FR3117856A1 - Cosmetic composition comprising a block copolymer based on acetoacetate functions - Google Patents

Abstract

Cosmetic composition comprising a block copolymer based on acetoacetate functions The present invention relates to a composition comprising at least one fatty phase containing at least one block copolymer comprising at least a first block having a glass transition temperature (Tg) greater than or equal to 40° C, and obtained from at least one monomer (A) of (alkyl)acrylate of formula (I); and at least one second block having a glass transition temperature (Tg) less than or equal to 20°C, and obtained from at least: (i) a monomer (B) of formula (II), (ii) a monomer (C) of (alkyl)acrylate of formula (III), and (iii) a monomer (D) chosen from ethylenically unsaturated monomers comprising at least one carboxylic, phosphoric and/or sulphonic acid function, maleic anhydride and its derivatives, and itaconic anhydride and its derivatives. Figure for abstract: None

Description

Cosmetic composition comprising a block copolymer based on acetoacetate functions

The present invention relates more particularly to the cosmetic field of keratin materials, and in particular to that of care and/or makeup for the skin and/or lips and/or eyelashes and/or eyebrows, and that of care, styling and/or coloring keratin fibers and preferably the hair. It thus aims to propose new compositions, in particular cosmetics, comprising a copolymer with acetoacetate units, which are quite particularly interesting with regard to their technical performance, in particular in terms of the resistance of the deposits which they make it possible to obtain, and the sensory feelings which they provide the user with corresponding treatment methods, in particular cosmetics.

Cosmetic products conventionally require the implementation of one or more film-forming polymers in order to obtain a quality deposit of these products on keratin materials, and in particular satisfying the expectations detailed below.

Thus, in the field of making up the skin and/or the lips, it is very particularly expected that the deposit formed does not transfer upon contact with the fingers or the clothing.

It must also have good resistance in contact with water, in particular rain or during the shower or even perspiration as well as sebum, even in contact with fatty substances in food, in particular edible oils when this deposit is formed on the lips. In addition, this deposit must be comfortable or even shiny.

To do this, it is used in make-up products such as mascaras, eyeliners, eye shadows or lipsticks, and more particularly in their organic and in particular oily phases, dispersions of polymer particles of nanometric size, as a film-forming agent.

Document WO 2013/103528 proposes copolymers, not organized in the particulate state, one of the monomers of which bears an acetoacetate function, in particular for hair applications. Documents WO 93/24098 and WO 95/06454 describe aqueous dispersions containing copolymers, one of the monomers of which bears an acetoacetate function, intended for application to the nails. As for the document WO 2014/098052, it proposes an acrylic resin emulsion for styling agents which has been stably dispersed by a poly(vinyl alcohol) resin. The compositions of these documents, however, exhibit unsatisfactory styling hold over time.

Furthermore, in the hair sector, a new range of products called hair make-up or “Hair Make-up” has recently been developed. These products guarantee temporary hair coloring that lasts after 1 to 3 shampoos. They therefore constitute a particularly attractive alternative for consumers, to permanent hair colour, provided of course that the color effect is effectively guaranteed to last in contact with water and a few shampoos. This imperative is also notably satisfied thanks to the implementation of effective film-forming agents. Thus, document FR 2 741 530 proposes for this purpose, for the temporary coloring of keratin fibers, the use of a dispersion of film-forming polymer particles 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 nevertheless have the disadvantage of being easily removed with shampoo.

It is also proposed in document 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 EP 1 392 222 to use a cosmetic composition for the care and/or treatment of keratin materials comprising a supramolecular polymer comprising a polymer backbone and at least two groups capable of forming at least three hydrogen bonds, and of patent EP 1 435 900 to use a hair composition comprising a supramolecular polymer comprising a polymeric backbone and at least two groups capable of forming at least three hydrogen bonds and a surfactant or a hair conditioning agent. However, with these two composition alternatives, the styling performance over time or in water obtained remains insufficient.

In general, the polymers described above do not allow access to deposits, both on the keratin fibers and on the skin and the lips, which satisfy all of the aforementioned requirements, namely a very good resistance to water, in particular to shampoos for the hair, and/or to fatty substances, in particular for the lips, the wearing of which is also comfortable for the users, which make it possible to adjust the qualities of shine or invisibility and which, in the case of capillary use, provide very satisfactory styling hold.

There therefore remains a need for cosmetic compositions intended for application to the skin which make it possible to obtain a non-sticky deposit which transfers little or not at all, which is shiny, comfortable and persistent.

There also remains a need for compositions which are resistant to water and to fatty substances, in particular to sebum.

There also remains a need for compositions making it possible to provide qualities of shine, invisibility and/or a volumizing effect.

