FR3117849A1 - Process for dyeing keratinous fibers using two distinct compounds capable of forming covalent bonds together as well as a particular metal salt - Google Patents

Abstract

The present invention relates to a process for dyeing keratin fibers comprising the application to the keratin fibers of two separate compositions comprising two separate compounds capable of forming covalent bonds together, the process also using one or more metal salt(s). s) particular(s) and one or more coloring agent(s).

Description

Process for dyeing keratinous fibers using two distinct compounds capable of forming covalent bonds together as well as a particular metal salt

Technical field of the invention

The present invention relates to a process for dyeing keratin fibers comprising the application to the keratin fibers of two separate compositions comprising two separate compounds capable of forming covalent bonds together, the process also using one or more metal salt(s). s) particular(s) and one or more coloring agent(s).

Background of the invention

Cosmetic products often require the use of film-forming polymers to obtain a deposit of the product on keratin materials with good cosmetic properties. In particular, it is necessary for the film-forming deposit to have good hold, in particular for the deposit not to transfer on contact with fingers, clothing, as well as good hold in contact with water, in particular rain. or when showering or even sweating. Skin sebum can also damage the film-forming deposit.

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

Non-permanent coloring or direct coloring consists in dyeing the keratin fibers with dye compositions containing direct dyes. These dyes are colored and coloring molecules with an affinity for keratin fibres. They are applied to the keratin fibers for the time necessary to obtain the desired coloration, then rinsed off.

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

Some of these dyes can be used under lightening conditions, which makes it possible to obtain visible colorations on dark hair.

It is also known to dye keratin fibers permanently by oxidation dyeing. This coloring technique consists in applying to the keratin fibers a composition containing dye precursors such as oxidation bases and couplers. These precursors under the action of an oxidizing agent will form one or more colored species in the hair.

The variety of molecules involved in oxidation bases and couplers makes it possible to obtain a rich palette of colors and the resulting colorations are generally permanent, powerful, and resistant to external agents, in particular to light, bad weather, washing, perspiration and rubbing.

To be visible on dark hair, these two coloring techniques require prior or simultaneous bleaching of the keratin fibres. This bleaching step implemented with an oxidizing agent such as hydrogen peroxide or persalts can alter the cosmetic properties of the hair, which then tends to become rough, more difficult to disentangle and more fragile.

Another coloring method is to use pigments. Indeed, the use of pigment on the surface of keratin fibers generally makes it possible to obtain visible colorings on dark hair since the pigment on the surface masks the natural color of the fiber. The use of pigment for coloring keratin fibers is for example described in patent application FR 2 741 530, which recommends the use for the temporary coloring of keratin fibers of a composition comprising at least one dispersion of particles of film-forming polymer comprising at least one acid function and at least one pigment dispersed in the continuous phase of said dispersion.

The colors obtained by this method of coloring have the disadvantage of being easily removed with shampoo.

It is also known from patent application FR 2 907 678 to produce colored coatings for the hair from a composition comprising a polysiloxane/polyurea block copolymer and a pigment. However, with such a composition, the coatings obtained are not always very homogeneous and the individualization of the hair is not always very good.

It is also known from patent application FR 3 087 123 to implement a process for dyeing keratinous fibers in at least two steps comprising in a first step the application to said fibers of an oily dispersion comprising i) particles copolymers of alkyl acrylates and acrylic anhydrides, ii) stabilizers, iii) one or more hydrocarbon oils and; then in a second step the application to said fibers of a composition comprising iv) one or more amine compounds, it being understood that the process of the invention uses v) one or more dye(s) and/or pigment( s) which can be found in the oily dispersion and/or in the composition comprising the amino compound(s), and/or in another composition. This process makes it possible in particular to obtain a color that remains after shampoos.

However, the inventors realized that the shampoo protocol could vary from one user to another, in particular with regard to the length of the shampoo exposure time, a longer exposure time possibly being the cause a less good resistance of the color to the shampoo. Furthermore, the selectivity of the coloring obtained by this process can sometimes be significant, that is to say that sometimes significant differences in coloring can be observed throughout the same keratin fiber which generally comprises zones differently sensitized from root to tip.

There is therefore a real need to develop a process for coloring keratin fibers which makes it possible to obtain a coloring having a better remanence to shampoos, the remanence being independent of the shampoo protocol followed by the user and being observed in particular for long leave-on times for the shampoo, i.e. at least one minute. Such a process should also make it possible to obtain a coloring with low selectivity, that is to say low differences in coloring observed throughout the same keratin fiber which generally comprises zones sensitized differently from its root to The point. Finally, such a process must not lead to degradation of the keratin fibers and make it possible to preserve perfectly individualized keratin fibers.

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

According to a first aspect, the subject of the present invention is a process for dyeing keratin fibers comprising:
▪ the application to the keratin fibers of a composition (A) comprising at least one compound A carrying at least one chemical function A ; And
▪ the application to the keratin fibers of a composition (B) comprising at least one compound B carrying at least one chemical function B , the compound B being different from the compound A ;
in which :
- the chemical functions A and B are capable of forming covalent bonds together; And
- the process implements:
α) one or more metal salt(s) chosen from transition metal salts, alkali metal salts, alkaline-earth metal salts, aluminum salts, boron salts, salts of tin, magnesium salts, hydrates thereof and mixtures thereof, the metal salt(s) being included in composition (A) and/or in composition (B) and/or in a separate composition ( C) , composition (C) also being applied to the keratin fibres; And
β) one or more coloring agent(s) chosen from direct dyes, oxidation dyes, pigments and mixtures thereof, the coloring agent(s) being included in the composition (A) and/or in composition (B) and/or in composition (C) and/or in a separate composition (D) , composition (D) also being applied to the keratin fibres.

According to a second aspect, the subject of the present invention is a composition (A0) comprising:
- the dispersion (A′) as defined below;
- one or more metal salt(s) as defined above;
- optionally one or more coloring agent(s) as defined above.

According to a third aspect, the subject of the present invention is a composition (B0) comprising:
- at least one compound B as defined previously;
- one or more metal salt(s) as defined previously;
- optionally one or more coloring agent(s) as defined above.

According to a fourth aspect, the subject of the present invention is a composition (C0) comprising:
- one or more metal salt(s) as defined previously;
- one or more coloring agent(s) as defined above.

According to a fifth aspect, the subject of the present invention is a kit or device with several separate compartments comprising:
▪ in a first compartment: the composition (A) as defined above;
▪ in a second compartment distinct from the first: the composition (B) as defined previously; And
▪ optionally in a third compartment separate from the other two: the composition (C) as defined above; And
▪ optionally in a fourth compartment separate from the other three: the composition (D) as defined previously;
in which :
- at least one of the compositions of the kit comprises one or more metal salt(s) as defined previously; And
- at least one of the compositions of the kit comprises one or more coloring agent(s) as defined previously.

Detailed description of the invention

Within the meaning of the present invention, and unless a different indication is given:

▪ “keratin fibres” means fibers of human or animal origin such as hair, body hair, eyelashes, eyebrows, wool, angora, cashmere or fur. According to the present invention, the keratin fibers are preferably human keratin fibers, more preferably the hair.

▪ by "alkyl group" is meant a saturated C ₁ -C ₈ hydrocarbon group, linear or branched, in particular C ₁ -C _6, preferably C ₁ -C ₄ such as methyl, ethyl, isopropyl, and t -butyl;

▪ “alkoxy group” means an alkyl-oxy group with alkyl as defined above, preferably C ₁ -C ₄ alkoxy such as methoxy, ethoxy;

▪ the expression "optionally substituted" attributed to the alkyl group implies that said alkyl group may be substituted by one or more groups chosen from the groups i) hydroxy, ii) C ₁ -C ₄ alkoxy, iii) acylamino, iv ) amino optionally substituted by one or two identical or different C ₁ -C ₄ alkyl groups, said alkyl radicals possibly forming with the nitrogen atom which carries them a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom different or not from nitrogen;

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

▪ by “alkylene group” is meant a divalent C ₁ -C ₈ saturated hydrocarbon group, linear or branched, in particular C ₁ -C _{6 ,} preferably C ₁ -C ₄ such as methylene, ethylene or propylene;

▪ by "cycloalkyl group" is meant a saturated cyclic hydrocarbon 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 by one or more (C ₁ -C ₄ )alkyl groups such as methyl, preferably the cycloalkyl group is an isobornyl group.

▪ by "cyclic group" is meant a cyclic hydrocarbon group, saturated or unsaturated, aromatic or non-aromatic, comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms such as cyclohexyl or phenyl;

▪ by "heterocyclic group" is meant a cyclic hydrocarbon group, saturated or unsaturated, aromatic or non-aromatic, comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms, and from 1 to 5 heteroatoms selected from O, S, and N such as morpholinyl, piperazinyl, piperidinyl, furyl, pyridinyl, indolyl;

▪ by “aryl group” is meant an aromatic unsaturated cyclic group, comprising from 6 to 12 carbon atoms, mono or bicyclic, fused or not, preferably the aryl group comprises 1 ring and 6 carbon atoms such as phenyl;

▪ by "aryloxy group" is meant an aryl-oxy group i.e. aryl-O- with aryl as defined above, preferably phenoxy;

▪ by “aryl(C ₁ -C ₄ )alkoxy group” is meant an aryl-(C ₁ -C ₄ )alkyl-O- group, preferably benzoxy.

▪ by "heteroaryl group" is meant a mono or polycyclic group, condensed or not, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, and of which at least one ring is aromatic; préférentiellement un groupe hétéroaryle est choisis parmi acridinyle, benzimidazolyle, benzobistriazolyle, benzopyrazolyle, benzopyridazinyle, benzoquinolyle, benzothiazolyle, benzotriazolyle, benzoxazolyle, pyridinyle, tetrazolyle, dihydrothiazolyle, imidazopyridinyle, imidazolyle, indolyle, isoquinolyle, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyle, oxazolyle, oxazolopyridyle , phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl.

▪ the "aryl" or "heteroaryl" groups or the aryl or heteroaryl part of a group can be substituted by at least one substituent carried by a carbon atom, chosen from:
- a C ₁ -C ₈ alkyl group, optionally substituted by one or more groups chosen from hydroxy, C ₁ -C ₂ alkoxy, (poly)-hydroxy C ₂ -C ₄ alkoxy, acylamino, amino substituted by two identical or different C ₁ -C ₄ alkyl groups, optionally carrying at least one hydroxy group or, the two groups being able to form, with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members , preferably 5 or 6 membered, saturated or unsaturated, optionally substituted optionally comprising another heteroatom identical to or different from nitrogen;
- a halogen atom;
- a C ₁ -C ₂ alkoxy group;
- a 5- or 6-membered heterocycloalkyl group;
- an acylamino group (-NR-COR') in which the R group is a hydrogen atom, a C ₁ -C ₄ alkyl group and the R' group is a C ₁ -C ₂ alkyl group; a carbamoyl group ((R) ₂ N-CO-) in which the R groups, which may or may not be identical, represent a hydrogen atom, a C ₁ -C ₄ alkyl group; an alkylsulfonylamino group (R'SO ₂ -NR-) in which the R group represents a hydrogen atom, a C ₁ -C ₄ alkyl group and the R' group represents a C ₁ -C ₄ alkyl group, a phenyl group; an aminosulfonyl group ((R) ₂ N-SO ₂ -) in which the R groups, which may or may not be identical, represent a hydrogen atom or a C ₁ -C ₄ alkyl group;
- a carboxylic group in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not);
- a cyano group;
- a polyhaloalkyl group, preferably trifluoromethyl;

▪ the cyclic or heterocyclic part of a non-aromatic group can be substituted by at least one substituent chosen from the groups:
- C-alkoxy₁-VS₄ ;
- C-alkyl₁-VS₄ ;
- alkylcarbonylamino (RCO-NR'-) in which the radical R' is a hydrogen atom, an alkyl group in C₁-VS₄and the group R is a C alkyl group₁-VS₂;
- alkylcarbonyloxy (RCO-O-) in which the radical R is an alkyl group in C₁-VS₄, amino group optionally substituted by one or two identical or different C alkyl groups₁-VS₄, said alkyl groups being able to form with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from nitrogen;
- alkoxycarbonyl (RG-CO-) in which the R group is a C-alkoxy group₁-VS₄, G is an oxygen atom, or an amino group optionally substituted by a C-alkyl group₁-VS₄itself, said alkyl group being able to form with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from nitrogen;

▪ a cyclic or heterocyclic group, or a non-aromatic part of an aryl or heteroaryl group, can also contain one or more oxo groups;

▪ a hydrocarbon chain is unsaturated when it contains 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 application, it is also meant their optical isomers, their geometric isomers, their tautomers, their salts or their solvates, alone or as a mixture.

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

Process for coloring keratin fibers

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

The Applicant has found, surprisingly, that the process according to the invention makes it possible in particular to obtain on keratin fibers colored sheathings having a visible coloring on all types of fibers, in particular on dark hair, the coloring being remanent to shampoos independently of the shampoo protocol followed by the user, the remanence being observed in particular for long exposure times of the shampoo, i.e. of at least one minute. In addition, the process makes it possible in particular to obtain a smooth and homogeneous deposit and the keratin fibers remain perfectly individualized, could be styled without problem. Finally, the coloration obtained by the method according to the invention is characterized by low selectivity.

The term "individualized keratin fibers" means keratin fibers, in particular hair which, after application of the compositions and drying, is not stuck together (or is all separated from one another) and therefore does not form clusters of fibers, the sheathing being formed around virtually every fiber.

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 brought into contact, possibly with a chemical and/or physical stimulus, the function chemical A reacts with chemical function B to form a covalent bond.

Thus, chemical function A can react with chemical function B spontaneously or for example by activation by temperature, pH, a co-reactant or a chemical or biochemical catalyst, such as an enzyme.

Composition (A) can be applied after composition (B) or composition (B) can be applied after composition (A) .

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

Membership (A)

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

When the compound(s) A carry 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 does not comprise a chemical function B .

According to a particular embodiment, the composition(AT)comprises less than 10% by weight of compoundB, of preferably less than 5% by weight of compoundB, more preferably less than 2% by weight of compoundBrelative to the total weight of the composition(AT), even more preferably the composition(AT)is compound freeB.

Preferably, the chemical function(s) A are chosen from the following functions:
- epoxy;
- 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, hemi-acetals, aminals, hemi-aminols;
- isocyanates;
- thiocyanate;
- ketones including alpha-hydroxyketones, alpha-haloketones;
- lactones, thiolactones;
- imines;
- imides;
- N-hydroxysuccinimide esters;
- imidates;
- thiosulphate;
- oxazine and oxazoline;
- oxazinium and oxazolinium;
- C ₁ to C ₃₀ alkyl or C ₆ to C ₃₀ aryl or aralkyl halides, in particular iodides, chlorides, bromides;
- unsaturated, carbon or heterocycle halides;
- sulphonyl halides of formula RSO ₂ X, in which X=Cl or F and R is an alkyl group in C ₁ to C ₃₀ ;

- cyclic carbonates;
- diazonium;
- carbodiimide;
- and mixtures thereof.

According to a preferred embodiment, the chemical function(s) A are chosen from the functions anhydride, acid chloride, carboxylic acid esters, epoxide, and mixtures thereof, preferably from the functions anhydride, acid chloride, esters of carboxylic acid, and mixtures thereof.

According to a more preferred embodiment, the chemical function or functions A are anhydride functions.

Preferably, the compound(s) A are polymers.

The polymer(s) can be synthetic or natural.

According to a particularly preferred embodiment, the polymer or polymers 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 compound(s) A .

According to another preferred embodiment, the composition (A) is an oily dispersion (A') which comprises the compound or compounds A.

By “ anhydrous ” dispersion or composition is meant a dispersion or composition containing less than 2% by weight of water, preferably less than 0.5% by weight of water, more preferably free of water. Where appropriate, such small amounts of water can in particular be supplied by ingredients of the composition which can contain residual amounts thereof.

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

Preferably, composition (A) is anhydrous.

According to a preferred embodiment, the oily dispersion (A′) is an oily dispersion of i) one or more particle(s) of at least one polymer stabilized at the surface by ii) one or more agent(s) stabilizer(s) in a preferably anhydrous medium, additionally containing iii) one or more hydrocarbon oil(s).

i) Polymer particle(s)

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

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

The particles of polymer(s) preferably have a number-average size ranging from 5 and 500 nm, in particular ranging from 10 to 400 nm, and better still ranging from 20 to 300 nm.

The particle or particles i) of the oily dispersion (A') consist of one or more ethylenic copolymer(s) of a) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ ) alkyl and b) ethylenically unsaturated anhydride compound.

By "ethylenic copolymer" is meant a polymer resulting from the polymerization of two monomers: monomer a) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl and monomer b) anhydride compound with unsaturation ethylenic.

By “ethylenically unsaturated anhydride compound” is meant a carboxylic acid anhydride compound comprising at least one ethylenic unsaturation –(R _a )C=C(R _b )–, –C(R _a )=C(R _b )– R _c or >C=C(R _a )–R _b , with R _a , R _b , and R _c , identical or different, representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl , preferably hydrogen. In particular, the ethylenically unsaturated anhydride compound is a cyclic compound, preferably having 5 or 6 members, and comprising ethylenic unsaturation.

Monomer a) (C ₁ -VS ₄ (C) )(alkyl)acrylate ₁ -VS ₄ )alkyl

Preferably, the monomer a) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl is of formula H ₂ C=C(R)-C(O)-O-R' with R representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl, and R' representing a (C ₁ -C ₄ )alkyl group such as methyl or ethyl.

More preferably, the (C ₁ -C ₄ )alkyl)acrylate (C ₁ -C ₄ )alkyl monomer a) is a (C ₁ -C ₄ )alkyl (meth)acrylate monomer.

Even more preferably, the monomer a) (C ₁ -C ₄ )(alkyl) acrylate (C ₁ -C ₄ )alkyl 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;

Advantageously, a (C ₁ -C ₄ )alkyl acrylate monomer a) is used.

