive shampoo washes, but still remains quite visible. In addition, the hair strands appear separated after treatment, and after 8 shampoo washes. The feel is very pleasant. Examples 2B to 9B

Compositions tested

The following compositions were used in Examples 2B to 9B below. The amounts are given in g per 100 g of composition. Composition (A1b)

[Table 16]

AM: Active Material

Composition (B1b) [Table 17]

AM: Active Material

Composition (B2b)

[Table 18]

Composition (C1b)

[Table 191

Composition (C2b)

[Table 201

Application protocol

The application protocol followed in Examples 2BA to 9B below involves applying either two different compositions or three different compositions.

Application protocol No. 1 (with two different compositions)

- applying to a lock of dry hair composition (A1 b) in a bath ratio of 0.5 g of composition (A1b)/g of hair; and then

- drying the lock with a hairdryer; and then

- applying to the lock composition (B1 b) or (B2b) in a bath ratio of 0.5 g of composition (B1 b) or (B2b)/g of hair; and then

- drying the lock with a hairdryer. Application protocol No. 2 (with three different compositions)

- applying to a lock of dry hair composition (C1b) or (C2b) in a bath ratio of 0.5 g of composition (C1 b) or (C2b)/g of hair; and then

- applying to the lock composition (A1b) in a bath ratio of 0.5 g of composition (A1b)/g of hair; and then

- drying the lock with a hairdryer; and then

- drying the lock with a hairdryer.

Intensive shampoo washing protocol

Evaluation of the persistence of the colour with respect to shampoo washing

In this L*a*b* system, L* represents the intensity of the colour, a* indicates the green/red colour axis and b* the blue/yellow colour axis.

The persistence of the colouring is evaluated by the colour difference AE between the dyed locks before shampooing, then after having undergone eight shampoo washes according to the protocol described above. The lower the AE value, the more persistent the colour with respect to shampoo washing.

The AE value is calculated according to the following equation:

Example 2B (Comparative)

Composition (A1b) and composition (B1 b) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 1 described previously.

Colorimetric measurements:

[Table 21]

It is seen visually that the red colouring obtained after applying composition (A1b) and composition (B1 b) has almost completely disappeared after eight shampoo washes.

Example 3B

Composition (C1 b), composition (A1 b) and composition (B1b) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 22]

Example 4B

Composition (C2b), composition (A1b) and composition (B1b) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 23]

Example 5B (Comparative)

Composition (A1b) and composition (B1b) were applied to a lock of alkaline solubility 20 (AS20) sensitized hair according to the application protocol No. 1 described previously.

The shampoo-washing resistance evaluations were conducted according to the intensive shampoo washing protocol described previously. Colorimetric measurements:

[Table 24]

It is seen visually that the red colouring obtained after applying composition (A1b) and composition (B1b) to the sensitized hair (AS20) has almost completely disappeared after eight shampoo washes.

Example 6B

Composition (C1b), composition (A1b) and composition (B1b) were applied to a lock of alkaline solubility 20 (AS20) sensitized hair according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 25]

Example 7B (Comparative)

Composition (A1b) and composition (B1b) were applied to a lock of permanent-waved sensitized hair according to the application protocol No. 1 described previously. The shampoo-washing resistance evaluations were conducted according to the intensive shampoo washing protocol described previously.

Colorimetric measurements:

[Table 26]

It is seen visually that the red colouring obtained after applying composition (A1b) and then composition (B1 b) to the permanent-waved sensitized hair has almost completely disappeared after eight shampoo washes.

Example 8B

Composition (C1 b), composition (A1 b) and composition (B1b) were applied to a lock of permanent-waved sensitized hair according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 27]

Visually, the red colouring appears to have slightly disappeared between the colouring obtained just after having performed the process of the invention and after 8 successive shampoo washes, but still remains quite visible. In addition, the hair strands appear separated after treatment, and after 8 shampoo washes. The feel is very pleasant. Example 9B: Measurement of the dyeing selectivity

The dyeing selectivity is the variation of the colour between natural hair and permanent- waved hair. The natural hair is representative of the nature of the hair at the root, whereas the permanent-waved hair is representative of the nature of the hair at the end.