There also remains a need for coloring cosmetic compositions intended for hair application which have good resistance to water and shampoos to guarantee color fastness over time comparable to direct coloring.

There is also also a need for cosmetic compositions, in particular non-coloring, intended for hair application which have styling properties, in particular holding curls, that are resistant to water.

The present invention aims precisely to meet all or part of these needs.

Thus, according to a first of its aspects, the present invention relates to a so-called “C1” composition, in particular cosmetic for keratin materials, and in particular for the care and/or makeup of the skin, lips, eyelashes and/or or the eyebrows and/or for the care, styling and/or coloring of keratin fibres, preferably the hair, comprising at least one fatty phase containing at least one block copolymer called “CP” comprising:
- at least one first block having a glass transition temperature (T _g ) greater than or equal to 40 ° C, and obtained from at least one monomer (A) of (alkyl) acrylate of formula (I):

in which :
• R ¹ represents hydrogen or a (C ₁ -C ₄ )alkyl group, linear or branched, preferably R ¹ represents a methyl group; And
• R ² represents a C ₄ to C ₁₂ cycloalkyl group; And
- at least one second sequence having a glass transition temperature (T _g ) less than or equal to 20°C, and obtained from at least:
(i) a monomer (B) of formula (II):

in which :
• R ^a represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, linear or branched, preferably R ^a represents a methyl group;
• R ^b and R ^c , identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group, linear or branched, preferably R ^b and R ^c represent a hydrogen atom;
• R ^d represents a (C ₁ -C ₄ )alkyl group, linear or branched, preferably R ^d represents a methyl group; And
• L represents a (C ₁ -C ₆ )alkylene group, linear or branched, or cycloalkylene, in particular L represents a (C ₁ -C ₄ )alkylene group, preferably L represents ethylene;
and preferably monomer (B) is acetoacetoxyethyl methacrylate;
(ii) an (alkyl)acrylate monomer (C) of formula (III):

in which :
• R ¹ represents a hydrogen atom or a radical (C ₁ -C ₄ )alkyl, linear or branched, preferably R ¹ represents a methyl group; And
• R ³ represents an unsubstituted (C ₁ -C ₄ )alkyl group, linear or branched, with the exception of the tert-butyl group, or a methoxyethyl group; And
(iii) a monomer (D) chosen from ethylenically unsaturated monomers comprising at least one carboxylic, phosphoric and/or sulphonic acid function, maleic anhydride and its derivatives, and itaconic anhydride and its derivatives.

To the knowledge of the inventors, obtaining a cosmetic composition from a copolymer comprising a first block obtained from at least one monomer (A) and a second block obtained from at least one monomer ( B), at least one monomer (C) and at least one monomer (D) according to the invention, and exhibiting glass transition temperatures (T _g ) as defined above, has never been described in the prior art.

According to another aspect, the present invention relates to a so-called "C2" composition, in particular cosmetic for keratin materials, and in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows and / or for the care, styling and / or coloring of keratin fibres, preferably the hair, comprising:
i) at least one fatty phase;
ii) at least one CP copolymer as defined above;
iii) at least one crosslinking agent called “R” as defined below.

Preferably, the present invention relates to a composition C2 comprising at least one crosslinking agent, called "R", and optionally at least one cosmetic active ingredient, called "AC", chosen from a) coloring agents chosen from pigments, direct dyes , and mixtures thereof, b) active ingredients for caring for keratin materials, preferably the skin, c) UV filters, and d) mixtures thereof.

According to yet another aspect, the present invention relates to a so-called “C3” composition, in particular cosmetic for keratin materials, and in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows and/or for the care, styling and/or coloring of keratin fibres, preferably the hair, comprising:
i) at least one fatty phase
ii) at least one CP copolymer as defined above;
iii) at least one crosslinking agent R as defined below,

at least one cosmetic active ingredient, called "AC", in particular chosen from a) coloring materials chosen from pigments, direct dyes, and mixtures thereof, b) active ingredients for the care of keratin materials, preferably the skin, c) UV filters and d) mixtures thereof.

Thus, preferably, the present invention also relates to a composition C3, comprising at least one cosmetic active ingredient, called "AC", chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b) active ingredients care for keratin materials, preferably the skin, c) UV filters, and d) mixtures thereof.

According to another of its aspects, the present invention relates to a particularly cosmetic process for keratin materials, and in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows and/or for the care, styling and/or coloring of keratin fibres, preferably the hair, comprising a step of applying to said keratin materials a C1, C2 or C3, preferably C2 or C3 composition according to the invention.