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

Monomer b) ethylenically unsaturated anhydride

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

Formulas (Ib) and (IIb) in which R _a , R _b and R _c , identical or different, representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably R _a , R _b , and R _c represent a hydrogen atom.

More preferably, the ethylenically unsaturated anhydride monomer b) is of formula (Ib) . 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) can be chosen from:
- methyl acrylate/maleic anhydride copolymers;
- ethyl acrylate/maleic anhydride copolymers; And
- methyl acrylate/ethyl acrylate/maleic anhydride copolymers.

Advantageously, the polymer of particles i) is a non-crosslinked polymer.

The polymer of particles i) preferably has a number average molecular weight ranging from 2,000 to 10,000,000.

The particles of polymer(s) 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 preferably ranging from 30 to 50% by weight, even more preferably ranging from 36% to 42% by weight relative to the total weight of the oily dispersion (A′) .

ii) Stabilizing agent(s)

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

The stabilizing agent(s) ii) consist of ethylenic polymers chosen from c) polymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl monomers; and d) copolymers of (C ₁ -C ₆ )(alkyl)acrylate, (C ₃ -C ₁₂ )cycloalkyl and (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl.

Preferably, the stabilizing agent(s) ii) consist of ethylenic polymers chosen from:
c) polymers of monomers of formula H₂C=C(R)-C(O)-O-R’’ withRrepresenting a hydrogen atom or a group (C₁-VS₄)alkyl such as methyl, andR''representing a group (C₅-VS₁₀)cycloalkyl 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’’ withR,R'AndR''as previously defined.

According to a preferred embodiment, the stabilizing agent(s) ii) are chosen from isobornyl (meth)acrylate polymers, preferably from isobornyl (meth)acrylate homopolymer and random copolymers of isobornyl (meth)acrylate and of C ₁ -C ₄ alkyl (meth)acrylate preferably present in a weight ratio of isobornyl (meth)acrylate/C ₁ alkyl (meth)acrylate -C ₄ greater than 4. Advantageously, said weight ratio ranges from 4.5 to 19.

For these random copolymers, the defined weight ratio makes it possible to obtain a stable polymer dispersion, in particular after storage for 7 days at room temperature.

Advantageously, the stabilizing agent ii) is chosen from:
- isobornyl acrylate homopolymers;
- random copolymers of isobornyl acrylate/methyl acrylate;
- random copolymers of isobornyl acrylate/ethyl acrylate; And
- random copolymers of isobornyl acrylate/methyl acrylate/ethyl acrylate according to the weight ratio described above.

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

Preferably, the combination of particle(s) of polymer(s) i) + stabilizing agent(s) ii) present in the oily dispersion (A′) comprises from 15 to 30% by weight of copolymers d) and of 70 to 85% by weight of polymers a) + b), relative to the total weight of the particle(s) of polymer(s) i) + stabilizing agent(s) ii).

Composition (A) preferably comprises a total content of particle(s) i) + stabilizing agent(s) ii) ranging from 1 to 50% by weight, preferably ranging from 2 to 30% by weight, per relative to the total weight of the composition (A)

iii) Hydrocarbon oil(s)

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

By "oil" is meant a fatty substance that is liquid at ambient temperature at ambient temperature (25° C.) and atmospheric pressure.

By "hydrocarbon oil" is meant an oil formed essentially, or even consisting, of carbon and hydrogen atoms, and optionally of oxygen and nitrogen atoms, and not containing any silicon or fluorine. It may contain hydroxy, ester, ether, carboxylic acid, amine and/or amide groups.

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

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

According to another particular embodiment, the hydrocarbon oil or oils are a mixture of a volatile oil and a non-volatile oil.

By "volatile oil" is meant an oil (or non-aqueous medium) capable of evaporating 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, liquid at ambient temperature, having in particular a non-zero vapor pressure, at ambient temperature and at atmospheric pressure, in particular, having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (10 ^-3 to 300 mm Hg), and preferably ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01 to 10mm Hg).

By "non-volatile oil" is meant an oil having a vapor pressure of less than 0.13 Pa.

The hydrocarbon oil(s) can be chosen from:

▪ hydrocarbon oils having 8 to 14 carbon atoms, and in particular:
- branched C ₈ -C ₁₄ alkanes such as C ₈ -C ₁₄ isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, and for example the oils sold under the trade names Isopars' or Permetyls,
- linear alkanes, for example such as n-dodecane (C12) and n-tetradecane (C14) sold by Sasol respectively under the references PARAFOL 12-97 and PARAFOL 14-97 , as well as their mixtures, the undecane- tridecane, the mixtures of n-undecane (C11) and n-tridecane (C13) obtained in examples 1 and 2 of application WO2008/155059 from the company Cognis, and
- their mixtures;
▪ short chain esters (having 3 to 8 carbon atoms in total) such as ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate;
▪ hydrocarbon oils of plant origin such as triglycerides consisting of esters of fatty acids and glycerol, the fatty acids of which may have chain lengths varying from C ₄ to C ₂₄ , the latter possibly being linear or branched, saturated or unsaturated; these oils are in particular triglycerides of heptanoic acid or octanoic acid, or alternatively wheat germ, sunflower, grapeseed, sesame, corn, apricot, castor, shea, avocado, olive, soy, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, sesame, squash, rapeseed, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, bancoulier, passionflower, muscat rose; shea butter; or alternatively caprylic/capric acid triglycerides such as those sold by the company Stéarineries Dubois or those sold under the names Miglyol ^810® , ^812® and ^818® by the company Dynamit Nobel;
▪ synthetic ethers having 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, paraffin oils, and mixtures thereof;
▪ synthetic esters such as oils of formula R ₁ C(O)-OR ₂ in which R ₁ represents the residue of a linear or branched fatty acid comprising from 1 to 40 carbon atoms and R ₂ represents a hydrocarbon chain in particular branched chain containing from 1 to 40 carbon atoms provided that R ₁ + R ₂ is ≥ 10, such as Purcellin's oil (cetostearyl octanoate), isopropyl myristate, isopropyl palmitate, benzoates of C ₁₂ to C ₁₅ alcohols, hexyl laurate, diisopropyl adipate, isononyl isononanoate, 2-ethyl-hexyl palmitate, isostearyl isostearate, 2-hexyl laurate -decyl, 2-octyl-decyl palmitate, 2-octyl-dodecyl myristate, heptanoates, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate; hydroxylated esters such as isostearyl lactate, di-isostearyl malate, 2-octyl-dodecyl lactate; polyol esters and pentaerythritol esters;
▪ fatty alcohols that are liquid at room temperature with a branched and/or unsaturated carbon chain having 12 to 26 carbon atoms, such as octyldodecanol, isostearyl alcohol, oleyl alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol.

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

The term “silicone oil” means an oil comprising at least one silicon atom, and in particular at least one Si—O group. Silicone oil can be volatile or non-volatile.

As volatile silicone oils, mention may be made of volatile linear or cyclic silicone oils, in particular those having a viscosity ≤ 8 centistokes (cSt) (8 x 10 ^-6 m ² /s), and having, in particular, from 2 to 10 silicon atoms, and in particular, from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms. As volatile silicone oil that can be used in the invention, mention may be made, in particular, of dimethicones with a viscosity of 5 and 6 cSt, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, l hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof.

As non-volatile silicone oils, mention may be made of non-volatile, linear or cyclic polydimethylsiloxanes (PDMS); polydimethylsiloxanes comprising alkyl, alkoxy and/or phenyl groups, pendent or at the end of the silicone chain, groups having from 2 to 24 carbon atoms; phenyl silicones such as phenyl trimethicones, phenyl dimethicones, phenyl trimethylsiloxy diphenyl siloxanes, diphenyl dimethicones, diphenyl methyldiphenyl trisiloxanes, 2-phenyl ethyl trimethyl-siloxysilicates and pentaphenyl silicone oils.

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

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

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

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

More preferably, the hydrocarbon oil is isododecane.

According to another advantageous embodiment of the invention, the hydrocarbon oil or oils 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 can be prepared in the following way:

The polymerization is carried out in "dispersion", that is to say by precipitation of the polymer during formation, with protection of the particles formed with one or more stabilizing agents, preferably a stabilizing agent.

- In a first step, the stabilizing polymer (or stabilizing agent ii)) is prepared by mixing the monomer or monomers constituting the stabilizing polymer c) or d), with vi) a radical initiator, in a solvent called synthetic solvent, and by polymerizing these monomers;

- In a second step, the monomers constituting the polymer of the particles i) are added to the stabilizing polymer formed in the previous step and the polymerization of these added monomers is carried out in the presence of the radical initiator.

When the non-aqueous medium is a non-volatile iii) hydrocarbon-based oil, the polymerization can be carried out in an apolar organic solvent (synthetic solvent) then add the non-volatile hydrocarbon-based oil (which must be miscible with said synthetic solvent) and distill selectively the synthesis solvent.

The coloring agent(s) can be added during the first stage. According to another variant, the coloring agent(s) are added during the second stage or after the second stage.

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

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

When the non-aqueous medium is a volatile iii) hydrocarbon-based oil, the polymerization can be carried out directly in said oil, which therefore also acts as a synthesis solvent. The monomers must also be soluble therein, as well as the radical initiator, and the polymer of the particles obtained must be insoluble therein.

The monomers are preferably present in the synthesis solvent, before polymerization, in a proportion of 5% to 45% by weight. All of the monomers can be present in the solvent before the start of the reaction, or part of the monomers can be added as the polymerization reaction progresses.

The polymerization is preferably carried out in the presence vi) of one or more radical initiators, in particular of the type:
- peroxide in particular chosen from tert-Butyl peroxy-2-ethylhexanoate: Trigonox 21S; 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane: Trigonox 141; tert-butyl peroxypivalate: Trigonox 25C75 from AkzoNobel; Or
- azo in particular chosen from AIBN: azobisisobutyronitrile; V50: 2,2'-azo-bis(2-amidinopropane) dihydrochloride.

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

The polymer particles i) are stabilized at the surface, when they form during the polymerization, thanks to the stabilizer ii).

The stabilization can be carried out 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, in particular when the monomers of the polymer of the particles i) are also continuously added.

It is possible to use from 10 to 30% by weight of the stabilizing agent(s) relative to the total weight of monomers used (stabilizing agents ii)+polymer particles i)), and preferably from 15 to 25% by weight.

The oily dispersion of polymer particles (A′) obtained by this preparation process advantageously comprises from 30 to 65% by weight of dry matter, relative to the total weight of said dispersion, and preferably from 40 to 60% by weight per relative to the total weight of said dispersion.

Membership (B)

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 carry several chemical functions B , the chemical functions B can 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 function A .

According to a particular embodiment, the composition(B)comprises less than 10% by weight of compoundAT, of preferably less than 5% by weight of compoundAT, more preferably less than 2% by weight of compoundATrelative to the total weight of the composition(B), even more preferably the composition(B)is compound freeAT.

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

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

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

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

According to a preferred embodiment, composition (B) comprises as compound(s) B :
iv) one or more amino compound(s) chosen from polyamino compounds having at least two primary amine and/or secondary amine groups; and or
v) one or more organic or inorganic hydroxylated compound(s), polymeric or not, preferably organic(s) or silicone(s), chosen from polyhydroxylated compounds having at least two hydroxyl groups; and or
vi) one or more thiol compound(s), organic(s) or inorganic(s), polymer(s) or not, preferably organic(s) or silicone(s), chosen from polythiol compounds having at least two thiol groups.

iv) the amino compound(s)

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

The polyamino compounds can be chosen from diamino compounds, triamino compounds and mixtures thereof.

Polyamine compounds can be polymeric or non-polymeric.

“Non-polymeric” compound(s) means one or more compound(s) which is or are not directly obtained by a polymerization reaction of monomers.

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

As polyamino compounds, mention may in particular be made of 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, methyl bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4 -diaminobutane, N,N-dimethyldipropylene, triamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, ethylene diamine, 1,3-propylenediamine, 1,4-butylenediamine, lysine, cystamine, xylene diamine, tris(2-aminoethyl)amine, spermidine.

The polyamino compounds may have 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.

The polyamino compound(s) can be chosen from:
▪ poly((C ₂ -C ₅ )alkylene imines), and in particular polyethyleneimines and polypropyleneimines, in particular poly(ethylene imine) (for example that sold under the reference 46,852-3 by the company Aldrich Chemical);
▪ poly(allylamines) for example poly(allylamine) sold under the reference 47,913-6 by the company Aldrich Chemical);
▪ polyvinylamines and their copolymers, in particular with vinylamides; mention may in particular be made of vinylamine/vinylformamide copolymers such as those marketed under the name LUPAMIN® 9030 by the company BASF;
▪ polyamino acids having NH ₂ groups such as polylysine, for example that sold by the company JNC Corporation (formerly Chisso);
▪ amino dextran, such as that sold by the company CarboMer Inc;
▪ polyvinyl amino alcohol such as that sold by the company CarboMer Inc;
▪ copolymers based on acrylamidopropylamine;
▪ chitosan; And
▪ polydi(C ₁ -C ₄ )alkylsiloxanes, in particular polydimethylsiloxanes, comprising amine groups at the end of the chain or on the side chains, in particular terminal or side amino(C ₁ -C ₆ )alkyl groups such as aminopropyl , more particularly those of formula (IVb) or (IVc) or (IVd) :

Formula (IVb) in which R ^a , and R ^b , which are identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, aryl such as as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl, R ^c and R' ^c , identical or different, preferably identical, represent a hydrogen atom, a (C ₁ -C ₄ )alkyl group, an amino(C ₁ -C ₄ )alkyl or (C ₁ -C ₄ )alkylamino(C ₁ -C ₄ )alkyl, preferably a hydrogen atom or an amino(C ₁ -C ₄ )alkyl group such as aminoethyl; X represents a covalent bond, an oxygen atom, preferably a covalent bond, ALK and ALK' , identical or different, preferably identical, represent a (C ₁ -C ₆ )alkylene group, preferably (C ₁ -C ₄ ) 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 55,000;
Preferably, the polydi(C ₁ -C ₄ )alkylsiloxanes of formula (IVb) are of the following formula (IV'b) or (IV''b) :


Formula (IVb') in which the value of n is such that the weight-average molecular weight of the silicone is between 500 and 55,000. As an example of amino silicone (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, “DMS-A35” by the company GELEST;
Formula (IV''b) with R ^c , R' ^c , ALK , ALK' , and n as defined above for (IVb) . Preferably ALK and ALK' are identical and represent a (C ₁ -C ₄ )alkylene group such as propylene, R ^c and R' ^c are identical and represent an amino(C ₁ -C ₄ )alkyl group such as aminoethyl.
Mention may be made in particular of Dimethoxysilyl Ethylenediaminopropyl Dimethicone (RN: 71750-80-6), under the trade name GP-RA-157, marketed by Genesee Polymers.

Formula (IVc) in which R ^a , R ^b , and R ^d , which are identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy , aryl such as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl, R ^d may also represent a (C ₁ -C ₆ )alkyl group substituted by a (C ₁ -C ₄ )alkylamino or amino group, R ^c represents a hydrogen atom or a (C ₁ -C ₄ ) group alkyl, preferably hydrogen atom; ALK represents a (C ₁ -C ₆ )alkylene group, preferably (C ₁ -C ₄ )alkylene such as propylene; n and m , which are 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 is between 1000 and 55,000;
Preferably, the polydi(C ₁ -C ₄ )alkylsiloxanes of formula (IVc) are of the following formula (IV'c) :

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

Formula (IVd) in which R ^a , and R ^b , which are identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl, and R ^d represents a (C ₁ -C ₆ )alkyl group optionally substituted by a (C ₁ -C ₄ )alkylamino or amino group, preferably (C ₁ -C ₄ )alkyl, such as isobutyl, terbutyl or n -butyl, R ^c represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably a hydrogen atom; ALK represents a (C ₁ -C ₆ )alkylene group, preferably (C ₁ -C ₄ )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;

Preferably, the polydi(C ₁ -C ₄ )alkylsiloxanes of formula (IVd) are of the following formula (IV'd) :

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 an example of silicone (IVd), mention may be made of those sold under the names "MCR -A11”, “MCR-A12” by the company GELEST;
▪ amodimethicones of formula (IVe) :

Formula (IVe) in which:
R ^a , and R ^b , which are identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl;
R ^c represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably a hydrogen atom;
R ^e represents a hydroxy, (C ₁ -C ₄ )alkoxy, amino, (C ₁ -C ₄ )alkylamino group;
R ^f represents a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, a hydroxy group or -O–(SiR ₂ ) _x -R' with R representing a group ( C ₁ -C ₄ )alkyl or (C ₁ -C ₄ )alkoxy and R' representing a (C ₁ -C ₄ )alkoxy or hydroxy group, preferably R ^f represents a (C ₁ -C ₄ )alkyl group, ( C1-C4)alkoxy, or -O–(SiR ₂ ) _x -R' with R representing a (C ₁ -C ₄ )alkyl group such as methyl and R' a hydroxy or (C ₁ -C ₄ )alkoxy group such as than methoxy;
ALK and ALK′ , which are identical or different, represent a (C ₁ -C ₆ )alkylene group, preferably (C ₁ -C ₄ )alkylene such as ethylene or propylene; n and m , identical or different, representing 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 2,000 and 700,000, preferably between 5,000 and 500,000;
Preferably, the amodimethicones of formula (IVe) are of the following formula (IV'e) or (IV''e) :

Formula (IV'e) in which ALK represents a (C ₁ -C ₆ )alkylene group, preferably ethylene, ALK' represents a (C ₁ -C ₆ )alkylene group, preferably propylene, and m , n and p represent higher to 2, with m , n and p such that the weight-average molecular mass of the compound is between 5,000 and 500,000 approximately; preferably p represents an integer between 8 and 20;

Formula (IV''e) in which:
R ^a , and R ^b , identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, preferably (C ₁ -C ₄ ) alkyl such as methyl;
R ^c represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably a hydrogen atom;
R ^g represents a hydrogen atom, or a (C ₁ -C ₄ )alkyl group;
R ^f represents a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, or -O–(SiR ₂ ) _x -R' with R representing a (C ₁ - C ₄ )alkyl such as methyl and R' a hydroxy or (C ₁ -C ₄ )alkoxy group such as methoxy;
ALK represents a (C ₁ -C ₆ )alkylene group, preferably ethylene;
ALK' represents a (C ₁ -C ₆ )alkylene group, preferably propylene;
n and m , 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 2,000 and 700,000, preferably between 5,000 and 500,000.
Even more preferably, the amodimethicones of formula (IVe) are of the following formula (IV'''e) :

Formula (IV'''e) in which:
R ^f , R ^g , ALK , ALK' , m and n are as defined for (IV''e) . The amodimethicone and trimethylsiloxyamodimethicone belonging to the formula (IV''e) and to the formula (IV'''e) above are, for example, the amodimethicone and trimethylsiloxyamodimethicone of the ADM type sold by the company Wacker-Belsil®, it is possible also mention polydimethylsiloxane with aminoethylaminopropyl groups, with methoxy and/or hydroxy function and alpha-omega silanols in 60% aqueous cationic emulsion (Supplier reference: XIAMETER MEM-8299 EMULSION for DOW CORNING or Supplier reference: BELSIL ADM 4000 E for WACKER) ; polydimethylsiloxane with an aminoethyl iminopropyl group in nonionic microemulsion at 15% preserved (Supplier reference: BELSIL ADM LOG 1);
▪ polyether amines, in particular known under the reference JEFFAMINE from the company HUNSTMAN; and in particular: Polyethylene glycol and/or polypropylene glycol α, ω-diamine (with amine function at the end of the chain) 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) α, ω-diamine, polybutadienes α, ω-diamine;
▪ polyamidoamine dendrimers (PAMAM) with terminal amine functions;
▪ poly(meth)acrylates or poly(meth)acrylamides carrying lateral primary or secondary amine functions such as poly(3-aminopropyl)methacrylamide, poly(2-aminoethyl) methacrylate; And
▪ their mixtures.