The selectivity is evaluated in the CIE L* a* b* system, using a Minolta CM-3610d spectrophotometer.

AEi, which is the variation in colour between the natural hair and the permanent-waved hair, is obtained from the formula:

In this formula, L*, a* and b* represent the values measured after dyeing the natural hair, and Lo*, ao* and bo* represent the values measured after dyeing the permanent-waved hair. The lower the value of AEi, the lower the selectivity and the more uniform the colouring along the hair strands.

[Table 28]

The colouring obtained is sparingly selective.

Examples 2C to 14C

Compositions tested

The following compositions were used in Examples 2C to 14C below. The amounts are given in g per 100 g of composition.

Composition (A1c)

[Table 29]

AM: Active Material

Composition (B1c)

[Table 30]

AM: Active Material

Composition (B2c)

[Table 31]

Composition (B3c)

[Table 32]

AM: Active Material Composition (C1c)

[Table 33]

Composition (C2c)

[Table 34]

Composition (C3c)

[Table 35]

Application protocol

The application protocol followed in Examples 2C to 14C below involves applying either two different compositions or three different compositions.

Application protocol No. 1 (with two different compositions)

- applying to a lock of dry hair composition (A1c) in a bath ratio of 0.5 g of composition (A1c)/g of hair; and then

- drying the lock with a hairdryer; and then

- applying to the lock composition (B1c) to (B3c) in a bath ratio of 0.5 g of composition (B1c) to (B3c)/g of hair; and then

- drying the lock with a hairdryer.

Application protocol No. 2 (with three different compositions)

- applying to a lock of dry hair composition (C1c) to (C3c) in a bath ratio of 0.5 g of composition (C1c) to (C3c)/g of hair; and then

- applying to the lock composition (A1c) in a bath ratio of 0.5 g of composition (A1c)/g of hair; and then

- drying the lock with a hairdryer; and then

- drying the lock with a hairdryer.

Intensive shampoo washing protocol

The locks of hair are then placed on a watch glass and left to stand for 1 minute. Next, the locks of hair are rinsed with water while passing the locks between the fingers (15 passes). The locks of hair are then squeezed dry between two fingers before the next shampoo wash.

Evaluation of the persistence of the colour with respect to shampoo washing

The AE value is calculated according to the following equation:

Example 2C (Comparative)

Composition (A1c) and composition (B1c) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 1 described previously.

Colorimetric measurements:

[Table 36]

It is seen visually that the red colouring obtained after applying composition (A1c) and composition (B1c) has almost completely disappeared after eight shampoo washes.

Example 3C

Composition (C1c), composition (A1c) and composition (B1c) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 37]

Example 4C

Composition (C2c), composition (A1c) and composition (B1c) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 38]

Example 5C

Composition (C3c), composition (A1c) and composition (B1c) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 39]

Example 6C

Composition (A1c) and composition (B2c) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 1 described previously. The shampoo-washing resistance evaluations were conducted according to the intensive shampoo washing protocol described previously.

Colorimetric measurements:

[Table 40]

obtained just after having performed the process of the invention and after 8 successive shampoo washes, but still remains quite visible. In addition, the hair strands appear separated after treatment, and after 8 shampoo washes. The feel is very pleasant.

Example 7C

Composition (C1c), composition (A1c) and composition (B3c) were applied to a lock of natural hair containing 90% white hairs (also referred to as 90% NW) according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 41]

Visually, the red colouring appears to have slightly disappeared between the colouring obtained just after having performed the process of the invention and after 8 successive shampoo washes, but still remains quite visible. In addition, the hair strands appear separated after treatment, and after 8 shampoo washes. The feel is very pleasant. Example 8C (comparative)

Composition (A1c) and composition (B1c) were applied to a lock of alkaline solubility 20 (AS20) sensitized hair according to the application protocol No. 1 described previously.