Thus, the inventors have found, surprisingly, that a CP copolymer in accordance with the invention makes it possible to obtain cosmetic compositions C1, C2 or C3, in particular C2 or C3, leading to deposits for making up the skin, lips, eyelashes and/or eyebrows exhibiting good resistance to external attacks such as, for example, water, oils, in particular food oils, sweat and/or sebum and therefore endowed with very good resistance over time. Advantageously, the deposits obtained with such compositions are also very comfortable.

The inventors have also found that a composition C1, C2 or C3 in accordance with the invention, in particular a composition C2 or C3, makes it possible to obtain a deposit that is more resistant to external attacks such as, for example, water, oils, in particular food oils, sweat and/or sebum and therefore has a very good hold over time.

The inventors have also observed that cosmetic compositions C1, C2 or C3, in particular C2 or C3, in accordance with the invention and more particularly intended for hair application, make it possible to obtain deposits having a very good resistance to shampoos and to 'water.

According to one of its aspects, the present invention relates to a particularly cosmetic process for keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows and/or for caring for, styling and/or coloring keratin fibers and preferably the hair, consisting in applying to said keratin materials a composition C1 according to the invention, optionally at least one crosslinking agent R, in particular according to the invention, and optionally at least one AC cosmetic active ingredient, said AC being chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b) active ingredients for caring for keratin materials, preferably the skin, c) filters UV, and d) mixtures thereof.

According to another of its aspects, the present invention relates to a process for making up the skin, in particular the lips, comprising a step of applying to said skin at least one composition C1, C2 or C3 according to the invention, and at least one dyestuff with in particular said method comprising at least the two successive steps consisting in applying sequentially to said skin i) at least one composition C1 according to the invention, and ii) a crosslinking agent R or a composition CR containing at least one crosslinking agent R in particular according to the invention, it being understood that said composition C1 and/or said composition CR contains at least one dyestuff or said method comprising at least the three successive steps consisting in applying sequentially to the skin i) a CAC composition containing at least one dyestuff, ii) a composition C1 according to the invention, and iii) a crosslinking agent R or a composition CR containing at least one crosslinking agent lant R in particular according to the invention with said composition C1 and/or said composition CR containing, where appropriate, at least one dyestuff.

According to another of its aspects, the present invention relates to a care process, in particular non-therapeutic and cosmetic, for the skin, in particular of the face or the lips, comprising a step of applying to said skin at least one composition C1, C2 or C3 according to the invention and at least one moisturizing cosmetic active; with in particular said method comprising at least the two successive steps consisting in applying sequentially to: said skin: i) a composition C1 according to the invention, and ii) a crosslinking agent R or a composition CR containing at least one crosslinking agent R in particular according to the invention; it being understood that said composition C1 and/or said composition CR contains at least one moisturizing cosmetic active ingredient, in particular glycerol, and optionally at least one coloring material or said method comprising at least the three successive steps consisting in applying sequentially to the skin i) a composition CAC, ii) a composition C1 according to the invention, and iii) a crosslinking agent R or a composition CR containing at least one crosslinking agent R in particular according to the invention with said composition CAC and/or composition C1 and/or composition CR containing at least one moisturizing cosmetic active ingredient in particular glycerol and optionally a coloring matter.

According to another of its aspects, the present invention relates to a process for styling keratin fibers, in particular human keratin fibers, in particular hair, comprising a step of applying to said keratin fibers a composition C1, C2 or C3 according to the invention.

According to yet another of its aspects, the present invention relates to a process for dyeing keratin fibers, preferably human keratin fibers such as the hair and the eyebrows, comprising a step of applying to said keratin fibers a composition C1, C2, or C3 according to the invention, and at least one coloring agent with in particular said method comprising at least the two successive steps consisting in applying sequentially to said fibers i) at least one composition C1 according to the invention, and ii) a crosslinking agent R or a composition CR containing at least one crosslinking agent R in particular according to the invention, it being understood that said composition C1 and/or said composition CR contains at least one dyestuff or said process comprising at least the three successive steps consisting in applying sequentially i) a composition CAC containing at least one dyestuff, ii) a composition C1 according to the invention and ii i) a crosslinking agent R or a composition CR containing at least one crosslinking agent R in particular according to the invention with said composition C1 and/or said composition CR containing, where appropriate, at least one dyestuff.