As polyamino compounds having at least two primary amine and/or secondary amine groups, polydi(C ₁ -C ₄ )alkylsiloxanes comprising primary amine groups at the end of the chain and/or on the side chains are preferably used.

More preferentially, the amino compound(s) iv) comprised in composition (B) are chosen from those of formulas (IVb) and (IVe) as defined previously and even more preferentially from those of formulas (IV′ b) and (IV'e) as previously defined.

v) the hydroxy compound(s)

According to one embodiment, composition (B) comprises as compound(s) B : v) one or more hydroxylated, organic(s) or inorganic, polymer(s) or no, preferably organic(s) or silicone(s), chosen from polyhydroxylated compounds having at least two hydroxyl groups.

“Non-polymeric” compound(s) means one or more compound(s) which is or are not directly obtained by a polymerization reaction of monomers.

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

According to an advantageous variant, the hydroxylated compound(s) are silicone-based, that is to say they comprise at least two hydroxyl groups, and at least one siloxane chain.

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

Polyhydroxylated compounds can include other non-reactive chemical functions such as esters, amides, ketones, urethanes. It is possible to use a mixture of distinct polyhydroxy compounds such as a mixture of organic and inorganic polyhydroxy compound(s).

Non-polymeric hydroxy compounds

According to one embodiment of the invention, the hydroxylated compound(s) is (are) non-polymeric of formula(II):

Formula(II)in which :
qrepresents an integer greater than or equal to 2, preferably ranging from 2 to 10, more preferably ranging from 2 to 5;
Idenotes a 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, preferably 6 to 20 carbon atoms, linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated;
Ibeing optionally interrupted and/or terminated by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their combinations such as –O-, –O-C(X)-, -N(R) -C(X)-, -Si(R_vs)(R_d)-O- withRrepresenting a hydrogen atom or a group (C₁-VS₆)alkyl such as methyl; and or
Ibeing optionally substituted by one or more halogen atoms, or a group chosen from R_To(R_b)N-, -(X’)_To-C(X)-(X’’)_b-R_To,
-X,X'AndX'', identical or different, represent an oxygen atom, a sulfur atom, or an N(R_b);
-ToAndbequal to 0 or 1, preferably the sumTo+bis worth 1,
-R _To AndR _b , identical or different, represent a hydrogen atom, or a group (C₁-VS₆)alkyl, or aryl(C₁-VS₄)alkyl such as benzyl, preferablyR _To AndR _b represent a hydrogen atom;
-R _vs AndR _d , identical or different, represent a group (C₁-VS₆)alkyl, aryl(C₁-VS₄)alkyl or (C₁-VS₆)alkoxy.

According to a particular embodiment of the invention , the hydroxylated compound(s) is (are) of formula (II) in which:
q represents an integer greater than or equal to 2, preferably ranging from 2 to 10, more preferably ranging from 2 to 5;
L denotes a 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, linear or branched, saturated or unsaturated, or (hetero ) cyclic, saturated or unsaturated, L possibly also being interrupted by one or more oxygen atoms, and/or comprising one or more functions chosen from amino, ether, thioether, ester, thioester, ketone, thioketone, amide and thioamide.

According to this particular embodiment, the polyol compound is preferably a diol compound.

According to this particular embodiment, L preferably denotes a C ₈ -C ₁₈ multivalent radical, in particular linear.

Preferably, the polyol is a C ₈ -C ₁₈ diol, in particular linear, in particular liposoluble. Advantageously, the C ₈ -C ₁₈ chain is a hydrocarbon chain, ie formed from carbon and hydrogen.

In particular, the polyol is a linear C ₈ -C ₁₆ diol, in particular C ₁₀ -C ₁₄ .

As polyol 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, 1,18-octadecanediol.

Preferably, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol are used. Preferably, 1,12-dodecanediol is used.

Polymeric hydroxy compounds

According to one embodiment of the invention, the hydroxylated compound(s) is (are) polymeric. The polymeric hydroxylated compound(s) of the invention may be homopolymers, copolymers, star, combe, brush and dendritics with hydroxy units. The polymers can be of natural origin such as polysaccharides, polypeptides, or synthetic such as (meth)acrylic polymers, polyesters, polyglycols. The hydroxy units can be present as terminal or pendent groups.

The polymeric hydroxy compound(s) is (are) preferably organic or silicone compound(s), more preferably of formula (V) :

Formula (V) in which:
p represents an integer greater than or equal to 2;
POLY denotes a polymeric radical, preferably carbonaceous or silicone;
POLY being optionally interrupted by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their associations such as –O-, –OC(X)-, -N(R)-C( X)-, -Si(R _c )(R _d )-O- with R representing a hydrogen atom or a (C ₁ -C ₆ )alkyl group such as methyl; and or
POLY being optionally substituted by one or more halogen atoms, or a group chosen from R _a (R _b )N-, -(X') _a -C(X)-(X'') _b -R _a ,
- X , X' and X'' , which are identical or different, represent an oxygen or sulfur atom, or an N(R _b ) group;
- a and b being 0 or 1, preferably the sum a + b is 1;
- R _a and R _b , identical or different, represent a hydrogen atom, or a group (C ₁ -C ₁₀ )alkyl, or aryl (C ₁ -C ₄ )alkyl such as benzyl, preferably R _a and R _b represent a hydrogen atom; And
- R _c and R _d , which are identical or different, represent a (C ₁ -C ₁₀ )alkyl, aryl (C ₁ -C ₄ )alkyl or (C ₁ -C ₁₀ )alkoxy group.

According to a particular embodiment of the invention, the polymeric hydroxy compound(s) are of formula (V) in which:
p represents an integer greater than or equal to 2;
POLY denotes a carbonaceous or silicone polymeric radical, POLY possibly also containing one or more heteroatoms such as O, N, S, and/or one or more functions chosen from amino functions, (thio)esters, (thio)ketones, ( thio)amides, (thio)ureas, (thio)carbamates, and/or be substituted by one or more (C ₁ -C ₁₀ )alkyl groups, linear or branched, (C ₁ -C ₁₀ )alkoxy groups, linear or branched, it being understood that when POLY is substituted, the hydroxy functions can be carried by the substituent(s).

The average molecular weight by molar weight of the polymer polyol compounds, such as those of formula (V) , is generally between 500 and 400,000, preferably between 500 and 150,000.

Preferably, the polymeric hydroxy compound(s) may be polymer (poly)ols, in particular polyolefin (poly)ols, polydi(C ₁ -C ₆ )alkylsiloxane (poly)ols, polyester (poly)ols.

Preferably, the (poly)ols are diols.

The polyolefin (poly)ols can be polydienes with hydroxy ends, such as for example those described in FR-A-2782723. They can be chosen from (poly)ols derived from homopolymers and copolymers of polybutadiene, polyisoprene and poly(1,3-pentadiene). Preferably, they 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 marketed by the company CRAY VALLEY under the trademarks POLY BD R45HTLO, POLY BD R45V, and POLY BD R-20 LM, which will preferably be used hydrogenated; as well as hydrogenated (poly)hydroxylated (1,2-polybutadienes), such as GI3000 with Mn=3100, GI2000 (Mn=2100) and GI1000 (Mn=1500) marketed by the company Nisso.

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

Formula (VI) in which:
ALK ⁴ and ALK ⁵ , identical or different, preferably different, represent a (C ₁ -C ₆ )alkylene group, linear or branched, optionally substituted by one or more hydroxy, thiol or amino groups, preferably ALK ⁴ represents a linear (C ₁ -C ₆ )alkylene group such as n -butylene, and ALK ⁵ represents a branched (C ₃ -C ₆ )alkylene group such as i -butylene;
X represents an oxygen or sulfur atom or an N( Ra ) group with Ra representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably X represents an oxygen or sulfur atom, more preferably an oxygen atom, and
n and m , identical or different, represent an integer, with n + m representing an integer greater than or equal to 1.

Among the polyolefins with hydroxy ends of formula (VI) , mention may preferably be made of polyolefins, homopolymers or copolymers, with α,ω hydroxy ends, such as polyisobutylenes with α,ω hydroxy ends and the copolymers of formula (VI′) :

in particular those marketed by Mitsubishi under the POLYTAIL brand. Preferably, hydrogenated polybutadienes diols are used.

The polydi(C ₁ -C ₆ )alkylsiloxane (poly)ols are particularly chosen from those of formula (VII) :

Formula (VII) in which:
R ^a , and R ^b , identical or different, preferably identical, represent a (C ₁ -C ₆ )alkyl group optionally substituted by one or more hydroxy, amino or thiol groups, (C ₁ -C ₆ )alkoxy such as methoxy , aryl such as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )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; particularly n is an integer ranging from 1 to 100, preferably ranging from 5 to 50, and preferentially ranging from 10 to 30, and
L ⁴ and L ⁵ , identical or different, represent a covalent bond, or a hydrocarbon chain comprising from 1 to 100 carbon atoms, saturated or unsaturated, linear or branched, optionally cyclic, optionally interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen, more preferably a (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene group -oxy(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylenoxy or oxy(C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene;
X represents an oxygen or sulfur atom, preferably oxygen.

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

Formula(VII')in which :
I ⁴ AndI ⁵ are as defined above, preferably represent a divalent group chosen from –R₂-, -GOLD₂-, -R₂-GOLD₂-GOLD'₂–, preferably –R₂-GOLD'₂-, withR ₂ AndR' ₂ , identical or different, representing a group (C₂-VS₆)alkylene, linear or branched, such as ethylene or propylene, and
notrepresents an integer ranging from 1 to 100, preferably ranging from 5 to 50, and preferentially ranging from 10 to 30.

It is possible to use as polydimethylsiloxane diols those sold under the names KF-6000, KF-6001, KF-6002, KF-6003 by the company Shin-Etsu Chemicals.

The polydimethylsiloxane diol of formula (VII'') is preferably used:

It is also possible to use dimethiconols which are polydimethylsiloxanes having terminal OH functions. Mention may be made, for example, of that 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 the compounds of formula(IIIa)next :

Formula(IIIa)in which :
R ₁ , identical or different, independently represents a hydroxy group; an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, especially 1 to 2 carbon atoms such as a methyl; an alkoxy group having 1 to 2 carbon atoms; or a group –(CH₂)_s-Si(R₄)₃in which s stands for an integer ranging from 1 to 4 such as 2 and R₄independently denotes an alkoxy group having 1 to 2 carbon atoms;
R' ₂ AndR'' ₂ independently represent an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, especially 1 to 2 carbon atoms such as methyl;
Todenotes an integer ranging from 0 to 10,bdesignates an integer ranging from 0 to 500, withTo+b≥4

Among the silicones of formula (IIIa) , mention may be made of polydimethylsiloxanes (PDMS) with terminal hydroxy 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 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 (IIIa) used in the context of the invention are chosen from the compounds of formula (IIIa) in which:
R ₁ independently represents an alkyl group having 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' ₂ AndR'' ₂ independently represent an alkyl group having from 1 to 10 carbon atoms, preferably an alkyl group having from 1 to 4 carbon atoms and more particularly from 1 to 2 carbon atoms such as 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 polymer compounds of the hyperbranched polymer and dendrimer type.

"Hyperbranched polymers" are molecular constructs with a branched structure, usually around a core. Their structure is as a rule free of symmetry. Indeed, the basic units or monomers having been used for the construction of the hyperbranched polymer can be of different natures and their distribution is irregular. The branches of the polymer can be of different natures and lengths. The number of basic units, or monomers, can be different according to the different ramifications. While being asymmetric, hyperbranched polymers can possess an extremely branched structure, around a core; layers or successive generations of ramifications; a layer of terminal chains.

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

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 the synthesis of dendrimers (see below), the degree of polymerization is less than 100%. A terminal group T can be reacted on the hyperbranched polymer to obtain a particular function at the end of the chains.

Several hyperbranched polymers can be associated with each other, by a covalent bond or another type of bond, through their terminal groups. Such so-called bridged polymers fall within the definition of hyperbranched polymers according to the present invention.

Many hyperbranched polymers and dendrimers have already been described. Reference may be made, for example, to: DA Tomalia et al, Angew. Chem. Int. English 29 138-175 (1990); N. Ardoin and D. Astruc, Bull. Soc. Chem. 132 , 875-909 (1995) ; BI Sees, Acta Polymer, 46 , 87-99 (1995).

Such polymers are described in particular in BI Voit, Acta Polymer., 46 , 87-99 (1995); EP-682059; WO-9614346; WO-9614345; WO-9612754. Several hyperbranched polymers can be associated with each other, by a covalent bond or another type of bond, through their terminal groups.

Such so-called bridged or “bridged” polymers fall within the definition of hyperbranched polymers according to the present invention.

"Dendrimers" are macromolecules made up of monomers that combine in a tree-like process around a central multifunctional core.

Dendrimers therefore have a fractal structure (or fractal molecule), consisting of a core, a determined number of generation of branches (or spindles), internal cavities originating from said ramifications of the molecule, and terminal functions.

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

Dendrimers can be in the form of a set of molecules of the same generation, sets called monodisperse; they can also take the form of sets of different generations, called polydisperse. The definition of dendrimers according to the present invention includes monodisperse as well as polydisperse sets of dendrimers.

The generations of branches are made up of structural units, which are identical for the same generation of branches and which can be identical or different for generations of different branches. All of the junction points of the branches of the same generation are located at an equal distance from the core corresponds to one generation.

The generations of branches extend radially in a geometric progression from the core. The terminal groups of a dendrimer of the N ^th generation are the terminal functional groups of the branches of the N ^th generation or called terminal generation.

The definition of dendrimers given above includes molecules with symmetrical branches; it also includes molecules with non-symmetrical branching, such as for example dendrimers whose branches are lysine groups, in which the branching of a generation of spindles on the previous one is done on the amines α and ε of lysine, which leads to a difference in the length of the spindles of the different ramifications.

Dendrimers are also called dense star polymers, or "dense star polymer", star burst polymers, or "starburst polymer", rod-shaped dendrimers, or "rod-shaped dendrimer", are included in the present definition of dendrimers . The molecules referred to as arborols and molecules in cascade also fall within the definition of the dendrimers according to the present invention.

Furthermore, several dendrimers can be associated with each other, by a covalent bond or another type of bond, through their terminal groups to give entities known as "bridged dendrimers", "aggregates of dendrimers" or bridged dendrimer. Such entities are included in the definition of dendrimers according to the present invention.

Dendrimers can be in the form of a set of molecules of the same generation, sets called monodisperse; they can also take the form of sets of different generations, called polydisperse. The definition of dendrimers according to the present invention includes monodisperse as well as polydisperse sets of dendrimers.

In the cases where the composition (B) comprises as compound(s) B : v) the hydroxylated compound(s) as defined above, the process according to the invention can advantageously implement one or several amine catalysts, the amine catalyst(s) preferably being present in composition (B) .

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

The catalysts with a tertiary amine function can 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"-pentamethyldiethylene-triamine, N,N,N',N '-tetramethylethylene-diamine, N-methyl morpholine, N-ethyl morpholine, 1,4-diazabicyclo[2.2.2]octane and mixtures thereof.

Diisopropylethylamine is preferably used.

Aminidin-functional catalysts are, for example, 1,5-Diazabicyclo[4.3.0]non-5-ene (or DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (or DBU).

The guanidine function catalysts can be chosen from the compounds of formula (Ia) below:

in which R1, R2, R3, R4, 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 can also denote an acetyl radical;; 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 C1-C4 lower alkyl radical, linear or branched; or a phenyl radical,
when R1=R2=R3=H, R4 and R5 can also form, with the nitrogen atom which carries them, a pyrrolidine, piperidine, pyrazole or 1,2,4-triazole ring,
when R1=R2=H, and R4=H or methyl, R3 and R5 can also together form a 5-membered ring optionally containing an oxo group,
and their organic or inorganic salts.