Colorimetric measurements:

[Table 42]

It is seen visually that the red colouring obtained after applying composition (A1c) and composition (B1c) to the sensitized hair (AS20) has almost completely disappeared after eight shampoo washes.

Example 9C

Composition (C1c), composition (A1c) and composition (B1c) were applied to a lock of alkaline solubility 20 (AS20) sensitized hair according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 43]

Visually, the red colouring appears unchanged between the colouring obtained just after having performed the process of the invention and after 8 successive shampoo washes, but still remains quite visible. In addition, the hair strands appear separated after treatment, and after 8 shampoo washes. The feel is very pleasant. Example 10C

Composition (C3c), composition (A1c) and composition (B1c) were applied to a lock of alkaline solubility 20 (AS20) sensitized hair according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 44]

Visually, the red colouring appears unchanged between the colouring obtained just after having performed the process of the invention and after 8 successive shampoo washes, but still remains quite visible. In addition, the hair strands appear separated after treatment, and after 8 shampoo washes. The feel is very pleasant.

Example 11C (comparative)

Composition (A1c) and composition (B1c) were applied to a lock of permanent-waved sensitized hair according to the application protocol No. 1 described previously.

Colorimetric measurements:

[Table 45]

It is seen visually that the red colouring obtained after applying composition (A1c) and then composition (B1c) to the permanent-waved sensitized hair has almost completely disappeared after eight shampoo washes. Example 12C

Composition (C1c), composition (A1c) and composition (B1c) were applied to a lock of permanent-waved sensitized hair according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 46]

Example 13C

Composition (C3c), composition (A1c) and composition (B1c) were applied to a lock of permanent-waved sensitized hair according to the application protocol No. 2 described previously.

Colorimetric measurements:

[Table 47]

Example 14C: Measurement of the dyeing selectivity

[Table 48]

The colouring obtained is sparingly selective.

Claims

1 . Process for dyeing keratin fibres, involving:

P) one or more colouring agents chosen from direct dyes, oxidation dyes, pigments and mixtures thereof, the colouring agent(s) being included in composition (A) and/or in composition (B) and/or in composition (C) and/or in a different composition (D), composition (D) also being applied to the keratin fibres; it being understood that:

- the metal salts are chosen from the salts of transition metals, alkali metal salts, alkaline- earth metal salts, aluminium salts, boron salts, tin salts, magnesium salts, hydrates thereof and mixtures thereof; and

M-(ORi)_n (la)

R-M-(ORi)_n-i (lb)

(RlO)n-1-M-R”-M’-(ORl)n-1 (Ic)

RR’-M-(ORi)_n-2 (Id) in which formulae (la), (lb), (Ic) and (Id):

- n represents the valency of the atom;

- Ri, which may be identical or different, represent a linear or branched, saturated or unsaturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 1 to 6 carbon atoms, optionally interrupted with 1 to 20 heteroatoms chosen from O, N, S and/or P; - R and R’, independently of each other, represent a hydrogen atom or a linear, branched or cyclic, saturated or unsaturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, optionally interrupted with 1 to 20 heteroatoms chosen from O, N, S and/or P;

2. Process according to the preceding claim, in which composition (A) is applied after composition (B) or composition (B) is applied after composition (A); preferably, composition (B) is applied after composition (A).