According to yet another of its aspects, the present invention also relates to a kit, in particular cosmetic, for keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows, and / or for the care, styling and / or coloring of keratin fibers and preferably the hair, comprising:
- a first compartment containing at least one composition C1 according to the invention, and preferably devoid of crosslinking agent R;
- a second compartment distinct from said first compartment and comprising at least one crosslinking agent R, in particular according to the invention; And
- where applicable, a third compartment distinct from the first and second compartments containing at least one cosmetic active ingredient, called “AC”, identical to or different from that/those possibly contained in the first and/or second compartments;
it being understood that the first and/or second compartments may also contain one or more identical or different AC cosmetic active agents and in that said AC active agent is chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof , b) active ingredients for caring for keratin materials, preferably the skin, c) UV filters, and d) mixtures thereof.

According to yet another of its aspects, the present invention also relates to a kit, in particular cosmetic, for keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows and/or the care, styling and/or coloring of keratin fibers and preferably the hair, comprising:
- a first compartment containing at least one fatty phase, at least one copolymer CP as defined above and preferably devoid of crosslinking agent R as defined below;
- A second compartment distinct from said first compartment, comprising at least one crosslinking agent, in particular a crosslinking agent R, in particular suitable for the present invention; And
- where appropriate, a third compartment, separate from the first and second compartments and containing at least one cosmetic active ingredient, called “AC”, identical to or different from that/those possibly contained in the first and/or second compartment(s) );
it being understood that the first and/or second compartments may also contain one or more identical or different AC cosmetic active ingredients, and that said AC active ingredient is chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b) active agents for caring for keratin materials, preferably the skin, c) UV filters and d) mixtures thereof.

By “keratin materials” within the meaning of the present invention, is meant in particular the lips, the skin, the nails and the keratin fibres, in particular the eyelashes, the eyebrows and the hair, preferably the lips and/or the hair.

A composition according to the invention is generally suitable for application to keratin materials, in particular application to the skin, lips and/or keratin fibres, and therefore generally comprises a physiologically acceptable medium, that is to say compatible with keratin materials, in particular an application to the skin, the lips and/or the keratin fibers, in particular the human keratin fibers such as the hair.

It is preferably a cosmetically acceptable medium, that is to say one that has a pleasant color, smell and feel and does not generate unacceptable discomfort, that is to say tingling, tightness , likely to divert the user from applying this composition.

Within the meaning of the present invention, the terms “dyeing material” and “dying agent” are equivalent.

detailed description

As specified above, a composition C1 according to the invention contains i) at least one fatty phase, and ii) at least one copolymer CP as defined previously.

CP copolymer

As mentioned above, a composition according to the invention contains at least one CP block copolymer comprising:
- at least one first block having a glass transition temperature (T _g ) greater than or equal to 40° C., and obtained from at least one monomer (A) of (alkyl)acrylate of formula (I) such that defined above; And
- at least one second sequence having a glass transition temperature (T _g ) less than or equal to 20°C, and obtained from at least:
(i) a monomer (B) of formula (II) as defined above;
and preferably monomer (B) is acetoacetoxyethyl methacrylate;
(ii) an (alkyl)acrylate monomer (C) of formula (III) as defined above; And
(iii) a monomer (D) chosen from ethylenically unsaturated monomers comprising at least one carboxylic, phosphoric and/or sulphonic acid function, maleic anhydride and its derivatives, and itaconic anhydride and its derivatives.

Within the meaning of the present invention, by “block copolymer”, is meant a copolymer consisting of a linear chain of blocks. A block is defined as a portion of the copolymer in which the monomeric units are structurally identical. In particular, it is understood a copolymer consisting of at least two distinct sequences of each of the monomers constituting the copolymer in the backbone of the copolymer. For example, the copolymer of the invention contains at least one block having a glass transition temperature (T _g ) greater than or equal to 40° C. and at least one block having a glass transition temperature (T _g ) less than or equal to 20°C, in the backbone of the copolymer.

Furthermore, the terms “first sequence” and “second sequence” in no way condition the order of said sequences in the structure of the copolymer.

According to the invention, the block copolymer can be an alternating or gradient copolymer.

Preferably, the copolymer is an alternating copolymer.

Within the meaning of the present invention, by “alternating copolymer”, is meant a copolymer in which the evolution of the monomers along the polymer chain is not systematic. For example, within a copolymer obtained from monomers M _i and M _j , within a sequence M _i , the concentration of monomers M _j is zero.

Thus, within the meaning of the present invention, by “gradient copolymer”, is meant a copolymer exhibiting a systematic evolution of the ratio of the various monomers throughout its polymer chain. This means that all the polymer chains have at least one monomer M _i for which, whatever the normalized position x on the polymer chain, there is a non-zero probability of finding this monomer M _i along the chain.

The glass transition temperatures of the first and second blocks as defined above can be theoretical glass transition temperatures determined from the theoretical glass transition temperatures of the constituent monomers of each of the blocks, which can be found in a manual reference such as the Polymer Handbook, 3rd ed, 1989, John Wiley, according to the following relationship, known as Fox's Law:

ω _i being the mass fraction of monomer i in the sequence considered and Tg _i being the glass transition temperature of the homopolymer of monomer i.