As salts, mention may be made of the hydrochloride, sulphate, sulfamate, carbonate, bicarbonate, phosphate and acetate salts.

Among the compounds of formula (Ia), mention may in particular 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, 1H-pyrazole-1-carboxamidine, 5-hydroxy-3-methyl-1H-pyrazole-1-carboximidamide, 3,5-diamino-1H-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, preferably ranging from 0.1% to 0.2% by weight relative to the weight total of the composition (B) .

vi) the thiolated compound(s)

According to one embodiment, composition (B) comprises as compound(s) B : vi) one or more thiolated, organic(s) or inorganic, polymeric or no, preferably organic(s) or silicone(s), chosen from polythiolated compounds having at least two thiol groups.

“Non-polymeric” compound(s) means one or more compound(s) which is or are not directly obtained by a polymerization reaction of monomers.

The thiolated compound(s) of the invention may be organic or inorganic, preferably organic.

According to an advantageous variant, the thiolated compound(s) are silicone-based, that is to say they contain at least two thiol groups and at least one siloxane chain.

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

The thiolated compounds of the invention may or may not be fat-soluble.

By “fat-soluble” compound is meant 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 thiolated compound(s) is (are) non-polymeric of formula(IIA):

Formula(IIA)in which :
qrepresents an integer greater than or equal to 2, preferably ranging from 2 to 10, more preferably ranging from 2 to 5;
Idenotes a 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, preferably 6 to 20 carbon atoms, linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated;
Ibeing optionally interrupted and/or terminated by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their combinations such as –O-, –O-C(X)-, -N(R) -C(X)-, -Si(R_vs)(R_d)-O- withRrepresenting a hydrogen atom or a group (C₁-VS₆)alkyl such as methyl; and or
Ibeing optionally substituted by one or more halogen atoms, or a group chosen from R_To(R_b)N-, -(X’)_To-C(X)-(X’’)_b-R_To,
-X,X'AndX'', identical or different, represent an oxygen atom, a sulfur atom, or an N(R_b);
-ToAndbequal to 0 or 1, preferably the sumTo+bis worth 1,
-R _To AndR _b , identical or different, represent a hydrogen atom, or a group (C₁-VS₆)alkyl, or aryl(C₁-VS₄)alkyl such as benzyl, preferablyR _To AndR _b represent a hydrogen atom;

- R _c and R _d , which are identical or different, represent a (C ₁ -C ₆ )alkyl, aryl (C ₁ -C ₄ )alkyl or (C ₁ -C ₆ )alkoxy group.

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

According to this embodiment, L preferably denotes a multivalent C ₈ -C ₁₈ radical, in particular linear. Preferably, the polythiol is a C ₈ -C ₁₈ dithiol, in particular linear. Advantageously, the C ₈ -C ₁₈ chain is a hydrocarbon chain, ie formed from carbon and hydrogen. In particular, the liposoluble polythiol is a linear C ₈ -C ₁₆ dithiol, in particular C ₁₀ -C ₁₄ .

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

Preferably, 1,10-decanedithiol, 1,12-dodecanedithiol, 1,14-tetradecanedithiol are used. Preferably, 1,12-dodecanedithiol is used.

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

Formula (IB) in which:
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 multivalent (at least divalent) C ₂ -C ₈₀ linear or branched or (hetero)cyclic radical, saturated, an aromatic radical, a heteroaromatic cyclic radical, W possibly containing one or more heteroatoms such as O, N, S, and/or one or more functions chosen from esters, ketones, amides, ureas, preferably esters , ketones and/or be substituted by one or more linear or branched C ₁ -C ₁₀ alkyl groups, linear or branched C ₁ -C ₁₀ alkoxy groups, it being understood that when the radical W is substituted, the thiol functions can be carried by the /substituent(s).

By cyclic radical is meant a saturated monocyclic, hydrocarbon-based or heterocyclic radical, a saturated or aromatic polycyclic radical, for example biphenyl, or condensed cycles such as for example the naphthyl radical.

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

According to a first more specific embodiment, the thiolated compound(s) of formula (IB) is (are) such that n=2 and W denotes a divalent saturated hydrocarbon radical C ₂ -C ₂₀ linear or branched, preferably C ₂ -C ₁₂ linear or branched.

According to this first more specific embodiment, the thiolated compound(s) can 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 second more specific embodiment, the thiol compound(s) of formula (IB) is (are) such that n =3 and W denotes a linear or branched C ₃ -C ₂₀ saturated hydrocarbon trivalent radical , preferably C ₂ -C ₁₂ linear or branched.

According to this second more specific embodiment, the thiolated compound(s) can be chosen from 1,1,1-tris(mercaptomethyl)ethane, 2-ethyl-2 -mercaptomethyl-1,3-propanedithiol, 1,2,3-propanetrithiol.

According to a third more specific embodiment, the thiolated compound(s) of formula (IB) is (are) such that n =2 or 3 and W denotes a divalent or trivalent saturated C ₃ -C hydrocarbon radical. _linear or branched, preferably C ₂ -C ₁₂ linear or branched, said radical containing one or more non-adjacent heteroatom(s) chosen from O, S.

According to this third more specific embodiment, the thiolated compound(s) can be chosen from:

C ₂ -C ₁₂ bis mercaptoalkyl ethers and sulphides such as bis(2-mercaptoethyl)ether, bis(2-mercaptoethyl)sulphide, bis-(2-mercaptoethylthio-3-mercaptopropane)sulphide;

alkanes (C ₁ -C ₅ ) bis (2-mercapto alkyl (C ₁ -C ₃ )thio) or mercaptoalkanes (C ₁ -C ₅ ) bis (2-mercapto alkyl (C ₁ -C ₃ )thio) as by example 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, 1,2,3-tris(2-mercaptoethylthio)propane.

Preferably, according to this third more specific embodiment, the thiolated compound(s) is (are) chosen from 1,2-bis(2-mercaptoethylthio)propanethiol, 1,2, 3-tris(2-mercapto ethylthio) propane , tetrakis(2-mercaptoethylthiomethyl) methane.

According to a fourth more specific embodiment, the thiolated compound(s) of formula (IB) is (are) such that n denotes an integer greater than or equal to 2 and W denotes a multivalent radical ( at least divalent) linear or branched C ₃ -C ₂₀ saturated hydrocarbon, preferably linear or branched C ₂ -C ₁₂ , said radical containing at least one ester function.

According to this fourth more specific embodiment, the thiolated compound(s) can 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 (beta-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (.beta.-mercaptopropionate), dipentaerylthritol hexakis (.beta.-mercaptoproprionate ), tris(2-mercaptoacetate) trimethylolpropane, tris(3-mercaptopropionate) trimethylolpropane, tris(3-mercaptopropionate) pentaerythritol, tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), tetrakis(3-mercaptobutanate), pentaerythritol hex -3-mercaptopropionate,

Preferably, according to this fourth more specific embodiment, the thiolated compound(s) is (are) chosen from among trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutanate), dipentaerythritol hex-3-mercaptopropionate.

Particularly preferably, the thiolated compound is pentaerythritol tetrakis(3-mercaptopropionate).

According to a fifth more specific embodiment, the thiolated compound(s) of formula (IB) is (are) such that n =4 and W denotes a tetravalent saturated hydrocarbon radical C ₄ -C ₂₀ , preferably C ₈ -C ₁₄ , branched interrupted by one or more non-adjacent sulfur atoms.

According to this fifth more specific embodiment, the thiolated compound(s) can be chosen from tetrakis(2-mercaptoethylthiomethyl) methane, bis-(2-mercaptoethylthio-3- mercaptopropane)sulfide.

According to a sixth more specific embodiment, the thiolated compound(s) of formula (IB) is (are) such that n =2 and W denotes a divalent cyclic hydrocarbon radical optionally containing one or more non-adjacent sulfur atoms, optionally substituted by one or more linear or branched C ₁ -C ₁₀ alkyl radicals.

According to this sixth more specific embodiment, the thiolated compound(s) can be chosen from 1,4-cyclohexane dithiol, 1,4-bis(mercaptomethyl)cyclohexane, 1,1-cyclohexane dithiol, 1,2-cyclohexane dithiol, 1,1-bis(mercaptomethyl)cyclohexane, 2,5-dimercapto-1,4-dithiane.

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

According to this seventh more specific embodiment, the thiolated compound(s) can be chosen from polythiols of the isocyanurate class described in US patents 3,676,440 and US20110230585 such as tris(( mercaptopropionyloxy)-ethyl)isocyanurate.

According to an eighth more specific embodiment, the thiolated compound(s) of formula (IB) is (are) such that n =2 or 3 or 4 and W denotes an aromatic radical optionally substituted by one or more identical or different radicals of (C ₁ -C ₁₀ )alkyl, (C ₁ -C ₁₀ )alkoxy type, it being understood that when the radical W is substituted, the thiol functions can be carried by the substituent(s) ).

According to this eighth more specific embodiment, the thiolated compound(s) can 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 eighth more specific embodiment, the thiolated compound(s) can be chosen from 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-tris(mercaptomethyl)benzene, 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, the 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, 3,4-thiophenedithiol.

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

According to another particular embodiment of the invention, the thiolated compound(s) is (are) chosen from derivatives of triglycerides of thiolated fatty acids, such as those of formula (IV) below:

Formula (IV) in which:
R ¹ , R ² and R ³ , identical or different, represent a hydrogen atom or a thiol group;
ALK ¹ , ALK ² , and ALK ³ , which are identical or different, represent a (C ₁ -C ₃₀ )alkylene group optionally substituted by one or more thiol groups;
X ¹ , X ² and X ³ , identical or different, preferably identical, represent a -C(Y)-Y'- or -Y'-C(Y)- group with Y and Y' , identical or different, of preferably identical, represent a heteroatom such as O, S, and N, preferably O.

Preferably, the compounds of formula (IV) are such as:
R ¹ , R ² and R ³ represent a hydrogen atom;
ALK ¹ represents a (C ₁₀ -C ₂₄ )alkylene group, particularly (C ₁₄ -C ₂₀ )alkylene group, preferably linear;
ALK ² represents a represents a (C ₁₀ -C ₂₄ )alkylene group, particularly (C ₁₄ -C ₂₀ )alkylene group, preferably linear, substituted by one or more thiol groups;
ALK ³ represents a (C ₁₀ -C ₂₄ )alkylene group, particularly (C ₁₄ -C ₂₀ )alkylene group, preferably linear, substituted by one or more thiol groups, preferably two thiol groups;
X ¹ , X ² and X ³ which are identical, represent a -C(O)-O- or -OC(O)- group;

More preferably, the thiolated fatty acid triglyceride derivatives are those of the following formula (IV′) :

According to this other particular embodiment, the thiolated compound(s) can be chosen from: fatty acid triglycerides or vegetable oils modified with thiol groups by chemical reaction such as for example thiolated soybean oils and hydroxylated and thiolated soybean oils, in particular the polymercaptan® products from the company Chevron Phillips such as polymercaptan 358 (mercaptanised soybean oil) and polymercaptan 407 (mercapto hydroxy soybean oil)

According to a particular embodiment of the invention, the thiolated compound(s) is (are) chosen from polythiolated compounds having 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, 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 preferably ranging from 3 to 5, will be preferred.

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

Particularly preferably, according to this variant, the thiolated compound(s) designate(s) trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate) , pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutanate), dipentaerythritol hex-3-mercaptopropionate, tris((mercaptopropionyloxy)-ethyl)isocyanurate.

Polymeric thiol compounds

According to one embodiment of the invention, the thiolated compound(s) is (are) polymeric. The polymeric hydroxylated compound(s) of the invention may be homopolymers, copolymers, star, combe, brush and dendritic with thiol units. Polymers can be of natural origin such as polysaccharides, polypeptides, or synthetic such as acrylics, polyesters. The thiol units can be present as terminal or pendent groups.

The polymeric thiolated compound(s) is (are) preferably organic or silicone compound(s), more preferably of formula (VB) :

Formula (VB) in which:
q represents an integer greater than or equal to 2;
POLY denotes a polymeric radical, preferably carbonaceous or silicone;
POLY being optionally interrupted by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their associations such as –O-, –OC(X)-, -N(R)-C( X)-, -Si(R _c )(R _d )-O- with R representing a hydrogen atom or a (C ₁ -C ₆ )alkyl group such as methyl; and or
POLY being optionally substituted by one or more halogen atoms, or a group chosen from R _a (R _b )N-, -(X') _a -C(X)-(X'') _b -R _a ,
- X , X' and X'' , which are identical or different, represent an oxygen or sulfur atom, or an N(R _b ) group;
- a and b being 0 or 1, preferably the sum a + b is 1;
- R _a and R _b , identical or different, represent a hydrogen atom, or a group (C ₁ -C ₁₀ )alkyl, or aryl (C ₁ -C ₄ )alkyl such as benzyl, preferably R _a and R _b represent a hydrogen atom; And
- R _c and R _d , which are identical or different, represent a (C ₁ -C ₁₀ )alkyl, aryl (C ₁ -C ₄ )alkyl or (C ₁ -C ₁₀ )alkoxy group.

The methods for preparing the thiolated polymers according to the invention are known to those skilled in the art, several methods are reported below in a non-limiting manner.

The following thiolated polymers of the invention can be obtained by polymerization, polycondensation of monomer units with thiol functions or protected thiols, optionally by co-polymerization or co-polycondensation of monomer units devoid of thiol functions or protected thiols.

Alternatively, the thiolated polymers according to the invention can be obtained by adding hydrogen sulphide, its salts such as sodium hydrogen sulphide or potassium sulphide or else a group capable of forming a carbon-sulfur bond such as derivatives of thioureas, thiosulphate, on a polymer containing at least one double bond.

The thiolated polymers according to the invention can also be obtained by nucleophilic substitution of a leaving group present on a polymer chain (for example halogen such as chlorine, bromine, a sulphonic ester such as mesylate or tosyltate) by a compound comprising at least one sulfur atom such as those mentioned above

The thiolated polymers according to the invention can also be obtained by reaction of polymers comprising nucleophilic groups such as amines on electrophilic compounds comprising a sulfur atom such as 2-oxo-4-thiazolidine carboxylic acid also known under the name of procysteine:

- N-acetyl homocysteine-thiolactone:

- γ-thiobutyrolactone:

- imino thiolane:

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

Formula (VIIIB) in which:
q denotes an integer greater than or equal to 2, and
POLY denotes a carbonaceous and/or silicone, preferably silicone, polymeric radical, POLY possibly also containing one or more heteroatoms such as O, N, S, and/or one or more functions chosen from the functions, (thio)esters, ( thio)ketones, (thio)amides, (thio)ureas, (thio)carbamates, and/or be substituted by one or more (C ₁ -C ₁₀ )alkyl, linear or branched, (C ₁ -C ₁₀ )alkoxy groups , linear or branched, it being understood that when POLY is substituted, the thiol functions may be carried by the substituent(s).

The molecular weight average molecular weight of 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 thiolated compound(s) is (are) chosen from polyorganosiloxanes of formula(VIIIB'):

Formula(VIIIB')in which :
R ^To AndR ^b , identical or different, preferably identical, represent a group (C₁-VS₄)alkyl such as methyl, (C₁-VS₄)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C₁-VS₄)alkyl such as benzyl, or aryl(C₁-VS₄)alkoxy such as benzoxy, preferably (C₁-VS₄)alkyl such as methyl,
notrepresents an integer greater than or equal to 1 and more particularly the value ofnotis such that the weight average molecular weight of the silicone ranges from 500 to 55,000; particularly n is an integer ranging from 1 to 100, preferably ranging from 5 to 50, and preferably included ranging from 10 to 30, and
I ⁴ AndI ⁵ , identical or different, represent a covalent bond, or a hydrocarbon chain comprising from 1 to 100 carbon atoms, saturated or unsaturated, linear or branched, optionally cyclic, optionally interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen, preferablyI ⁴ AndI ⁵ , identical or different, represent a covalent bond or a group (C₁-VS₆)alkylene, (C₁-VS₆)alkylene-oxy, oxy-(C₁-VS₆)alkylene, (C₁-VS₆)alkylene-oxy(C₁-VS₆)alkylene, (C₁-VS₆)alkylene-oxy(C₁-VS₆)alkylenoxy or oxy(C₁-VS₆)alkylene-oxy(C₁-VS₆)alkylene, preferably a group (C₁-VS₆)alkylene, (C₁-VS₆)alkylene-oxy, oxy-(C₁-VS₆)alkylene, or (C₁-VS₆)alkylene-oxy(C₁-VS₆)alkylene.

Preferably, the polydimethylsiloxane thiols are chosen from those of formula(VIIIB''):

Formula(VIIIB'')in which :
I ⁴ AndI ⁵ represent a hydrocarbon chain comprising from 1 to 100 carbon atoms, saturated or unsaturated, linear or branched, optionally cyclic, optionally interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen, preferablyI ⁴ AndI ⁵ represent a group (C₁-VS₆)alkylene, (C₁-VS₆)alkylene-oxy, oxy-(C₁-VS₆)alkylene, or (C₁-VS₆)alkylene-oxy(C₁-VS₆)alkylene, more preferably a divalent group chosen from –R₂-, -GOLD₂-, -R₂-GOLD₂-GOLD₂–, preferably –R₂-GOLD₂-, withR ₂ representing a group (C₂-VS₆) linear or branched, preferably linear, alkylene, such as ethylene or n-propylene;
notrepresents an integer ranging from 1 to 100, preferably ranging from 5 to 50, and preferentially ranging from 10 to 30.