3. Process according to any one of the preceding claims, in which the chemical function(s) A are chosen from the following functions:

- epoxide;

- anhydride, acid chloride and carboxylic acid esters;

- aldehydes, acetals, hemiacetals, aminals, hemiaminals;

- isocyanate;

- thiocyanate;

- ketones, including a-hydroxy ketones and a-halo ketones;

- lactones, thiolactones;

- imines;

- imides;

- N-hydroxysuccinimide esters;

- imidates;

- thiosulfate;

- oxazine and oxazoline;

- oxazinium and oxazolinium; - Ci to C30 alkyl halides or Ce to C30 aryl or aralkyl halides, notably iodides, chlorides or bromides;

- halides of an unsaturated carbon-based ring or heterocycle;

- cyclic carbonates;

- diazonium;

- carbodiimide;

- and mixtures thereof; preferably from anhydride, acid chloride, carboxylic acid ester and epoxide functions, and mixtures thereof, more preferentially from anhydride, acid chloride and carboxylic acid ester functions, and mixtures thereof; even more preferentially, the chemical function(s) A are anhydride functions.

4. Process according to any one of the preceding claims, in which the compound(s) A are polymers, preferably polymers containing the maleic anhydride unit.

5. Process according to any one of the preceding claims, in which the chemical function(s) B are chosen from hydroxyl, primary amine, secondary amine, thiol and carboxylic acid functions, and mixtures thereof, preferably from primary hydroxyl, amine, secondary amine and thiol functions, and mixtures thereof.

6. Process according to any one of the preceding claims, in which the compound(s) E are chosen from metal salts, preferably from aluminium salts, hydrates thereof, and mixtures thereof.

7. Process according to any one of the preceding claims, in which the metal salts are organic or mineral salts, preferably organic salts, more preferentially chosen from citrates, lactates, glycolates, gluconates, acetates, propionates, fumarates, oxalates, glycinates and tartrates, hydrates thereof, and mixtures thereof, even more preferentially chosen from basic aluminium acetate, aluminium oxalate, hydrated or non-hydrated aluminium citrate, aluminium lactate and aluminium glycinate, and mixtures thereof; more preferentially, the metal salt is basic aluminium acetate.

8. Process according to any one of Claims 1 to 5, in which the compound(s) E are chosen from salts of a metal belonging to the rare-earth metal group, the metal belonging to the rare-earth metal group preferably being chosen from cerium, yttrium, ytterbium, lanthanum and europium, and mixtures thereof, more preferentially from cerium and yttrium, and mixtures thereof.

9. Process according to any one of the preceding claims, in which the salts of a metal belonging to the rare-earth metal group are organic or mineral, preferably mineral, more preferentially chosen from halides such as chlorides, fluorides, iodides and bromides, carbonates, sulfates, phosphates, nitrates and perchlorates, hydrates thereof, and mixtures thereof, even more preferentially chosen from halides such as chlorides, fluorides, iodides and bromides, and nitrates, hydrates thereof, and mixtures thereof, more preferentially chosen from chlorides and nitrates, hydrates thereof, and mixtures thereof, and better still chosen from Ce(NOs)3, Y(NOs)3, La(NOs)3, CeC , YCh and LaCh, and mixtures thereof, and even better still chosen from CeCh, YC and mixtures thereof.

10. Process according to any one of Claims 1 to 5, in which the compound(s) E are chosen from organometallic compounds as defined in Claim 1 with M and M’, independently of each other, preferably representing an atom chosen from titanium, zirconium and magnesium, more preferentially chosen from titanium and zirconium.

11. Process according to any one of the preceding claims, in which the organometallic compounds are chosen from the alkoxides of formula (la), preferably from the alkoxides of formula (la) in which Ri, which may be identical or different, represent a linear or branched, saturated hydrocarbon-based group containing from 1 to 30 carbon atoms, preferably from 1 to 6 carbon atoms, more preferentially chosen from the alkoxides of formula (la), in which Ri represents a methyl, ethyl, 2-ethylhexyl, propyl, isopropyl, n-butyl, isobutyl or t-butyl group, even more preferentially from zirconium ethoxide (Zr(OC2Hs)4), zirconium propoxide (Zr(OCH2CH2CH3)4), zirconium isopropoxide (Zr(OCH(CH3)2)4), zirconium butoxide Zr(OCH2CH2CH2CH3)4, zirconium tert-butoxide (Zr(OC(CH3)3)4), titanium ethoxide (Ti(OC2Hs)4), titanium propoxide (Ti(OCH2CH2CH3)4), titanium isopropoxide (Ti(OCH(CH3)2)4), titanium butoxide (Ti(OCH2CH2CH2CH3)4), titanium tert-butoxide (Ti(OC(CH3)3)4), titanium 2-ethylhexyloxide (Ti(OCH2CH(C2H5)(CH2)3CH3)4), and mixtures thereof, more preferentially from zirconium propoxide (Zr(OCH2CH2CH3)4), titanium propoxide (Ti(OCH2CH2CH3)4), titanium butoxide (Ti(OCH2CH2CH2CH3)4), and mixtures thereof.