Unless otherwise indicated, the glass transition temperatures indicated for the first and second blocks according to the present invention are theoretical glass transition temperatures.

The difference between the glass transition temperatures of the first and second sequences is generally greater than 20°C, preferably greater than 40°C, and better still greater than 60°C.

According to a particular embodiment, the block copolymer included in a composition according to the invention comprises from 60% to 80% by weight of the first block and from 20% to 40% by weight of the second block, and preferably comprising 65% to 75% by weight of the first block and 25% to 35% by weight of the second block, based on its total weight.

According to another particular embodiment, the first and the second blocks of the copolymer are linked together by an intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block.

A composition C1 according to the invention may comprise from 1% to 60% by weight, preferably from 2% to 30% by weight of the block copolymer, relative to the total weight of the composition.

Preferably, the copolymer is a film-forming polymer.

The term "film-forming polymer" means a polymer capable of forming, on its own or in the presence of an auxiliary film-forming agent, a continuous and adherent film on a support, in particular on keratin materials.

Preferably, the polydispersity index of the copolymer included in a composition according to the invention is greater than 2.

The polydispersity index of the block copolymer is equal to the ratio of the weight-average mass (Mw) of the copolymer to its number-average mass (Mn).

The weight-average (Mw) and number-average (Mn) molar masses are determined by liquid chromatography by gel permeation using a refractometric detector, in tetrahydrofuran (THF) as solvent, from a calibration curve established with linear polystyrene standards.

Preferably, the weight-average mass (Mw) of the copolymer comprised in a composition according to the invention is less than or equal to 300,000 g.mol ⁻¹ .

Preferably, the weight-average mass (Mw) of the copolymer is between 35,000 and 200,000 g.mol ⁻¹ , and better still between 45,000 and 150,000 g.mol ⁻¹ .

Preferably, the number-average mass (Mn) of the copolymer is less than or equal to 70,000 g.mol ⁻¹ .

Preferably, the number-average mass (Mn) of the copolymer is between 10,000 and 60,000 g.mol ⁻¹ , and better still between 12,000 and 50,000 g.mol ⁻¹ .

Preferably, the copolymer has a polydispersity index greater than 2, for example ranging from 3 to 20, preferably greater than or equal to 4, for example ranging from 4 to 18.

First sequence

As mentioned above, the first block of a copolymer comprised in a composition according to the invention has a glass transition temperature (T _g ) greater than or equal to 40° C., and is obtained from at least one monomer (A) (alkyl)acrylate of formula (I) as defined above.

In a particular embodiment, the glass transition temperature (T _g ) of the first sequence ranges from 40°C to 150°C.

In a particular embodiment, the glass transition temperature (T _g ) of the first sequence is greater than or equal to 60°C, in particular, the glass transition temperature (T _g ) of the first sequence varies by 60°C at 150°C, more particularly varies from 60°C to 140°C, and preferably varies from 80°C to 120°C.

In a particular embodiment, the first sequence of a copolymer comprised in a composition according to the invention is obtained from:
a) at least one acrylate monomer (A1) of formula (V):

in which R ² represents a C ₄ to C ₁₂ cycloalkyl group, in particular R ² represents an (iso)bornyl group; And
b) at least one (alkyl)acrylate monomer (A2) of formula (VI):

in which R' ¹ represents a (C ₁ -C ₄ )alkyl group, linear or branched, preferably R' ¹ represents a methyl group and R ² represents a C ₄ to C ₁₂ cycloalkyl group.

Preferably, the first block is obtained exclusively from at least one monomer (A1) and at least one monomer (A2).

Preferably, the first block is obtained from isobornyl methacrylate and isobornyl acrylate.

Isobornyl acrylate is a compound with the molecular formula C ₁₃ H ₂₀ O ₂ , and with the condensed structural formula:

Mention may in particular be made, as isobornyl acrylate, of that marketed under the name Isobornyl acrylate by the company Sigma-Aldrich.

Isobornyl methacrylate is a compound with the molecular formula C ₁₄ H ₂₂ O ₂ , and the structural formula:

Mention may in particular be made, as isobornyl methacrylate, of that marketed under the name Isobornyl methacrylate by the company Sigma-Aldrich.

According to a preferred embodiment, the first block of a copolymer comprised in a composition according to the invention is obtained from monomers (A1) and (A2) as defined above, in a mass ratio (A1)/ (A2) varying from 30:70 to 70:30, in particular varying from 40:60 to 60:40, and preferably varying from 45:55 to 55:45.