As thiolated poly(C ₁ -C ₄ )alkylsiloxanes, mention may be made of thiolated mercaptosiloxanes or siloxanes, in which the thiol functions are located at the chain ends, marketed by the company SHIN-ETSU under the reference X-22-167B and mercaptosiloxane, in which the mercapto functions are pendant, marketed by the company SHIN-ETSU under the reference KF-2001, or the polydimethylsiloxane in which the thiol functions are located at the chain ends marketed by the company Gelest under the name DMS – SM 21, of formula (VIII''') :

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

Formula (IX) in which:
R ^a , R ^b , and R ^d , identical or different, preferably identical, represent a group (C ₁ -C ₆ )alkyl optionally substituted by a hydroxy group, or amino, preferably (C ₁ -C ₄ )alkyl such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl (C ₁ -C ₄ )alkyl such as benzyl, or aryl (C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl,
R ^d can also represent a (C ₁ -C ₆ )alkyl group substituted by a (C ₁ -C ₄ )alkylamino or amino group, or thiol, preferably (C ₁ -C ₄ )alkyl such as methyl;
ALK represents a hydrocarbon chain comprising from 1 to 100 carbon atoms, saturated or unsaturated, linear or branched, optionally cyclic, optionally interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen (in particular O), a group (thio) carbonyl C(X) with X representing O, or S, or their combinations such as –O–, –OC(O)– or –C(O)-O–, preferably ALK represents a group (C ₁ -C ₆ )alkylene, more preferably (C ₁ -C ₄ )alkylene such as propylene; n and m , which are 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;

Preferably, the polydi(C ₁ -C ₄ )alkylsiloxanes of formula (IX) are of the following formula (IX') :

Formula (IX') , in which the values of n and m are such that the weight-average molecular weight of the silicone ranges from 1,000 to 55,000. As examples of silicone (IX'), mention may be made of those sold by Genesee GP- 367 and other Polymers. Polythiol silicones are in particular polydimethylsiloxane comprising two or more thiol groups such as, for example, 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 thiolated compound(s) are chosen from polymer compounds of the hyperbranched polymer and dendrimer type.

"Hyperbranched polymers" are molecular constructs with a branched structure, usually around a core. Their structure is as a rule free of symmetry. Indeed, the basic units or monomers having been used for the construction of the hyperbranched polymer can be of different natures and their distribution is irregular. The branches of the polymer can be of different natures and lengths. The number of basic units, or monomers, can be different according to the different ramifications. While being asymmetric, hyperbranched polymers can possess an extremely branched structure, around a core; layers or successive generations of ramifications; a layer of terminal chains.

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

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 the synthesis of dendrimers (see below), the degree of polymerization is less than 100%. A terminal group T can be reacted on the hyperbranched polymer to obtain a particular function at the end of the chains.

Several hyperbranched polymers can be associated with each other, by a covalent bond or another type of bond, through their terminal groups. Such so-called bridged polymers fall within the definition of hyperbranched polymers according to the present invention.

Many hyperbranched polymers and dendrimers have already been described. Reference may be made, for example, to: DA Tomalia et al, Angew. Chem. Int. English 29 138-175 (1990); N. Ardoin and D. Astruc, Bull. Soc. Chem. 132 , 875-909 (1995) ; BI Sees, Acta Polymer, 46 , 87-99 (1995).

Such polymers are described in particular in BI Voit, Acta Polymer., 46 , 87-99 (1995); EP-682059; WO-9614346; WO-9614345; WO-9612754. Several hyperbranched polymers can be associated with each other, by a covalent bond or another type of bond, through their terminal groups.

Such so-called bridged or “bridged” polymers fall within the definition of hyperbranched polymers according to the present invention.

"Dendrimers" are macromolecules made up of monomers that combine in a tree-like process around a central multifunctional core.

Dendrimers therefore have a fractal structure (or fractal molecule), consisting of a core, a determined number of generation of branches (or spindles), internal cavities originating from said ramifications of the molecule, and terminal functions.

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

Dendrimers can be in the form of a set of molecules of the same generation, sets called monodisperse; they can also take the form of sets of different generations, called polydisperse. The definition of dendrimers according to the present invention includes monodisperse as well as polydisperse sets of dendrimers.

The generations of branches are made up of structural units, which are identical for the same generation of branches and which can be identical or different for generations of different branches. All of the junction points of the branches of the same generation are located at an equal distance from the core corresponds to one generation.

The generations of branches extend radially in a geometric progression from the core. The terminal groups of a dendrimer of the N ^th generation are the terminal functional groups of the branches of the N ^th generation or called terminal generation.

The definition of dendrimers given above includes molecules with symmetrical branches; it also includes molecules with non-symmetrical branching, such as for example dendrimers whose branches are lysine groups, in which the branching of a generation of spindles on the previous one is done on the amines α and ε of lysine, which leads to a difference in the length of the spindles of the different ramifications.

Dendrimers are also called dense star polymers, or "dense star polymer", star burst polymers, or "starburst polymer", rod-shaped dendrimers, or "rod-shaped dendrimer", are included in the present definition of dendrimers . The molecules referred to as arborols and molecules in cascade also fall within the definition of the dendrimers according to the present invention.

Furthermore, several dendrimers can be associated with each other, by a covalent bond or another type of bond, through their terminal groups to give entities known as "bridged dendrimers", "aggregates of dendrimers" or bridged dendrimer. Such entities are included in the definition of dendrimers according to the present invention.

Dendrimers can be in the form of a set of molecules of the same generation, sets called monodisperse; they can also take the form of sets of different generations, called polydisperse. The definition of dendrimers according to the present invention includes monodisperse as well as polydisperse sets of dendrimers.

According to one embodiment, the polymeric thiol compound(s) is (are) of formula (II'B) :

Formula (II'B) in which n denotes an integer greater than or equal to 5, preferably ranging from 5 to 5000, more preferably ranging from 5 to 1000;
and POL denotes a multivalent (at least pentavalent) carbon or silicone polymeric radical, POL possibly also containing one or more heteroatoms such as O, N, S, and/or one or more functions chosen from esters, ketones, amides, ureas, carbamates, and/or be substituted by one or more linear or branched C ₁ -C ₁₀ alkyl groups, linear or branched C ₁ -C ₁₀ alkoxy groups, it being understood that when POL is substituted, the thiol functions can be carried by the /substituent(s).

The molar mass of the compounds of formula (II'B) generally ranges from 500 to 400,000, preferably from 500 to 150,000.

POL can designate a multivalent radical of the homopolymer or copolymer type;

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

The thiol functions (-SH) can be terminal and/or pendent groups.

According to a first embodiment, the polymeric thiol compound(s) of formula (II′B) is (are) such that POL designates a polymeric hydrocarbon radical.

Examples include the polymers described in the following articles: Polymers containing groups of biological activity, CG 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, pp 61-90.

In particular, mention may be made of the polymeric thiol compounds of formula (II'B) such as poly(vinylmercaptan), poly(4-mercaptostyrene), poly(vinylbenzylmercaptan), poly(4-mercaptostyrene)-co-poly(methylmethacrylate), as well as polymers containing amide functions in the polymer such as poly(hexamethylene adipamide thiolated).

The polymeric thiol compounds of formula (II'B) also designate the proteins and peptides with thiol units, such as for example the structures represented in the following table:

The polymeric thiol compounds of formula (II'B) also denote the compounds of formula (II'B) such that POL denotes a so-called dendrimer, branched or hyperbranched polymer radical and the thiol groups are terminal. Examples include the polymers described in the article Progress in Organic Coatings, Volume 63, Issue 1, July 2008, Pages 100–109.

As an example of the synthesis of such polymers, mention may be made of the synthesis described in this article, where the Boltorn H40 polymer is converted into a thiolated polymer of formula (II'B) according to the scheme below:

The structure of the thiolated polymer (II'B) obtained is given below:

The polymeric thiolated compound(s) of formula (II'B ) can also designate a hyperbranched or dendritic polymer modified by thiol functions as described in application FR 2761691.

By way of example of hyperbranched polymers and dendrimers comprising thiol functional groups, mention may be made of hyperbranched polymers and dendrimers comprising functional groups of formula (X) below:

Formula (X) in which:
Y represents an oxygen or sulfur atom, or an NR' group,
X represents i) an oxygen atom or ii) an –N(R')- group in which R' is chosen from a) a hydrogen atom, b) a C ₁ -C ₆ alkyl group, linear or branched, saturated or unsaturated, c) a mono- or poly-hydroxyalkyl group in C ₁ -C ₆ , linear or branched, saturated or unsaturated, d) an aminoalkyl group in C ₁ -C ₆ or a polyalkyleneimine group; preferably X represents -N(R')- with R' representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl; And
A represents a (C ₁ -C ₁₂ )alkylene group, linear, branched or cyclic, saturated or unsaturated; this group being optionally interrupted by one or more heteroatoms such as O, S, N and/or optionally substituted by one or more groups chosen from amino (-NH ₂ ), acylamino (-N(H)-C(O)-R ) or aminoacyl (RN(H)-C(O)-) in which R represents a linear, branched or cyclic, saturated or unsaturated C ₁ -C ₁₀ alkyl group, carboxy (-C(O)OH), ester ( -C(O)-OR) in which R represents a linear, branched or cyclic, saturated or unsaturated C ₁ -C ₁₀ alkyl group.

Preferably, the polymeric thiolated compound(s) according to the invention is (are) chosen from hyperbranched polymers, and in particular polyethyleneimine, comprising at least one group chosen from the groups of formula (X ) as previously defined.

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

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

Advantageously, A represents a radical corresponding to one of the following formulas (a) to (d) :

Formulas (a) , (b) , (c) , and (d) in which:
R ¹ , R ² , R ³ , R' ¹ , R' ² , R' ³ and R' ⁴ , R''' ¹ , R''' ² , which are identical or different, represent: the hydrogen atom; a C ₁ -C ₆ alkyl group, linear, branched or cyclic, saturated or unsaturated; an amino group (-NH ₂ ); a carboxylic acid group (-COOH); a C ₁ -C ₁₀ alkylamino group; a C ₁ -C ₁₀ acylamino group;
R'' ¹ , R'' ² , R'' ³ and R'' ⁴ , which are identical or different, represent the hydrogen atom or a C ₁ -C ₄ alkyl group, linear or branched, saturated or unsaturated; the arrows indicating the positions of the substitutions; And
k is an integer, preferably 0 or 1;
represents the point of attachment with 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'' ₁ , R'' ₂ , and R'' ₃ 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 thiolated compound(s) are hyperbranched polymers and dendrimers comprising functional groups of formula (X) such that A is chosen from:
-CH ₂ -CH(CO ₂ H)-NH- and Y represents an oxygen atom;
-(CH ₂ ) ₂ -(CH ₃ CONH)CH- and Y represents an oxygen atom;
-(CH ₂ ) ₃ - and Y represents an oxygen atom or an NH group.

In particular, A is the propylene group -CH ₂ -CH ₂ -CH ₂ -, and Y represents an oxygen atom, the compound according to the invention then corresponding to the following formula (XI) :

Formula (XI) in which X is as defined above, preferably X represents -N(R')- with R' representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl.

Preferably, according to the invention, X of formula (X) and (XI) is chosen from the oxygen atom and an NH group.

According to one of the preferred embodiments of the invention, the thiolated polymers are as described in document FR 2 853 533, they are poly N-α- and N-ε- lysine and ornithine of formula I, at thiol function, which can be obtained from poly N-α- and N-ε- lysine and ornithine by reaction with a thiolactone such as, for example, thiobutyrolactone (dihydrothiophen-2(3H)-one).

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

Formula (XII) in which:
p different from p' and p , p' are 0 or 1;
n is 3 or 4;
if p' is 0, then the neighboring NH is involved in an N-ε polymerization;
if p is 0, then the neighboring NH is involved in an N-α polymerization;
if p or p' equals 1, then R or R' represents -B-SH, with B representing a C ₁ -C ₃₀ hydrocarbon chain, saturated or not, linear or branched which can be interrupted by one or more heteroatoms or groups, alone or in combinations, such as: -N(R ¹ )-, -O-, -S(O) _r -, -C(O)-, -C(S)-, -C(NR ¹ )-, with r equal to 0, 1 or 2, or/and by one or more aryl, heteroaryl, cycloalkyl or heterocycloalkyl with 5, 6 or 7 members and which may be substituted by one or more halogen atoms or groups: hydroxy, amino, carboxy , (di)(C ₁ -C ₈ )alkylamino, (C ₁ -C ₈ )acylamino, (C ₁ -C ₈ )acyloxy, (C ₁ -C ₈ )alkyloxycarbonylamino, (C ₁ -C ₈ )alkylamino-carbonyloxy , (C ₁ -C ₈ )alkyl aminocarbonyl;
knowing that R or R' can, in part only, also represent a hydrogen atom,
and/or –C(NH)- and its salts
and/or –C(NH)-N(H)-C(NH)-NH ₂ and its salts
R ₁ represents a hydrogen atom or a (C ₁ -C ₈ )alkyl, (C ₁ -C ₈ )acyl, (C ₁ -C ₈ )alkyloxycarbonyl, (C ₁ -C ₈ )alkyl aminocarbonyl group, halogen;
B can also represent an aryl, heteroaryl, cycloalkyl or heterocycloalkyl group with 5, 6 or 7 members, optionally substituted;
m represents an integer ranging from 3 to 10000.

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

Advantageously, poly N-α- and N-ε- lysine and ornithine corresponding to formula (XII) exhibit: 5<m<1000.

The “theoretical thiol function grafting rate” represents the theoretical percentage of lysine or ornithine unit carrying the thiol function in the compound of formula (XII) .

By way of example of hyperbranched polymers, mention may very particularly be made of hyperbranched thiolated polyethyleneimines, such as those described in application EP103759 with a molecular molar mass ranging from 30.10 ⁴ to 50.10 ⁴ .

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

According to a particular embodiment of the invention, the branched or hyper-branched dendrimers and polymer(s) bear thiol end groups such as "dendritic polythiols of the Boltorn™ type" from the company BASF esterified with compounds such as thioglycolic acid and described in the literature.

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

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

Formula (XIII) in which:
R ₁ , R ₂ and R ₃ , which are identical or different, preferably identical, represent a group or thio(C ₁ -C ₆ )alkyl;
R ₄ represents a hydrogen atom, or a hydroxy, thiol, amino group, or a (C ₁ -C ₆ )alkyl group, preferably (C ₁ -C ₄ )alkyl such as ethyl;
X ₁ and X ₂ , identical or different, preferably identical, represent an oxygen, sulfur or amino atom, preferably oxygen;
m , n and l , identical or different, represent an integer greater than or equal to 1.

The thiolated 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-Trimethylolpropan Tri-3-Mercaptopropionate (CAS# 345352-19-4) and THIOCURE® ETTMP 700 (Ethoxylated-Trimethylolpropan Tri-3- Mercaptopropionate (CAS# 345352-19-4);

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

The metal salt(s) α)

The process according to the invention implements α) one or more metal salt(s) chosen from transition metal salts, alkali metal salts, alkaline earth metal salts, aluminum salts , boron salts, tin salts, magnesium salts, their hydrates and mixtures thereof, the metal salt(s) being included in composition (A) and/or in composition (B ) and/or in a separate composition (C) , the composition (C) also being applied to the keratin fibres.

According to a particular embodiment of the invention, composition (A) comprises the metal salt(s) as defined above.

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

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

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

According to another embodiment, compositions (A) and (C) comprise the metal salt(s) as defined above.

According to another embodiment, compositions (B) and (C) comprise the metal salt(s) as defined above.

According to another embodiment, the compositions (A) , ( B) and ( C) comprise the metal salt(s) as defined above.

When several compositions chosen from (A) , (B) and (C) comprise the metal salt(s) as defined above, the metal salt(s) included in each of the compositions having little (s)t be the same or different.

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

Preferably, the metal salt(s) are chosen from aluminum salts, their hydrates and mixtures thereof.

By "metallic salt" is meant a salt resulting in particular from the action of an acid on a metal.

The metal salt(s) may be in the form of hydrates.

The metal salt(s) can be organic or inorganic.

By "organic metal salt" is meant a salt resulting in particular from the action of an organic acid on a metal.

By "inorganic metal salt" is meant a salt resulting in particular from the action of an inorganic acid on a metal.

By "inorganic acid" is meant an acid which does not contain any carbon atoms except carbonic acid.

According to a particular embodiment of the invention, the inorganic metal salt(s) can be chosen from halides such as chlorides, fluorides, iodides and bromides, carbonates, sulfates, phosphates, nitrates, perchlorates, their hydrates, and mixtures thereof.

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

According to a more preferred embodiment, the metal salt(s) are chosen from basic aluminum acetate, aluminum oxalate, hydrated or non-hydrated aluminum citrate, aluminum lactate. aluminium, aluminum glycinate and mixtures thereof.

According to an even more preferred embodiment, the metal salt is basic aluminum acetate.

According to a preferred embodiment of the invention, the metal salt(s) as defined above 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.

The coloring agent(s) β)

The process according to the invention implements β) one or more coloring agent(s) chosen from direct dyes, oxidation dyes, pigments and mixtures thereof, the agent(s) dye(s) being included in composition (A) and/or in composition (B) and/or in composition (C) and/or in a separate composition (D) , composition (D) also being applied to keratin fibers.

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

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

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

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

According to another particular embodiment of the invention, the compositions (A) and (C)

include the coloring agent(s). When the compositions (A) and (C) comprise the coloring agent(s), the coloring agent(s) included in each of the compositions can be identical or different).

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

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

By "coloring agent" is meant an oxidation dye, a direct dye or a pigment.

By “oxidation dye” is meant an oxidation dye precursor chosen from oxidation bases and couplers. Oxidation bases and couplers are compounds with little or no color which, through a condensation reaction in the presence of an oxidizing agent, give rise to a colored species.

By "direct dye" is meant a natural and/or synthetic dye, including in the form of extract(s), different from oxidation dyes. These are colored compounds that will diffuse superficially on the fiber. They can be ionic or nonionic, i.e. anionic, cationic, neutral or nonionic.