12. Process according to any one of the preceding claims, in which the compound(s) E are included in composition (A) or in composition (C), preferably in composition (C).

13. Process according to any one of the preceding claims, in which the compound(s) E are present in a total content ranging from 0.1% to 30% by weight and preferably ranging from 0.5% to 20% by weight relative to the total weight of the composition comprising them.

14. Process according to any one of the preceding claims, in which composition (A) is or comprises an oily dispersion (A’) which comprises the compound(s) A.

15. Process according to the preceding claim, in which the oily dispersion (A’) comprises: i) the compound(s) A in the form of one or more particles consisting of one or more ethylenic copolymers: a) of (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate, and b) of ethylenically unsaturated anhydride compound; and ii) one or more stabilizer(s) consisting of ethylenic polymers chosen from: c) polymers of (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate monomers; and d) copolymers of (C3-Ci2)cycloalkyl (Ci-Ce)(alkyl)acrylate and (Ci-C4)alkyl (Ci- C4)(alkyl)acrylate; and iii) one or more hydrocarbon-based oils.

16. Process according to the preceding claim, in which the monomer a) (Ci-C4)alkyl (Ci- C4)(alkyl)acrylate is of formula H2C=C(R)-C(O)-O-R’ with R representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl, and R’ representing a (Ci-C4)alkyl group such as methyl or ethyl; preferably, the monomer a) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate is a (Ci- C4)alkyl (meth)acrylate monomer, more preferentially the monomer a) (Ci-C4)alkyl (Ci- C4)(alkyl)acrylate is chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate or tert-butyl (meth)acrylate; even more preferentially, the monomer a) (Ci-C4)alkyl (Ci-C4)(alkyl)acrylate is chosen from methyl acrylate and ethyl acrylate.

17. Process according to Claim 15 or 16, in which the ethylenically unsaturated anhydride monomer b) is chosen from derivatives of maleic anhydride (lb) and of itaconic anhydride (Hb):

in which formulae (lb) and (lib) R_a, Rb and R_c, which may be identical or different, represent a hydrogen atom or a (Ci-C4)alkyl group; preferably, R_a, Rb and R_c represent a hydrogen atom, preferably from the maleic anhydride derivatives (lb); more preferentially, the ethylenically unsaturated anhydride monomer b) is maleic anhydride.

18. Process according to any one of Claims 15 to 17, in which the polymer(s) of the particles i) of the oily dispersion (A’) comprise, or consist essentially of, from 80% to 99.99% by weight of monomer a) and from 0.01% to 20% by weight of monomer b), relative to the total weight of the polymer.

19. Process according to any one of Claims 15 to 18, in which the stabilizer(s) ii) of the oily dispersion (A’) consist of ethylenic polymers chosen from: c) polymers of monomers of formula H2C=C(R)-C(O)-O-R” with R representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl, and R” representing a (C5-Cio)cycloalkyl group such as norbornyl or isobornyl, preferably isobornyl; and d) copolymers of H₂C=C(R)-C(O)-O-R’ and of H₂C=C(R)-C(O)-O-R” with R and R” as defined previously and R’ representing a (Ci-C4)alkyl group such as methyl or ethyl; preferably, the stabilizer(s) ii) of the oily dispersion (A’) are chosen from isobornyl (meth)acrylate polymers; more preferentially, the stabilizer(s) ii) of the oily dispersion (A’) are chosen from isobornyl (meth)acrylate homopolymer and statistical copolymers of isobornyl (meth)acrylate and of C1-C4 alkyl (meth)acrylate preferably present in an isobornyl (meth)acrylate/Ci-C4 alkyl (meth)acrylate weight ratio of greater than 4; advantageously, said weight ratio ranges from 4.5 to 19.