The first block may also comprise at least one additional monomer chosen from linear or branched C ₈ -C ₂₂ alkyl (meth)acrylates.

In particular, the at least one additional monomer comprised in the first block is chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, behenyl acrylate, behenyl methacrylate, stearyl acrylate and stearyl methacrylate.

2-Ethylhexyl acrylate, also called 2-ethylhexyl prop-2-enoate, is a compound with the structural formula C ₁₁ H ₂₀ O ₂ , and with the condensed structural formula:

Mention may in particular be made, as 2-ethylhexyl acrylate, of that marketed under the name 2-Ethylhexyl acrylate by the company Sigma-Aldrich.

2-Ethylhexyl methacrylate, also called 2-ethylhexyl 2-methylprop-2-enoate, is a compound with the molecular formula C ₁₂ H ₂₂ O ₂ , and with the structural formula:

Mention may in particular be made, as 2-ethylhexyl methacrylate, of that marketed under the name 2-Ethylhexyl methacrylate by the company Sigma-Aldrich.

Lauryl acrylate, also called dodecyl acrylate, is a compound with the molecular formula C _{1 5} H _{2 8} O ₂ , and with the structural formula:

As lauryl acrylate, mention may in particular be made of that marketed under the name Lauryl acrylate by the Sigma-Aldrich company.

Lauryl methacrylate, also called dodecyl methacrylate, is a compound with the molecular formula C _{1 3} H _{2 4} O ₂ , and with the structural formula:

Mention may in particular be made, as lauryl methacrylate, of that marketed under the name Lauryl methacrylate by the Sigma-Aldrich Company.

Behenyl acrylate, also called docosyl acrylate, is a compound with the molecular formula C ₂₅ H ₄₈ O ₂ , and with the structural formula:

Mention may in particular be made, as behenyl acrylate, of that marketed under the name behenyl acrylate by the Sigma-Aldrich Company.

Behenyl methacrylate, also called docosyl methacrylate, is a compound with the structural formula C ₂₆ H ₅₀ O ₂ , and the structural formula:

Mention may in particular be made, as behenyl methacrylate, of that marketed under the name Behenyl Methacrylate 1822 F (BEMA 1822 F) by the company BASF.

Stearyl acrylate, also called octadecyl acrylate, is a compound with the molecular formula C ₂₁ H ₄₀ O ₂ , and with the structural formula:

Mention may in particular be made, as stearyl acrylate, of that marketed under the name Octadecyl acrylate by the company Sigma-Aldrich.

Stearyl methacrylate, also called octadecyl methacrylate, is a compound with the molecular formula C ₂₂ H ₄₂ O ₂ , and with the structural formula:

Mention may in particular be made, as stearyl methacrylate, of that marketed under the name Octadecyl methacrylate by the company Sigma-Aldrich.

The first block of a copolymer comprised in a composition according to the invention may contain from 0.1% to 15%, and in particular from 0.1% to 5% by weight of additional monomer as described above, for relative to the total weight of the monomers of the first block.

Preferably, the first block of a copolymer according to the invention represents from 60% to 80%, better still from 65% to 75% by weight, relative to the total weight of the copolymer CP.

In a particular embodiment, the first block represents from 60% to 80% by weight, preferably from 65% to 75% by weight, relative to the total weight of the copolymer CP.

Second sequence

As mentioned above, the second block of a copolymer included in a composition according to the invention has a glass transition temperature (T _g ) of less than or equal to 20° C., and obtained from at least:
(i) a monomer (B) of formula (II) as defined above;
(ii) an (alkyl)acrylate monomer (C) of formula (III) as defined above; And
(iii) a monomer (D) chosen from ethylenically unsaturated monomers comprising at least one carboxylic, phosphoric and/or sulphonic acid function, maleic anhydride and its derivatives, and itaconic anhydride and its derivatives.

Preferably, the second block of a copolymer according to the invention has a glass transition temperature (T _g ) ranging from -100°C to 20°C.

Preferably, the second block of a copolymer according to the invention has a glass transition temperature (T _g ) of less than or equal to 10°C, in particular ranging from -80°C to 15°C.

Preferably, the second block of a copolymer according to the invention has a glass transition temperature (T _g ) of less than or equal to 0°C, in particular ranging from -30°C to 0°C.

In a particular embodiment, the second block of a copolymer according to the invention has a glass transition temperature (T _g ) less than or equal to 10°C, in particular less than or equal to 0°C, preferably varying from -100°C to 0°C, and more preferably ranging from -30°C to 0°C.