Direct dyes and/or oxidation dyes

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

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 can 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 can in particular be chosen from meta-phenylenediamines, meta-aminophenols, meta-diphenols, naphthalene-based coupling agents and heterocyclic coupling agents, as well as the corresponding addition salts.

By way of example, the direct dyes can in particular 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. Direct dyes can be anionic, cationic or neutral.

The natural direct dyes can in particular be chosen from hennotannic acid, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin, curcumin , spinulosin, apigenidin and orcein as well as extracts or decoctions containing these natural colorants.

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

Pigments

The coloring 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 coloring agent(s) chosen from pigments.

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

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

According to one particular embodiment of the invention, composition (D) comprises one or more coloring agent(s) chosen from pigments.

According to one particular embodiment of the invention, composition (A) and/or composition (C) comprise one or more coloring agent(s) chosen from pigments.

According to a particular embodiment of the invention, compositions (A) and (C) comprise one or more coloring agent(s) chosen from pigments, the pigment(s) contained in compositions (A ) and (C) which may be identical or different

By "pigment" is meant all the pigments providing color to the keratinous 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%.

These are solid, white or colored particles, naturally insoluble in the liquid hydrophilic and lipophilic phases usually used in cosmetics or rendered insoluble by formulation in the form of a lacquer, where appropriate. More particularly, the pigments are little or not soluble in aqueous-alcoholic media.

The pigments which can be used are in particular chosen from the organic and/or inorganic pigments known in the art, in particular those which are described in the encyclopedia of chemical technology by Kirk-Othmer and in the encyclopedia of industrial chemistry by Ullmann. Mention may in particular be made, as pigments, of organic and inorganic pigments such as those defined and described in Ullmann's Encyclopedia of Industrial Chemistry "Pigment organics", 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, Weinheim10.1002/14356007.a20_243.pub3

These pigments can be in the form of powder or pigment paste. They can be coated or uncoated.

The pigments can for example be chosen from mineral pigments, organic pigments, lakes, special effect pigments such as nacres or glitter, and mixtures thereof.

The pigment can be an inorganic pigment. By "mineral pigment", we mean any pigment that meets the definition of the Ullmann encyclopedia in the chapter inorganic pigment. Mention may be made, among the mineral pigments useful in the present invention, of iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide.

The pigment may be an organic pigment. By "organic pigment" is meant any pigment that meets the definition of the Ullmann encyclopedia in the organic pigment chapter. The organic pigment can in particular be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, compounds of metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

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

According to a particular embodiment of the invention, pigment pastes of organic pigments such as the products sold by the company HOECHST under the name:
- YELLOW COSMENYL IOG: Pigment YELLOW 3 (Cl 11710);
- COSMENYL G YELLOW: Pigment YELLOW 1 (Cl 11680);
- ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);
- COSMENYL RED R: Pigment RED 4 (Cl 12085);
- CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);
- VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);
- COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);
- GREEN COSMENYL GG: Pigment GREEN 7 (Cl 74260);
- COSMENYL BLACK R: Pigment BLACK 7 (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 in particular of particles comprising:
- an inorganic core,
- at least one binder ensuring the fixing of the organic pigments on the core, and
- at least one organic pigment at least partially covering the core.

By "lacquer", we mean the dyes adsorbed on insoluble particles, the assembly thus obtained remaining insoluble during use. The inorganic substrates on which the dyes are adsorbed are for example alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum. Among the organic dyes, mention may be made of cochineal carmine.

Examples of lacquers include the products known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410 ), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 7 (CI 15 850:1), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D&C Green 3 (CI 42053), D&C Blue 1 (CI 42090).

The pigment or pigments can also be special effect pigments.

By "special effect pigments" is meant pigments which generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) which is not uniform and changes according to the conditions of observation (light , temperature, viewing angles, etc.). They are therefore opposed to colored pigments which provide a uniform opaque, semi-transparent or classic transparent shade.

There are several types of special effect pigments, those with a low refractive index such as fluorescent, photochromic or thermochromic pigments, and those with a higher refractive index such as pearlescent or glitter.

Examples of special effect pigments include pearlescent pigments such as titanium mica covered with an iron oxide, mica covered with an iron oxide, mica covered with bismuth oxychloride, titanium mica covered with chromium oxide, titanium mica covered with an organic dye, in particular of the aforementioned type, as well as pearlescent pigments based on bismuth oxychloride . They may also be particles of mica on the surface of which are superimposed at least two successive layers of metal oxides and/or of organic coloring materials.

The nacres may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or copper color or sheen.

By way of illustration of the nacres that can be used in the context of the present invention, mention may be made in particular of the gold-colored nacres marketed in particular by the company ENGELHARD under the name Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); mother-of-pearl bronzes sold in particular by the company MERCK under the name 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 in particular by the company ENGELHARD under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company MERCK under the name Passion orange (Colorona) and Matte orange (17449) (Microna); brown mother-of-pearl in particular marketed by the company ENGELHARD under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); mother-of-pearl with a copper sheen sold in particular by the company ENGELHARD under the name Copper 340A (Timica) and by the company Eckart under the name Prestige Copper; nacres with a red sheen in particular marketed by the company MERCK under the name Sienna fine (17386) (Colorona); nacres with a yellow sheen in particular marketed by the company ENGELHARD under the name Yellow (4502) (Chromalite); nacres of red tint with a gold sheen in particular marketed by the company ENGELHARD under the name Sunstone G012 (Gemtone); black mother-of-pearl with a gold sheen, in particular marketed by the company ENGELHARD under the name Nu antique bronze 240 AB (Timica), blue mother-of-pearl, in particular marketed by the company MERCK under the name Matte blue (17433) (Microna), Dark Blue (117324) (Colorona), white nacres with a silver sheen in particular marketed by the company MERCK under the name Xirona Silver and pinkish orange-golden nacres in particular marketed by the company MERCK under the name Indian summer (Xirona) and mixtures thereof.

In addition to nacres on a mica support, one can consider multilayer pigments based on synthetic substrates such as alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

Mention may also be made of pigments with an interference effect not fixed on a substrate, such as liquid crystals (Helicones HC from Wacker), holographic interference flakes (Geometric Pigments or Spectra f/x from Spectratek). Special effect pigments also include fluorescent pigments, whether fluorescent in daylight or which produce ultraviolet fluorescence, phosphorescent pigments, photochromic pigments, thermochromic pigments and quantum dots, marketed for example by the Quantum Dots Corporation.

The variety of pigments which can be used in the present invention makes it possible to obtain a rich palette of colors, as well as particular optical effects such as metallic and interference effects.

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

The pigments can be dispersed in the composition comprising them by means of a dispersing agent.

By "dispersing agent" is meant a compound which makes it possible to protect the dispersed particles against their agglomeration or flocculation. This dispersing agent can be a surfactant, an oligomer, a polymer or a mixture of several of them, carrying one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can cling physically or chemically to the surface of the pigments. These dispersing agents also have at least one functional group that is compatible or soluble in the continuous medium. Said agent can be charged, it can be anionic, cationic, zwitterionic or neutral.

According to a particular embodiment of the invention, the dispersing agents used are chosen from esters of 12-hydroxystearic acid more particularly and of C ₈ to C ₂₀ fatty acids and of polyol such as glycerol, diglycerin , such as poly(12-hydroxystearic) acid stearate with a molecular weight of approximately 750 g/mole such as that sold under the name Solsperse 21,000 by the company Avecia, the polygyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel or alternatively polyhydroxystearic acid such as that sold under the reference Arlacel P100 by the company Uniqema and mixtures thereof.

As other dispersant which can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17000 sold by the company Avecia, mixtures of polydimethylsiloxane/oxypropylene such as those sold by the company Dow Corning under the references DC2-5185, DC2-5225 C.

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

Thus the pigments previously surface-treated useful in the context of the invention are pigments which have undergone totally or partially a surface treatment of a chemical, electronic, electro-chemical, mechano-chemical or mechanical nature, with an organic agent such as those which are described in particular in Cosmetics and Toiletries, February 1990, Vol. 105, p. 53-64 before being dispersed in the composition in accordance with the invention. These organic agents can for example be chosen from amino acids; waxes, for example carnauba wax and beeswax; fatty acids, fatty alcohols and their derivatives, such as stearic acid, hydroxystearic acid, stearyl alcohol, hydroxystearyl alcohol, lauric acid and their derivatives; anionic surfactants; lecithins; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, for example aluminum stearate or laurate; metal alkoxides; polysaccharides, for example chitosan, cellulose and its derivatives; polyethylene; (meth)acrylic polymers, for example polymethylmethacrylates; polymers and copolymers containing acrylate units; the proteins ; alkanoamines; silicone compounds, for example silicones, polydimethylsiloxanes, alkoxysilanes, alkylsilanes, siloxysilicates; fluorinated organic compounds, for example perfluoroalkyl ethers; fluoro-silicone 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 have undergone several surface treatments.

The surface-treated pigments useful in the context of the present invention can be prepared according to surface treatment techniques well known to those skilled in the art or found as such in commerce.

Preferably, the surface-treated pigments are covered by an organic layer.

The organic agent with which the pigments are treated can be deposited on the pigments by solvent evaporation, chemical reaction between the molecules of the surfactant or creation of a covalent bond between the surfactant and the pigments. Surface treatment can thus be carried out, for example, by chemical reaction of a surfactant with the surface of the pigments and creation of a covalent bond between the surfactant and the pigments or the fillers. This method is described in particular in US patent 4,578,266.

Preferably, an organic agent bound to the pigments covalently will be used.

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

Preferably, the surface treatments of the pigments are chosen from the following treatments:
- a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW;
- a Chitosan treatment such as the CTS surface treatment marketed by LCW;
- a Triethoxycaprylylsilane treatment such as the AS surface treatment marketed by LCW;
- a Methicone treatment such as the SI surface treatment marketed by LCW;
- a Dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW;
- a Dimethicone/Trimethylsiloxysilicate treatment such as the Covasil 4.05 surface treatment marketed by LCW;
- a Lauroyl Lysine treatment such as the LL surface treatment marketed by LCW;
- a Lauroyl Lysine Dimethicone treatment such as the LL/SI surface treatment marketed by LCW;
- a Magnesium Myristate treatment such as the MM surface treatment marketed by LCW;
- an Aluminum Dimyristate treatment such as the MI surface treatment marketed by Miyoshi;
- a Perfluoropolymethylisopropyl ether treatment such as the FHC surface treatment marketed by LCW;
- an Isostearyl Sebacate treatment such as the HS surface treatment marketed by Miyoshi;
- a Disodium Stearoyl Glutamate treatment such as the NAI surface treatment marketed by Miyoshi;
- a Dimethicone/Disodium Stearoyl Glutamate treatment such as the SA/NAI surface treatment marketed by Miyoshi;
- a Perfluoroalkyl Phosphate treatment such as the PF surface treatment marketed by Daito;
- an acrylate copolymer/dimethicone and perfluoalkyl phosphate treatment such as the FSA surface treatment marketed by Daito;
- a Polymethylhydrogen siloxane/Perfluoroalkyl Phosphate treatment such as the FS01 surface treatment marketed by Daito;
- a Lauryl Lysine/Aluminum Tristearate treatment such as the LL-StAI surface treatment marketed by Daito;
- an Octyltriethylsilane treatment such as the OTS surface treatment marketed by Daito;
- an Octyltriethylsilane/Perfluoroalkyl Phosphate treatment such as the FOTS surface treatment marketed by Daito;
- an Acrylate/Dimethicone Copolymer treatment such as the ASC surface treatment marketed by Daito;
- an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito;
- a Microcrystalline Cellulose and Carboxymethyl Cellulose treatment such as the AC surface treatment marketed by Daito;
- a Cellulose treatment such as the C2 surface treatment marketed by Daito;
- an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito;
- a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito

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

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

According to a particular embodiment of the invention, the pigment or pigments are mineral pigments.

According to another particular embodiment of the invention, the pigment or pigments are chosen from nacres.

According to one particular embodiment of the invention, the dispersing agent is present with organic or inorganic pigments in particulate form of sub-micron size in the composition comprising them.

By "sub-micronic" or in English "sub-micronic", we mean pigments whose particle size has been micronized by micronization method and whose average particle size is less than one micrometer (μm), in particular ranging from 0 ,1 to 0.9 μm, and preferably ranging from 0.2 to 0.6 μm

According to one embodiment, the dispersing agent and the pigment(s) are present in an amount (dispersant: pigment) ranging from 0.5: 1 to 2: 1, particularly ranging from 0.75: 1 to 1.5: 1 or better ranging from 0.8:1 to 1.2:1.

According to a particular embodiment, the dispersing agent is suitable for dispersing the pigments and is compatible with a formulation curable by condensation.

By "compatible" is meant, for example, that said dispersing agent is miscible in the oily phase of the composition containing the pigment(s), it does not delay or reduce the hardening. The dispersing agent is preferably cationic.

The dispersing agent(s) can therefore have a silicone backbone, such as silicone polyether and dispersants of the amino-silicone type. Among the suitable dispersing agents, mention may be made of:
- amino-silicones, ie silicones comprising one or more amino groups such as those marketed 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, marketed by Genesee polymers,
- silicone acrylates such as Tego ^® RC 902, Tego ^® RC 922, Tego ^® RC 1041, and Tego ^® RC 1043, marketed by Evonik,
- polydimethylsiloxane (PDMS) silicones with carboxylic groups such as X-22162 and X-22370 by Shin-Etsu, silicone epoxy 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, Tego ^® RC 1412, by Evonik.

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

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

Preferably, the pigment(s) used in the process of the invention are chosen from carbon blacks such as Black 2, iron oxides, in particular red, brown or black, and micas coated with iron oxide, triarylmethane pigments, in particular blue and violet, such as BLUE 1 LAKE, azo pigments, in particular red, such as D&C RED 7, alkali 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 quantity of pigments varies from 0.5% to 40% by weight, preferably from 1% to 20% by weight relative to the weight of the composition(s) including.

Variants of the process according to the present invention

According to a preferred variant of the invention, the method comprises:
▪ the application to the keratin fibers of a composition (C) comprising the metal salt(s) as defined above; followed by
▪ the application to the keratin fibers of a composition (A) as defined previously; followed by
▪ the application to the keratin fibers of a composition (B) as defined previously;
it being understood that the coloring 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 preferably in composition (A) .

According to a more preferred variant of the invention, the method comprises:
▪ the application to the keratin fibers of a composition (C) comprising the metal salt(s) as defined previously; followed by
▪ the application to the keratin fibers of a composition (A) , the composition (A) being or comprising an oily dispersion (A') , the oily dispersion (A') comprising:
i) compound(s) A in the form of one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined above; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s); followed by
▪ the application to the keratin fibers of a composition (B) as defined above;
it being understood that the coloring 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 preferably in composition (A) .

According to an even more preferred variant of the invention, the method comprises:
▪ the application to the keratin fibers of a composition (C) comprising the metal salt(s) as defined previously; followed by
▪ the application to the keratin fibers of a composition (A) , the composition (A) being or comprising an oily dispersion (A') , the oily dispersion (A') comprising:
i) compound (s) A in the form of one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined previously; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s); followed by
▪ the application to the keratin fibers of a composition (B) comprising iv) one or more amino compound(s) chosen from polyamino compounds having at least two primary amine and/or secondary amine groups such as as previously defined;
it being understood that the coloring 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 preferably in composition (A) .

According to a particular variant of the invention, the method comprises:
▪ the application to the keratin fibers of a composition (C) comprising the metal salt(s) as defined above; followed by
▪ the application to the keratin fibers of a composition (B) as defined previously; followed by
▪ the application to the keratin fibers of a composition (A) as defined previously;
it being understood that the coloring 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 preferably in composition (A) .

According to a more particular variant of the invention, the method comprises:
▪ the application to the keratin fibers of a composition (C) comprising the metal salt(s) as defined previously; followed by
▪ the application to the keratin fibers of a composition (B) as defined previously; followed by
▪ the application to the keratin fibers of a composition (A) , the composition (A) being or comprising an oily dispersion (A') , the oily dispersion (A') comprising:
i) compound (s) A in the form of one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined previously; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s);
it being understood that the coloring 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 preferably in composition (A) .

According to an even more particular variant of the invention, the method comprises:
▪ the application to the keratin fibers of a composition (C) comprising the metal salt(s) as defined previously; followed by
▪ the application to the keratin fibers of a composition (B) comprising iv) one or more amino compound(s) chosen from polyamino compounds having at least two primary amine and/or secondary amine groups such as as previously defined;
followed by
▪ the application to the keratin fibers of a composition (A) , the composition (A) being or comprising an oily dispersion (A') , the oily dispersion (A') comprising:
i) compound (s) A in the form of one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined previously; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s);
it being understood that the coloring 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 preferably in composition (A) .

According to another preferred variant of the invention, the method comprises:
▪ the application to the keratin fibers of a composition (A) as defined above; followed by
▪ the application to the keratin fibers of a composition (B) as defined above;
Being heard that :
- the metal salt(s) are included in composition (A) and/or in composition (B) , preferably in composition (A)
- the coloring 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 method comprises:
▪ the application to the keratin fibers of a composition (A), the composition (A) being or comprising an oily dispersion (A') , the oily dispersion (A') comprising:
i) compound (s) A in the form of one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined previously; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s); followed by
▪ the application to the keratin fibers of a composition (B) as defined above;
Being heard that :
- the metal salt(s) are included in composition (A) and/or in composition (B) , preferably in composition (A) ; And
- the coloring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) , preferably in composition (A) .

According to another even more preferred variant of the invention, the method comprises:
▪ the application to the keratin fibers of a composition (A), the composition (A) being or comprising an oily dispersion (A') , the oily dispersion (A') comprising:
i) compound (s) A in the form of one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined previously; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s); followed by
▪ the application to the keratin fibers of a composition (B) comprising iv) one or more amino compound(s) chosen from polyamino compounds having at least two primary amine and/or secondary amine groups such as as previously defined;
Being heard that :
- the metal salt(s) are included in composition (A) and/or in composition (B) , preferably in composition (A) ; And
- the coloring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) , preferably in composition (A) .