20. Process according to any one of Claims 15 to 19, in which the sum of the particle(s) i) + stabilizer(s) ii) present in the oily dispersion (A’) comprises from 10% to 50% by weight and preferably from 15% to 30% by weight of copolymers d) and from 50% to 90% and preferably from 70% to 85% by weight of copolymers a) + b), relative to the total weight of the sum of particle(s) i) + stabilizer(s) ii).

21 . Process according to any one of Claims 15 to 20, in which the hydrocarbon-based oil(s) iii) of the dispersion (A’) are apolar, i.e. formed solely of carbon and hydrogen atoms, in particular are volatile; preferably chosen from hydrocarbon-based oils containing from 8 to 14 carbon atoms, more preferentially isododecane.

22. Process according to any one of the preceding claims, in which composition (B) comprises as compound(s) B: iv) one or more amine compounds chosen from polyamine compounds containing at least two primary amine and/or secondary amine groups; and/or v) one or more organic or mineral, polymeric or non-polymeric, preferably organic or silicone, hydroxylated compounds chosen from polyhydroxylated compounds containing at least two hydroxyl groups; and/or vi) one or more organic or mineral, polymeric or non-polymeric, preferably organic or silicone-based, thiol compounds chosen from polythiol compounds containing at least two thiol groups; preferably iv) one or more amine compounds chosen from polyamine compounds containing at least two primary amine and/or secondary amine groups.

23. Process according to the preceding claim, in which the polyamine compounds containing at least two primary amine and/or secondary amine groups are chosen from:

■ poly((C2-C5)alkyleneimines), and in particular polyethyleneimines and polypropyleneimines, preferentially poly(ethyleneimines); poly(allylamines); polyvinylamines and copolymers thereof, notably with vinylamides; polyamino acids containing NH2 groups, such as polylysine; aminodextran; amino polyvinyl alcohol; copolymers based on acrylamidopropylamine; chitosans; polydi(Ci-C4)alkylsiloxanes comprising amine groups at the chain end or on side chains, in particular terminal or side amino(Ci-Ce)alkyl groups such as aminopropyl, more particularly those of formula (IVb) or (IVc) or (IVd):

in which formula (IVb) R^a and R^b, which may be identical or different, preferably identical, represent a group from among: (Ci-C4)alkyl such as methyl, (Ci-C4)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(Ci-C4)alkyl such as benzyl, or aryl(Ci- C4)alkoxy such as benzoxy, preferably (Ci-C4)alkyl such as methyl, R^c and R’^c, which may be identical or different, preferably identical, represent a hydrogen atom, a (Ci-C4)alkyl group, an amino(Ci-C4)alkyl group or a (Ci-C4)alkylamino(Ci-C4)alkyl group, preferably a hydrogen atom or an amino(Ci-C4)alkyl group such as aminoethyl; X represents a covalent bond, an oxygen atom, preferably a covalent bond, ALK and ALK’, which may be identical or different, preferably identical, represent a (Ci-Ce)alkylene group, preferably (Ci- C4)alkylene group such as propylene; n representing an integer greater than 2 and more particularly the value of n is such that the weight-average molecular weight of the silicone is between 500 and 55 000; more preferentially, the polydi(Ci-C4)alkylsiloxanes of formula (IVb) are of formula (IV’b) or (IV’b) below:

in which formula (IV’b) the value of n is such that the weight-average molecular weight of the silicone is between 500 and 55 000; formula (IV’b) with R^c, R’^c, ALK, ALK’ and n as defined previously for (IVb); more preferentially, ALK and ALK’ are identical and represent a (Ci-C4)alkylene group such as propylene, R^c and R’^c are identical and represent an amino(Ci-C4)alkyl group such as aminoethyl;

in which formula (IVc) R^a, R^b and R^d, which may be identical or different, preferably identical, represent a group from among: (Ci-C4)alkyl such as methyl, (Ci-C4)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(Ci-C4)alkyl such as benzyl, or aryl(Ci- C4)alkoxy such as benzoxy, preferably (Ci-C4)alkyl such as methyl, R^d may also represent a (Ci-Ce)alkyl group substituted with a (Ci-C4)alkylamino or amino group, R^c represents a hydrogen atom or a (Ci-C4)alkyl group, preferably a hydrogen atom; ALK represents a (Ci- Ce)alkylene group, preferably (Ci-C4)alkylene such as propylene; n and m, which may be identical or different, represent an integer greater than 2 and more particularly the values of m and n are such that the weight-average molecular weight of the silicone is between 1000 and 55 000; more preferentially, the polydi(Ci-C4)alkylsiloxanes of formula (IVc) are of formula (IV’c) below:

in which formula (IV’c) the values of n and m are such that the weight-average molecular weight of the silicone is between 1000 and 55 000;

in which formula (IVd) R^a and R^b, which may be identical or different, preferably identical, represent a group from among: (Ci-C4)alkyl such as methyl, (Ci-C4)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(Ci-C4)alkyl such as benzyl, or aryl(Ci- C4)alkoxy such as benzoxy, preferably (Ci-C4)alkyl such as methyl, and R^d represents a (Ci-Ce)alkyl group optionally substituted with a (Ci-C4)alkylamino or amino group, preferably (Ci-C4)alkyl such as isobutyl, tert-butyl or n-butyl, R^c represents a hydrogen atom or a (Ci-C4)alkyl group, preferably a hydrogen atom; ALK represents a (Ci-Ce)alkylene group, preferably (Ci-C4)alkylene such as propylene, n representing an integer greater than 2 and more particularly the value of n is such that the weight-average molecular weight of the silicone is between 500 and 5000; more preferentially, the polydi(Ci-C4)alkylsiloxanes of formula (IVd) are of formula (IV’d) below:

in formula (IV’d), the value of n is such that the weight-average molecular weight of the silicone is between 500 and 3000;

■ the amodimethicones of formula (IVe):

in which formula (IVe):

R^e represents a hydroxyl, (Ci-C4)alkoxy, amino or (Ci-C4)alkylamino group;

R^f represents a (Ci-C4)alkyl group such as methyl, a (Ci-C4)alkoxy group such as methoxy, a hydroxyl or -O-(SiR2)x- ’ group with R representing a (Ci-C4)alkyl or (Ci-C4)alkoxy group and R’ representing a (Ci-C4)alkoxy or hydroxyl group; preferably, R^f represents a (Ci- C4)alkyl, (Ci-C4)alkoxy or -O-(SiR2)x- ’ group with R representing a (Ci-C4)alkyl group such as methyl and R’ a hydroxyl or (Ci-C4)alkoxy group such as methoxy;

ALK and ALK’, which may be identical or different, represent a (Ci-Ce)alkylene group, preferably (Ci-C4)alkylene such as ethylene or propylene; n and m, which may be identical or different, represent an integer greater than 2, p and x are integers greater than or equal to 0; preferably, p is between 2 and 20 and more particularly the values of m, n, p and x are such that the weight-average molecular weight of the silicone is between 2000 and 700 000, preferentially between 5000 and 500 000; more preferentially, the amodimethicones of formula (IVe) are of formula (IV’e) or (IV”e) below:

in which formula (IV”e):

R⁹ represents a hydrogen atom or a (Ci-C4)alkyl group;

ALK represents a (Ci-Ce)alkylene group, preferably ethylene;