Preferably, the monomer (B) is chosen from acetoacetoxyethyl acrylate, acetoacetoxyethyl methacrylate, and mixtures thereof.

Preferably, monomer (B) is acetoacetoxyethyl methacrylate.

Acetoacetoxyethyl acrylate is a compound with the molecular formula C ₉ H ₁₂ O ₅ , and with the condensed structural formula:

As acetoacetoxyethyl acrylate, mention may in particular be made of that marketed under the name Butanoic acid, 3-oxo-,2-[(1-oxo-2-propen-1-yl)oxy]ethyl ester by the company Alfa Chemistry.

Acetoacetoxyethyl methacrylate is a compound with the molecular formula C ₁₀ H ₁₄ O ₅ , and with the condensed structural formula:

Mention may in particular be made, as acetoacetoxyethyl methacrylate, of that marketed under the name Eastman ^TM AAEM by the Eastman Company.

Preferably, the ethylenically unsaturated monomer (D) comprises at least one carboxylic acid function.

In a particular embodiment, the ethylenically unsaturated monomer (D) is chosen from crotonic acid, itaconic acid, fumaric acid, maleic acid, styrenesulfonic acid, vinylbenzoic acid, vinylphosphoric acid, acrylic acid, methacrylic acid, acrylamiopropanesulfonic acid, acrylamidoglycolic acid, and their salts.

In a particular embodiment, the ethylenically unsaturated monomer (D) is chosen from maleic anhydride and its derivatives of formula (VII):

and itaconic anhydride and its derivatives of formula (VIII):

in which R _a , R _b and R _c , which are identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group, in particular R _a , R _b , and R _c represent a hydrogen atom ,
preferably, the monomer (D) is chosen from maleic anhydride and its derivatives of formula (VII), and more preferably the monomer (D) is maleic anhydride.

In a particular embodiment, the second block is obtained exclusively from at least one monomer (B), at least one monomer (C) and at least one monomer (D), as defined below. above.

In a preferred embodiment, the second block is obtained, preferably exclusively, from at least one monomer (B) as defined above, preferably from acetoacetoxyethyl methacrylate, from at least one monomer ( C) as defined above, preferably isobutyl acrylate and at least one monomer (D) as defined above, preferably acrylic acid.

In a particular embodiment, the monomers (B) and (C) as defined above are present in the second block of a copolymer according to the invention in a mass ratio (C)/(B) varying from 1 :1 to 10:1, in particular varying from 2:1 to 9:1, in particular varying from 3:1 to 8:1, and preferably varying from 4:1 to 7:1.

Preferably, the monomer (D) as defined above represents from 0% to 10% by weight, more preferably 5% by weight relative to the total weight of the monomers in a copolymer according to the invention.

In a preferred embodiment, the second block of a copolymer according to the invention is obtained from at least one acetoacetoxyethyl methacrylate monomer, from at least one isobutyl acrylate monomer and from at least one least one acrylic acid monomer.

The second block of a copolymer according to the invention may also comprise at least one additional silicone monomer of formula (IX):

in which :
- R ₈ represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, linear or branched, preferably R ₈ represents a methyl group;
- R ₉ represents a divalent hydrocarbon group, saturated or unsaturated, preferably saturated, linear or branched, having from 1 to 10 carbon atoms, and optionally containing one or two ether bonds -O-;
- R ₁₀ represents a linear or branched alkyl group having from 1 to 10 carbon atoms; And
- n represents an integer from 1 to 300;
and preferably the second block further comprises at least one additional silicone monomer chosen from monomethacryloyloxypropyl polydimethylsiloxanes.

Preferably, the at least one additional silicone monomer comprised in the second block of a copolymer according to the invention is chosen from polydimethylsiloxanes with a mono(meth)acryloyloxy terminal group.

Preferably, the at least one additional silicone monomer included in the second block of a copolymer according to the invention is chosen from monomethacryloyloxypropyl polydimethylsiloxanes.

Among the monomethacryloyloxypropyl polydimethylsiloxanes, mention may be made in particular of those marketed under the names MCR-M07, MCR-M17, MCR-M11, MCR-M22 by the company Gelest Inc as well as the silicone macromonomers marketed under the names X-22-2475, X-22-2426, X-22-174DX by Shin Etsu company.

In a particular embodiment, the second block of a copolymer according to the invention comprises from 0% to 15% by weight, and preferably from 0% to 5% by weight, of additional silicone monomers of formula (IX) such as defined above, relative to the total weight of the monomers.

In another embodiment, the second block of a copolymer according to the invention does not comprise any additional silicone monomer of formula (IX) as defined above.

In a particular embodiment, the second block represents from 20% to 40% by weight, preferably from 25% to 35% by weight, relative to the total weight of the copolymer according to the invention.