According to another particular variant of the invention, the method comprises:
▪ the application to the keratin fibers of a composition (B) as defined previously; followed by
▪ the application to the keratin fibers of a composition (A) as defined above;
Being heard that :
- the metal salt(s) are included in composition (A) and/or in composition (B) , preferably in composition (A) ; And
- the coloring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) , preferably in composition (A) .

According to another more particular variant of the invention, the method comprises:
▪ the application to the keratin fibers of a composition (B) as defined above; followed by
▪ the application to the keratin fibers of a composition (A), the composition (A) being or comprising an oily dispersion (A') , the oily dispersion (A') comprising:
i) compound(s) A in the form of one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined above; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s);
Being heard that :

- the metal salt(s) are included in composition (A) and/or in composition (B) , preferably in composition (A) ; And
- the coloring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) , preferably in composition (A) .

According to another even more particular variant of the invention, the method comprises:
▪ the application to the keratin fibers of a composition (B) comprising iv) one or more amino compound(s) chosen from polyamino compounds having at least two primary amine and/or secondary amine groups such as as previously defined; followed by
▪ the application to the keratin fibers of a composition (A), the composition (A) being or comprising an oily dispersion (A') , the oily dispersion (A') comprising:
i) compound(s) A in the form of one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined above; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s);
Being heard that :

- the metal salt(s) are included in composition (A) and/or in composition (B) , preferably in composition (A) ; And
- the coloring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) , preferably in composition (A) .

Additional Features Concerning the Compositions of the Present Invention

Compositions (A) , (B) , (C) and (D) are cosmetic, ie they only comprise cosmetically acceptable ingredients.

The compositions (A) , (B) , (C) and (D) according to the invention may also comprise a cosmetic additive chosen from perfumes, preservatives, fillers, UV filters, waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, free radical scavengers and thickeners.

The compositions (A) , (B) , (C) and (D) according to the invention can be in all the dosage forms conventionally used for hair application. In a non-limiting manner, the compositions (A) , (B) , (C) and (D) can be in the form of a lotion, a cream, a mousse, a gel, a spray or hairspray.

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

According to a particular embodiment of the invention, the 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 oil(s) iii) included in the oily dispersion (A′) and the composition (B) are identical.

According to a preferred embodiment of the invention, the hydrocarbon-based oil or oils iii) included in composition (B) are chosen from hydrocarbon-based oils having from 8 to 14 carbon atoms, in particular the apolar oils described previously. Even more preferably, the hydrocarbon 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 compound(s) chosen from polyamine compounds having at least two amine groups primary and/or secondary amine as defined previously in emulsion of the oil-in-water (O/W) or “oil-in-water (O/W)” type.

Compositions (A) , (B) , (C) and (D) can be applied to dry or wet keratin fibres, as well as to all types of fibres, light or dark, natural or colored, permed, bleached or straightened. .

The application to the fibers can be carried out by any conventional means, in particular by means of a comb, a paintbrush, a brush or the fingers.

After the application of each of the compositions (A) , (B) , (C) and (D) the fibers can be left to dry or dried, for example at a temperature 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 hair dryer, a heat lamp then optionally with a straightening iron.

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

During drying, a mechanical action on the locks can be exerted such as combing, brushing, the passage of the fingers. This operation can also be carried out once the fibers have dried, naturally or not.

The drying step of the method of the invention can be implemented with a drying device such as a helmet, a hair dryer, a straightening iron or a climazon.

When the drying step is implemented with a helmet or a hair dryer, the drying temperature ranges from 40°C to 110°C, preferably from 50°C to 90°C.

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

Once the drying is complete, a final rinse or shampoo can optionally be carried out.

According to an advantageous variant of the process of the invention, there is no rinsing and the keratin fibers are dried in the air or using a drying device such as a hair dryer. between the step of applying composition (A) to the keratin fibers and the step of applying composition (B) to the keratin fibers. Preferably, one waits between the two steps from 1 minute to 6 hours, in particular from 10 minutes to 5 hours, more particularly from 30 minutes to 4 hours, preferably around 3 hours.

According to another variant of the process of the invention, there is neither rinsing nor drying of the keratin fibers between the step of applying composition (A) to the keratin fibers and the step of applying the keratin fibers of composition (B). Preferably, one waits between the two steps from 1 minute to 6 hours, in particular from 10 minutes to 5 hours, more particularly from 30 minutes to 4 hours, preferably around 3 hours.

Special compositions

According to a second aspect, the subject of the present invention is a composition (A0) comprising:
- the dispersion (A′) as defined previously;
- one or more metal salt(s) as defined above;
- optionally one or more coloring agent(s), as defined above.

According to a third aspect, the subject of the present invention is a composition (B0) comprising:
- at least one compound B as defined above;
- one or more metal salt(s) as defined above;
- optionally one or more coloring agent(s) as defined above.

According to a fourth aspect, the subject of the present invention is a composition (C0) comprising:
- one or more metal salt(s) as defined previously;
- one or more coloring agent(s) as defined previously.

Multi-compartment kit or device

According to a fifth aspect, the subject of the present invention is a kit or device with several separate compartments comprising:
▪ in a first compartment: the composition (A) as defined above;
▪ in a second compartment distinct from the first: the composition (B) as defined previously; And
▪ optionally in a third compartment separate from the other two: the composition (C) as defined previously; And
▪ optionally in a fourth compartment separate from the other three: the composition (D) as defined above;
in which :
- at least one of the compositions of the kit comprises one or more metal salt(s) as defined previously; And
- at least one of the compositions of the kit comprises one or more coloring agent(s) as defined previously.

The packaging assembly for the compositions is, in a known manner, any packaging suitable for storing cosmetic compositions (bottles, tube, spray bottle, aerosol bottle in particular).

Examples

The examples which follow make it possible to better understand the invention without however presenting a limiting nature.

Example 1: Preparation of oily dispersions (A')

The oily dispersions (A') are formed as a whole [particles i) + stabilizing agent ii)] at:
- 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 carried out in a 1 liter controlled reactor. The synthesis is carried out in two steps:

During a first step, Isobornyl Acrylate is polymerized in Isododecane / Ethyl Acetate (60/40) in the presence of a small amount of Ethyl Acrylate and a radical initiator (T21S). In the first step, the Isobornyl Acrylate / Ethyl Acrylate mass ratio is 92/8.

During the second step, the rest of the Ethyl Acrylate and the Maleic Anhydride are poured in the presence of Isododecane / Ethyl Acetate (60/40) and Trigonox 21S (T21S) radical initiator.

After stripping, the polymer has a dry extract of 52% in isododecane. The ratios used to obtain the stabilizer and the particulate core are summarized in the table below:

Mass percentage
Stabilizing Agent – Particulate Core Monomer

Mass percentage in the stabilizer
and the particulate heart Stabilizing agent ii) 22 Isobornyl Acrylate 92 Ethyl acrylate 8 Particle core i) 78 Ethyl Acrylate 87 Maleic anhydride 13

Quantity of reagents:

Step 1 :

Reagents Mass (g) Isobornyl Acrylate 50 Ethyl Acrylate 4 T21S 0.54 Isododecane / AcOEt (60/40) 96

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

Reagent Mass (g) Isododecane / AcOEt (60/40) 80

2nd step :

Reagents Mass (g) Mass added in beaker for casting (g) Ethyl Acrylate 171 196.65 Maleic Anhydride 25 28.7 T21S 1.96 2.25 Isododecane / AcOEt (60/40) 196 225.4

Experimental protocol :

Isododecane/Ethyl Acetate (60/40), Isobornyl Acrylate, Ethyl Acrylate and T21S are introduced into a reactor at the bottom of the tank. The medium is heated to 90° C., under argon and with stirring. The dry extract during this first step is 35.9%.

After 2 h of heating, the NMR indicates a consumption of 97% of Isobornyl Acrylate (Consumption of Ethyl Acrylate: 97%).

After 2 hours of reaction, isododecane / ethyl acetate (60/40) are introduced into the base stock. Heat to 90°C in the middle.

Once the medium has reached 90°C, the Ethyl Acrylate/Maleic Anhydride, Isododecane/Ethyl Acetate (60/40), and T21S are introduced over 2 hours by pouring. At the end of the casting the medium is milky. The dry extract is 40%.

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

1L of isododecane and ethyl acetate are then stripped (the NMR indicates that there are no more monomers and the ethyl acetate is completely removed from the dispersion). The dry extract is about 52%.

Examples 2 to 6

Compositions tested

The following compositions were used in the examples which follow. The amounts are given in g per 100 g of composition.

Composition (A1)

Ingredients Quantity (g) Combination of particles from example 1, ingredients i), ii) 15 (M.A.) Red iron oxide, CI 77491 6 Isododecane Qsp 100

M.A.: Active Matter

Composition (A2)

Ingredients Quantity (g) Combination of particles from example 1, ingredients i), ii) 15 (M.A.) Red iron oxide, CI 77491 6 Aluminum acetate basic
(CAS# 142-03-0 marketed by the company Sigma-Aldrich) 5 Isododecane Qsp 100

M.A.: Active Matter

Membership (B1)

Ingredients Quantity (g) Chitosan
(Kionutrime CSG marketed by the company Kitozyme) 5
Acetic acid 2 Water 70 Bis-Cetearyl Amodimethicone
(Silsoft AX marketed by Momentive Performance Materials) 8 (M.A.) Cetyl PEG/PPG-10/1 Dimethicone
(Abil EM 90 marketed by the company Evonik Goldschmidt) 1 Isododecane Qsp 100

M.A.: Active Matter

Membership (B2)

Ingredients Quantity (g) Chitosan
(Kionutrime CSG marketed by the company Kitozyme) 5 Acetic acid 2 Aluminum acetate basic
(CAS# 142-03-0 marketed by the company Sigma-Aldrich) 0.5 Water Qsp 100

Membership (C1)

Ingredients Quantity (g) Aluminum acetate basic
(CAS# 142-03-0 marketed by the company Sigma-Aldrich) 0.5 Absolute Ethanol Qsp 100

Membership (C2)

Ingredients Quantity (g) Aluminum acetate basic
(CAS# 142-03-0 marketed by the company Sigma-Aldrich) 5 Absolute Ethanol Qsp 100

Application protocol

The application protocol followed in the following examples comprises the application either of two distinct compositions or of three distinct compositions.

Application protocol No. 1 (with two distinct compositions)

The application protocol with two distinct compositions includes the following steps:
- Application to a lock of dry hair of composition (A1) or (A2) according to a bath ratio of 0.5 g of composition (A1) or (A2)/g of hair; Then
- Drying the wick with a hair dryer; Then
- Application to the lock of composition (B1) or (B2) according to a bath ratio of 0.5 g of composition (B1) or (B2)/g of hair; Then
- Dry the wick with a hair dryer.

Application protocol No. 2 (with three distinct compositions)

The application protocol with three distinct compositions includes the following steps:
-Application to a lock of dry hair of composition (C1) or (C2) according to a bath ratio of 0.5 g of composition (C1) or (C2)/g hair; Then
- Application to the lock of composition (A1) or (A2) according to a bath ratio of 0.5 g of composition (A1) or (A2)/g of hair; Then
- Drying the wick with a hair dryer; Then
- Application to the lock of composition (B1) or (B2) according to a bath ratio of 0.5 g of composition (B1) or (B2)/g of hair; Then
- Dry the wick with a hair dryer.

Intensive shampoo protocol

The shampoo resistance evaluations were carried out according to the following shampoo protocol, 24 hours after application of the compositions according to the application protocol described above:
The locks of colored hair are combed, moistened under water at 35°C before being passed between the fingers 5 times for 5 seconds. The locks of hair are then wrung out between two fingers.
A standard shampoo (Garnier Ultra Doux) is applied evenly to the colored locks at the rate of 0.4 g of standard shampoo per gram of locks, gently kneading the locks of hair lengthwise (6 passes) for 15 seconds, root to tip.
The locks of hair are then placed in a watch glass and allowed to sit for 1 minute.
Then, the locks of hair are rinsed with water by passing the locks between the fingers (15 passages). The locks of hair are then wrung out between two fingers before the next shampoo.
After the proofs of several shampoos are carried out, the strands of hair are combed and dried with a hair dryer.

Assessment of color remanence to shampoo

The color retention 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 color, a* indicates the green/red color axis and b* the blue/yellow color axis.
The persistence of the coloring is evaluated by the difference in color ΔE between the colored locks before shampooing, then after having undergone 8 shampooings according to the protocol described above. The lower the value of ΔE, the more the color is remanent to shampoos.
The value of ΔE is calculated according to the following equation:

In this equation, L*a*b* represent the values measured after coloring the hair and after having undergone shampooing, and L ₀ *a ₀ *b ₀ * represent the values measured after coloring the hair but before shampooing.

Example 2 (Comparative)

Composition (A1) and composition (B1) were applied to a lock of 90% white natural hair type hair (also called 90% BN) according to application protocol No. 1 described above.

Shampoo resistance evaluations were conducted according to the intensive shampooing protocol described previously.

Color measurements:

Number of shampoos I* To* b* ΔE 0 shampoo 34.5 25.6 19.2 0 8 shampoos 48.7 12.4 15.0 19.8

It appears visually that the red coloring obtained after application of the composition (A1) and of the composition (B1) has almost completely disappeared after 8 shampooings.

Example 3

Composition (C1), composition (A1) and composition (B1) were applied to a lock of 90% white natural hair type hair (also called 90% BN) according to application protocol No. 2 described previously.

Shampoo resistance evaluations were conducted according to the intensive shampooing protocol described previously.

Color measurements: Number of shampoos I* To* b* ΔE 0 shampoo 34.5 25.6 19.2 0 8 shampoos 38.9 22.1 17.3 5.9

Visually, the red coloring seems unchanged between the coloring obtained just after having implemented the process of the invention, and after 8 successive shampoos. In addition the hair appears individualized after treatment, and at 8 shampoos. The touch is pleasant.

Example 4

Composition (C2), composition (A1) and composition (B1) were applied to a lock of natural hair type hair at 90% white (also called 90% BN) according to application protocol No. 2 described previously.

Shampoo resistance evaluations were conducted according to the intensive shampooing protocol described previously.

Color measurements: Number of shampoos I* To* b* ΔE 0 shampoo 34.5 25.6 19.2 0 8 shampoos 36.3 26.6 20.0 2.2

Visually, the red coloring seems unchanged between the coloring obtained just after having implemented the process of the invention, and after 8 successive shampoos. In addition the hair appears individualized after treatment, and at 8 shampoos. The touch is pleasant.

Example 5

Composition (A2) and composition (B1) were applied to a lock of 90% white natural hair type hair (also called 90% BN) according to application protocol No. 1 described above.

Shampoo resistance evaluations were conducted according to the intensive shampooing protocol described previously.

Color measurements: Number of shampoos I* To* b* ΔE 0 shampoo 34.5 25.6 19.2 0 8 shampoos 41.8 21.3 17.3 8.7

Visually, the red coloring seems to have slightly disappeared between the coloring obtained just after having implemented the process of the invention, and after 8 successive shampoos, but still remains clearly visible. In addition, the hair appears individualized after treatment, and after 8 shampoos. The touch is very pleasant.

Example 6

Composition (A1) and composition (B2) were applied to a lock of 90% white natural hair type hair (also called 90% BN) according to application protocol No. 1 described above.

Shampoo resistance evaluations were conducted according to the intensive shampooing protocol described previously.

Color measurements: Number of shampoos I* To* b* ΔE 0 shampoo 35.7 22.9 16.5 0 8 shampoos 47.3 15.3 15.2 13.9

Visually, the red coloring seems to have slightly disappeared between the coloring obtained just after having implemented the process of the invention, and after 8 successive shampoos, but still remains clearly visible. In addition the hair appears individualized after treatment, and at 8 shampoos. The touch is very pleasant.