ALK’ represents a (Ci-Ce)alkylene group, preferably propylene; n and m, which may be identical or different, representing an integer greater than 2, x is an integer greater than or equal to 0; preferably, the values of m, n and x are such that the weight-average molecular weight of the silicone is between 2000 and 700000, preferentially between 5000 and 500 000; even more preferentially, the amodimethicones of formula (IVe) are of formula (IV”’e) below:

(IV”’e) in which formula (IV”’e):

R^f, R⁹, ALK, ALK’, m and n are as defined for (IV”e);

■ polyether amines, notably polyethylene glycol and/or polypropylene glycol a,co-diamine (bearing chain-end amine function);

■ polyamidoamine (PAMAM) dendrimers bearing amine terminal functions;

■ poly(meth)acrylates or poly(meth)acrylamides bearing primary or secondary amine side functions, such as poly(3-aminopropyl)methacrylamide or poly(2-aminoethyl) methacrylate; and

■ mixtures thereof; preferably, the amine compound(s) iv) of composition (B) are chosen from those of formulae (IVb) and (IVe) as defined previously; more preferentially, the amine compound(s) iv) of composition (B) are chosen from those of formulae (IV’b) and (IV’e) as defined previously.

24. Process according to any one of Claims 15 to 23, in which composition (B) comprises one or more hydrocarbon-based oil(s) iii) as defined in Claim 15 or 21 ; preferably, the hydrocarbon-based oils iii) included in the oily dispersion (A’) and composition (B) are identical; more preferentially, the hydrocarbon-based oil iii) included in composition (B) is isododecane.

25. Process according to any one of the preceding claims, in which the colouring agent(s) P) are chosen from pigments, preferably from carbon blacks such as Black 2, iron oxides, notably red, brown or black iron oxides, and micas coated with iron oxide, triarylmethane pigments, notably blue and violet triarylmethane pigments, such as Blue 1 Lake, azo pigments, notably red azo pigments, such as D&C Red 7, alkali metal or alkaline-earth metal salts of lithol red, such as the calcium salt of lithol red B, and mixtures thereof.

26. Process according to any one of the preceding claims, in which the colouring agent(s) P) are included in composition (A).

27. Process according to any one of the preceding claims, involving:

■ applying to the keratin fibres a composition (C) comprising the compound(s) E as defined in any one of Claims 1 or 6 to 11 ; followed by

■ applying to the keratin fibres a composition (A) as defined in any one of Claims 1 , 3, 4, 12 or 14 to 21 ; followed by

■ applying to the keratin fibres a composition (B) as defined in any one of Claims 1 , 5 or 22 to 24; it being understood that the colouring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) and/or in composition (C), preferably in composition (A) and/or in composition (B), more preferentially in composition (A).

28. Process according to any one of Claims 1 to 26, involving

■ applying to the keratin fibres a composition (B) as defined in any one of Claims 1 , 5 or 22 to 24; it being understood that:

- the compound(s) E are included in composition (A) and/or in composition (B), preferably in composition (A); and

29. Kit or device with several separate compartments, comprising:

■ in a first compartment: composition (A) as defined in any one of Claims 1 , 3, 4, 12 or 14 to 21 ;

■ in a second compartment separate from the first: composition (B) as defined in any one of Claims 1 , 5, or 22 to 24; and

■ optionally in a third compartment separate from the other two: composition (C) as defined in Claim 1 or 12; and ■ optionally in a fourth compartment separate from the other three: composition (D) as defined in Claim 1 ; in which:

- at least one of the compositions of the kit comprises one or more compounds E as defined in any one of Claims 1 or 6 to 11 ; and

- at least one of the compositions of the kit comprises one or more colouring agents as defined in Claim 1 or 25.

30. Composition (AO) comprising: - the oily dispersion (A’) as defined in any one of Claims 14 to 21 ;

- one or more compounds E as defined in any one of Claims 1 or 6 to 11 ;

- optionally one or more colouring agent(s) as defined in Claim 1 or 25.