Claims (29)

Process for dyeing keratin fibers comprising:
▪ the application to the keratin fibers of a composition (A) comprising at least one compound A carrying at least one chemical function A ; And
▪ the application to the keratin fibers of a composition (B) comprising at least one compound B carrying at least one chemical function B , the compound B being different from the compound A ;
in which :
- the chemical functions A and B are capable of forming covalent bonds together; And
- the process implements:
α) one or more metal salt(s) chosen from transition metal salts, alkali metal salts, alkaline-earth metal salts, aluminum salts, boron salts, salts of tin, magnesium salts, hydrates thereof and mixtures thereof, the metal salt(s) being included in composition (A) and/or in composition (B) and/or in a separate composition ( C) , composition (C) also being applied to the keratin fibres; And
β) one or more coloring agent(s) chosen from direct dyes, oxidation dyes, pigments and mixtures thereof, the coloring agent(s) being included in the composition (A) and/or in composition (B) and/or in composition (C) and/or in a separate composition (D) , composition (D) also being applied to the keratin fibres. Process according to the preceding claim, in which the composition (A) is applied after the composition (B) or the composition (B) is applied after the composition (A) , preferably the composition (B) is applied after the composition (A ) . Process according to Claim 1, in which the chemical function or functions A are chosen from the following functions:
- epoxy;
- 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, hemi-acetals, aminals, hemi-aminols;
- isocyanates;
- thiocyanate;
- ketones including alpha-hydroxyketones, alpha-haloketones;
- lactones, thiolactones;
- imines;
- imides;
- N-hydroxysuccinimide esters;
- imidates;
- thiosulphate;
- oxazine and oxazoline;
- oxazinium and oxazolinium;
- C ₁ to C ₃₀ alkyl or C ₆ to C ₃₀ aryl or aralkyl halides, in particular iodides, chlorides, bromides;
- unsaturated, carbon or heterocycle halides;
- sulphonyl halides of formula RSO ₂ X, in which X=Cl or F and R is an alkyl group in C ₁ to C ₃₀ ;
- cyclic carbonates;
- diazonium;
- carbodiimide;
- and mixtures thereof;
preferably from the functions anhydride, acid chloride, carboxylic acid esters, epoxide, and their mixtures, more preferentially from the functions anhydride, acid chloride, carboxylic acid esters, and their mixtures, even more preferentially the or the chemical functions A are anhydride functions. Process according to any one of the preceding claims, in which the compound or compounds A are polymers, preferably polymers containing the maleic anhydride unit. Process according to any one of the preceding claims, in which the chemical function or functions B are chosen from the functions hydroxyl, primary amine, secondary amine, thiol, carboxylic acid and their mixtures, preferably from the functions hydroxyl, primary amine, amine secondary, thiol and mixtures thereof. Process according to any one of the preceding claims, in which the metal salt(s) are chosen from aluminum salts, their hydrates and their mixtures. Process according to any one of the preceding claims, in which the metal salt(s) are organic or inorganic, preferably organic, more preferably chosen from citrates, lactates, glycolates, gluconates, acetates , propionates, fumarates, oxalates, glycinates, tartrates, their hydrates and mixtures thereof, even more preferably chosen from basic aluminum acetate, aluminum oxalate, aluminum citrate, hydrated or not hydrated, aluminum lactate, aluminum glycinate and mixtures thereof, most preferably the metal salt is basic aluminum acetate. Process according to any one of the preceding claims, in which the metal salt(s) are included in composition (A) or in composition (C) , preferably in composition (C) . Process according to any one of the preceding claims, in which the metal salt(s) 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. Process according to any one of the preceding claims, in which the composition (A) is or comprises an oily dispersion (A') which comprises the compound or compounds A . Process according to the preceding claim, in which the oily dispersion (A') comprises:
i) compound(s) A in the form of one or more particles consisting of one or more ethylenic copolymer(s):
a) (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl, and
b) an ethylenically unsaturated anhydride compound; And
ii) one or more stabilizing agent(s) consisting of ethylenic polymers chosen from:
c) polymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl monomers; And
d) copolymers of (C ₁ -C ₆ )(alkyl)acrylate, (C ₃ -C ₁₂ )cycloalkyl and (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl; And
iii) one or more hydrocarbon oil(s). Process according to the preceding claim, in which the monomer a) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl is of formula H ₂ C=C(R)-C(O)-O-R 'with R representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl, and R' representing a (C ₁ -C ₄ )alkyl group such as methyl or ethyl, preferably the monomer a) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl is a monomer (meth)acrylate of (C ₁ -C ₄ )alkyl, more preferentially the monomer a) (C ₁ -C ₄ ) (C ₁ -C ₄ )alkyl (alkyl)acrylate is chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl, n-butyl (meth)acrylate, or tert-butyl (meth)acrylate; even more preferably monomer a) (C ₁ -C ₄ )(alkyl) acrylate (C ₁ -C ₄ )alkyl is chosen from methyl acrylate and ethyl acrylate. Process according to Claim 11 or 12, in which the ethylenically unsaturated anhydride monomer b) is chosen from derivatives of maleic anhydride (Ib) and itaconic anhydride (IIb) :

Formulas (Ib) and (IIb) in which R _a , R _b and R _c , identical or different, representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably R _a , R _b , and R _c represent a hydrogen atom, preferably from derivatives of maleic anhydride (Ib) , more preferably monomer b) anhydride containing ethylenic unsaturation is maleic anhydride. Process according to any one of Claims 11 to 13, 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. Process according to any one of Claims 11 to 14, in which the particles of polymer(s) i) are 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 the oily dispersion (A′) . Process according to any one of Claims 11 to 15, in which the stabilizing agent(s) ii) of the oily dispersion(AT')consist of ethylenic polymers chosen from:
c) polymers of monomers of formula H₂C=C(R)-C(O)-O-R’’ withRrepresenting a hydrogen atom or a group (C₁-VS₄)alkyl such as methyl, andR''representing a group (C₅-VS₁₀)cycloalkyl 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’’ withRAndR''as previously defined andR'representing a group (C₁-VS₄) alkyl such as methyl or ethyl; preferably, the stabilizing agent(s) ii) of the oily dispersion(AT')are chosen from isobornyl (meth)acrylate polymers, more preferably the stabilizing agent(s) ii) of the oily dispersion(AT')are chosen from isobornyl (meth)acrylate homopolymer and random copolymers of isobornyl (meth)acrylate and C-alkyl (meth)acrylate₁-VS₄preferably present in a weight ratio of isobornyl (meth)acrylate / C-alkyl (meth)acrylate₁-VS₄greater than 4; advantageously, said weight ratio ranges from 4.5 to 19. Process according to any one of Claims 11 to 16, in which the combination of particle(s) i) + stabilizing agent(s) ii) present in the oily dispersion (A') comprises from 10% to 50% by weight, preferably from 15% to 30% by weight of copolymers d) and from 50% to 90%, preferably from 70% to 85% by weight of copolymers a) + b), relative to the total weight of the particle(s) i)+stabilizing agent(s) ii). Process according to any one of Claims 11 to 17, in which the hydrocarbon oil(s) iii) of the oily dispersion (A') are apolar, ie formed solely of carbon and hydrogen atoms, especially volatile; preferably chosen from hydrocarbon oils having from 8 to 14 carbon atoms; more preferably isododecane Process according to any one of Claims 11 to 18, in which the composition (A) comprises a total content of particle(s) i) + stabilizing agent(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) . Process according to any one of Claims 11 to 19, in which the composition (A) comprises the oily dispersion (A') in the form of an inverse emulsion, ie of the water-in-oil (W/O) type and comprises one or several surfactants, preferably nonionic. Process according to any one of the preceding claims, in which the composition (B) comprises as compound(s) B :
iv) one or more amino compound(s) chosen from polyamino compounds having at least two primary amine and/or secondary amine groups; and or
v) one or more hydroxylated compound(s), organic(s) or inorganic(s), polymeric or not, preferably organic(s) or silicone(s), chosen from polyhydroxylated compounds having at at least two hydroxyl groups; and or
vi) one or more thiol compound(s), organic(s) or inorganic(s), polymer(s) or not, preferably organic(s) or silicone(s), chosen from polythiol compounds having at at least two thiol groups;
preferably iv) one or more amino compound(s) chosen from polyamino compounds having at least two primary amine and/or secondary amine groups. Process according to Claim 21, in which the polyamino compounds having at least two primary amine and/or secondary amine groups are chosen from:
▪ the poly((C₂-VS₅)alkyleneimines), and in particular polyethyleneimines and polypropyleneimines, preferably poly(ethyleneimine);
▪ poly(allylamines);
▪ polyvinylamines and their copolymers, in particular with vinylamides;
▪ polyamino acids with NH groups₂such as polylysine;
▪ amino dextran;
▪ polyvinyl amino alcohol;
▪ copolymers based on acrylamidopropylamine;
▪ chitosan;
▪ the polydi(C₁-VS₄)alkylsiloxanes comprising amino groups at the end of the chain or on the side chains, in particular amino terminal or side groups (C₁-VS₆) alkyl such as aminopropyl, more particularly those of formula(IVb)Or(IVc)Or(IVd):

Formula(IVb)in whichR ^To , AndR ^b , identical or different, preferably identical, represent a group (C₁-VS₄)alkyl such as methyl, (C₁-VS₄)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C₁-VS₄)alkyl such as benzyl, or aryl(C₁-VS₄)alkoxy such as benzoxy, preferably (C₁-VS₄)alkyl such as methyl,R ^vs AndR' ^vs , identical or different, preferably identical, represent a hydrogen atom, a group (C₁-VS₄)alkyl, an amino(C₁-VS₄)alkyl or (C₁-VS₄)alkylamino(C₁-VS₄)alkyl, preferably a hydrogen atom or an amino(C₁-VS₄)alkyl such as aminoethyl;Xrepresents a covalent bond, an oxygen atom, preferably a covalent bond,ALKAndALK', identical or different, preferably identical, represent a group (C₁-VS₆)alkylene, preferably (C₁-VS₄) alkylene such as propylene;notrepresenting an integer greater than 2 and more particularly the value ofnotis such that the weight-average molecular weight of the silicone is between 500 and 55,000; more preferably polydi(C₁-VS₄)alkylsiloxanes of formula(IVb)are of formula(IV'b)Or(IV''b)next :


Formula(IV'b)in which the value ofnotis such that the weight-average molecular weight of the silicone is between 500 and 55,000;
Formula(IV''b)withR ^vs ,R' ^vs ,ALK,ALK', Andnotas previously defined for(IVb), more preferablyALKAndALK'are identical and represent a group (C₁-VS₄)alkylene such as propylene,R ^vs AndR' ^vs are identical and represent an amino group (C₁-VS₄) alkyl such as aminoethyl;

Formula(IVc)in whichR ^To ,R ^b , AndR ^d , identical or different, preferably identical, represent a group (C₁-VS₄)alkyl such as methyl, (C₁-VS₄)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C₁-VS₄)alkyl such as benzyl, or aryl(C₁-VS₄)alkoxy such as benzoxy, preferably (C₁-VS₄)alkyl such as methyl,R ^d can also represent a group (C₁-VS₆)alkyl substituted by a group (C₁-VS₄)alkylamino or amino,R ^vs represents a hydrogen atom or a group (C₁-VS₄)alkyl, preferably a hydrogen atom;ALKrepresents a group (C₁-VS₆)alkylene, preferably (C₁-VS₄) alkylene such as propylene;notAndm, identical or different, representing an integer greater than 2 and more particularly the values ofmAndnotare such that the weight-average molecular weight of the silicone is between 1,000 and 55,000; More preferably polydi(C₁-VS₄)alkylsiloxanes of formula(IVc)are of formula(IV'c)next :

Formula(IV'c), in which the values ofnotAndmare such that the weight-average molecular weight of the silcone is between 1,000 and 55,000;

Formula(IVd)in whichR ^To , AndR ^b , identical or different, preferably identical, represent a group (C₁-VS₄)alkyl such as methyl, (C₁-VS₄)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C₁-VS₄)alkyl such as benzyl, or aryl(C₁-VS₄)alkoxy such as benzoxy, preferably (C₁-VS₄)alkyl such as methyl, andR ^d represents a group (C₁-VS₆)alkyl optionally substituted by a group (C₁-VS₄)alkylamino or amino, preferably (C₁-VS₄)alkyl, such as isobutyl, terbutyl ornot-butyl,R ^vs represents a hydrogen atom or a group (C₁-VS₄)alkyl, preferably hydrogen atom;ALKrepresents a group (C₁-VS₆)alkylene, preferably (C₁-VS₄) alkylene such as propylene;notrepresenting an integer greater than 2 and more particularly the value ofnotis such that the weight-average molecular weight of the silicone is between 500 and 5000; more preferably polydi(C₁-VS₄)alkylsiloxanes of formula(IVd)are of formula(IV’d)next :

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

Formula(IV)in which :
R ^To AndR ^b , identical or different, preferably identical, represent a group (C₁-VS₄)alkyl such as methyl, (C₁-VS₄)alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C₁-VS₄)alkyl such as benzyl, or aryl(C₁-VS₄)alkoxy such as benzoxy, preferably (C₁-VS₄) alkyl such as methyl;
R ^vs represents a hydrogen atom or a group (C₁-VS₄)alkyl, preferably a hydrogen atom;
R ^e represents a hydroxy group, (C₁-VS₄)alkoxy, amino, (C₁-VS₄)alkylamino;
R ^f , represents a group (C₁-VS₄)alkyl such as methyl, (C₁-VS₄)alkoxy such as methoxy, a hydroxy group or -O–(SiR₂)_x-R' withRrepresenting a group (C₁-VS₄)alkyl or (C₁-VS₄)alkoxy andR'representing a group (C₁-VS₄)alkoxy or hydroxy, preferablyR ^f represents a group (C₁-VS₄)alkyl, (C1-C4)alkoxy, or -O–(SiR₂)_x-R' withRrepresenting a group (C₁-VS₄)alkyl such as methyl andR'a hydroxy group or (C₁-VS₄)alkoxy such as methoxy;
ALKAndALK', identical or different, represent a group (C₁-VS₆)alkylene, preferably (C₁-VS₄) alkylene such as ethylene or propylene;notAndm, identical or different, representing an integer greater than 2,pAndxare integers greater than or equal to 0, preferablypis between 2 and 20 and more particularly the values ofm,not,pAndxare such that the weight-average molecular weight of the silicone is between 2,000 and 700,000, preferably between 5,000 and 500,000; more preferably the amodimethicones of formula(IV)are of formula(IV)Or(IV''e)next :

Formula(IV)in whichALKrepresents a group (C₁-VS₆)alkylene preferably ethylene,ALK'represents a group (C₁-VS₆)alkylene preferably propylene, andm,notAndprepresent values greater than 2, with m, n and p such that the weight-average molecular mass of the compound is between 5,000 and 500,000 approximately; preferablyprepresents an integer between 8 and 20;

Formula(IV''e)in which :
R ^To , AndR ^b , identical or different, preferably identical, represent a group (C₁-VS₄)alkyl such as methyl, (C₁-VS₄)alkoxy such as methoxy, preferably (C₁-VS₄) alkyl such as methyl;
R ^vs represents a hydrogen atom or a group (C₁-VS₄)alkyl, preferably hydrogen atom;
R ^g represents a hydrogen atom, or a group (C₁-VS₄)alkyl;
R ^f , represents a group (C₁-VS₄)alkyl such as methyl, (C₁-VS₄)alkoxy such as methoxy, or -O–(SiR₂)_x-R' withRrepresenting a group (C₁-VS₄)alkyl such as methyl andR'a hydroxy group or (C₁-VS₄)alkoxy such as methoxy;
ALKrepresents a group (C₁-VS₆) alkylene, preferably ethylene;
ALK'represents a group (C₁-VS₆) alkylene, preferably propylene;
notAndm, identical or different, representing an integer greater than 2,xis an integer greater than or equal to 0, preferably the values ofm,notAndxare such that the weight-average molecular weight of the silicone is between 2,000 and 700,000, preferably between 5,000 and 500,000;
Even more preferably amodimethicones of formula(IV)are of formula(IV'''e)next :

Formula(IV'''e)in which :
R ^f ,R ^g ,ALK,ALK',mAndnotare as defined for(IV''e);
▪ polyether amines, in particular polyethylene glycol and/or polypropylene glycol α, ω-diamine (with amine function at the end of the chain)
▪ polytetrahydrofuran (or polytetramethylene glycol) α, ω-diamine, polybutadienes α, ω-diamine;
▪ polyamidoamine dendrimers (PAMAM) with terminal amine functions;
▪ poly(meth)acrylates or poly(meth)acrylamides carrying lateral primary or secondary amine functions such as poly(3-aminopropyl)methacrylamide, poly(2-aminoethyl)methacrylate; And
▪ their mixtures;
preferably, the amino compound(s) iv) of the composition(B)are chosen from those of formulas(IVb)And(IV)as defined above, more preferably, the amino compound(s) iv) of the composition(B)are chosen from those of formulas(IV'b)And(IV)as previously defined. Process according to any one of Claims 11 to 22, in which the composition (B) comprises one or more hydrocarbon oil(s) iii) as defined in Claim 11 or 18; preferably, the hydrocarbon-based oil(s) iii) included in the oily dispersion (A′) and the composition (B) are identical; more preferably, the hydrocarbon-based oil iii) included in composition (B) is isododecane. Process according to any one of the preceding claims, in which the coloring agent(s) β) are chosen from pigments, preferably from carbon blacks such as Black 2, iron oxides, in particular red, brown or black, and micas coated with iron oxide, triarylmethane pigments, in particular blue and violet, such as BLUE 1 LAKE, azo pigments, in particular red, such as D&C RED 7, alkali metal or alkaline-earth metal salts of lithol red such as lithol red calcium salt B, and mixtures thereof. Process according to any one of the preceding claims, in which the coloring agent(s) β) are included in the composition (A) . A method according to any preceding claim comprising:
▪ the application to the keratin fibers of a composition (C) comprising the metal salt(s) as defined in any one of Claims 1, 6 or 7; followed by
▪ the application to the keratin fibers of a composition (A) as defined in any one of claims 1, 3, 4, 8 or 10 to 20; followed by
▪ the application to the keratin fibers of a composition (B) as defined in any one of Claims 1, 5 or 21 to 23;
it being understood that the coloring 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 preferably in composition (A) . A method according to any of claims 1 to 25 comprising:
▪ the application to the keratin fibers of a composition (A) as defined in any one of claims 1, 3, 4, 8 or 10 to 20; followed by
▪ the application to the keratin fibers of a composition (B) as defined in any one of Claims 1, 5 or 21 to 23;
Being heard that :
- the metal salt(s) are included in composition (A) and/or in composition (B) , preferably in composition (A) ; And
- the coloring agent(s), preferably chosen from pigments, are included in composition (A) and/or in composition (B) , preferably in composition (A) . Kit or device with several separate compartments comprising:
▪ in a first compartment: composition (A) as defined in any one of claims 1, 3, 4, 8 or 10 to 20;
▪ in a second compartment separate from the first: composition (B) as defined in any one of claims 1, 5 or 21 to 23; And
▪ optionally in a third compartment separate from the other two: composition (C) as defined in claim 1 or 8; And
▪ optionally in a fourth compartment distinct 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 metal salt(s) as defined in any one of claims 1, 6 or 7; And
- at least one of the compositions of the kit comprises one or more coloring agent(s) as defined in claim 1 or 24. Composition (A0) comprising:
- the oily dispersion (A') as defined in any one of claims 10 to 18;
- one or more metal salt(s) as defined in claim 1, 6 or 7;
- optionally one or more coloring agent(s) as defined in claim 1 or 24.