Preferably, the copolymer according to the invention comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in the first block and acetoacetoxyethyl methacrylate, isobutyl acrylate and acid acrylic in the second sequence.

In a particular embodiment, the copolymer according to the invention comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 30:70 to 70:30 in the first block and acetoacetoxyethyl methacrylate, isobutyl acrylate and acrylic acid monomers in the second block.

Preferably, the copolymer according to the invention comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 40:60 and 60:40 in the first block and methacrylate monomers of acetoacetoxyethyl, isobutyl acrylate and acrylic acid in the second block.

Preferably, the copolymer according to the invention comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 45:55 to 55:45 in the first sequence and isobornyl methacrylate monomers acetoacetoxyethyl, isobutyl acrylate and acrylic acid in the second block.

Preferably, the copolymer according to the invention comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 30:70 to 70:30 in the first sequence and isobornyl methacrylate monomers acetoacetoxyethyl, isobutyl acrylate and acrylic acid in the second block, the first block representing between 65% and 75% by weight, and in particular 70% by weight, relative to the total weight of the copolymer.

Preferably, the copolymer according to the invention comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 40:60 and 60:40 in the first block and methacrylate monomers of acetoacetoxyethyl, isobutyl acrylate and acrylic acid in the second block, the first block representing between 65% and 75% by weight, and in particular 70% by weight, relative to the total weight of the copolymer.

Preferably, the copolymer according to the invention comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 45:55 to 55:45 in the first sequence and isobornyl methacrylate monomers acetoacetoxyethyl, isobutyl acrylate and acrylic acid in the second block, the first block representing between 65% and 75% by weight, and in particular 70% by weight, relative to the total weight of the copolymer.

Preferably, the copolymer according to the invention comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 30:70 to 70:30 in the first sequence and isobornyl methacrylate monomers acetoacetoxyethyl, isobutyl acrylate and acrylic acid in the second block, the first block representing between 65% and 75% by weight, and in particular 70% by weight, relative to the total weight of the copolymer, and the methacrylate d acetoacetoxyethyl representing from 3% to 7% by weight, relative to the total weight of the copolymer.

Preferably, the copolymer according to the invention comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 40:60 and 60:40 in the first block and methacrylate monomers of acetoacetoxyethyl, isobutyl acrylate and acrylic acid in the second block, the first block representing between 65% and 75% by weight, and in particular 70% by weight, relative to the total weight of the copolymer, and the methacrylate d acetoacetoxyethyl representing from 3% to 7% by weight, relative to the total weight of the copolymer.

Preferably, the copolymer according to the invention comprises at least, or even consists of, isobornyl acrylate and isobornyl methacrylate monomers in a mass proportion ranging from 45:55 to 55:45 in the first sequence and isobornyl methacrylate monomers acetoacetoxyethyl, isobutyl acrylate and acrylic acid in the second block, the first block representing between 65% and 75% by weight, and in particular 70% by weight, relative to the total weight of the copolymer, and the methacrylate d acetoacetoxyethyl representing from 3% to 7% by weight, relative to the total weight of the copolymer.

Intermediate segment

The first and second sequences of a copolymer according to the invention as described above can be linked together by an intermediate segment comprising at least one constituent monomer of the first sequence and at least one constituent monomer of the second sequence.

Thus, by “intermediate segment” is meant within the meaning of the invention, a structural part of the chain of the copolymer, formed of monomers, and making it possible to connect the sequences of the copolymer.

Preferably, the intermediate segment comprising at least one constituent monomer of the first block and at least one constituent monomer of the second block of the polymer.

Preferably, the intermediate segment is a random copolymer.

Within the meaning of the present invention, by “random copolymer”, is meant a copolymer formed from macromolecules in which the sequential distribution of the monomer units obeys known statistical laws. In other words, in a random copolymer, the different monomers follow each other in any order. Statistical copolymers are also called random copolymers. For example, the sequence of a random copolymer, formed from monomers A and B, can be the following: A-A-B-A-B-B-B-B-A-A-B-A.

Preferably, the intermediate block is derived essentially from constituent monomers of the first block and of the second block.

“Essentially” means at least 85%, preferably at least 90%, better still 95% and even better still 100%.

Preferably, the intermediate block has a glass transition temperature (T _g ) between the glass transition temperatures of the first and second blocks as defined above.

Preparation of the copolymer

The copolymer CP included in a composition C1, C2 or C3 according to the invention can be prepared by mixing, in the same reactor, a polymerization solvent, an initiator, at least one monomer (A), of at least one monomer (B), of at least one monomer (C) and of at least one monomer (D), the monomers (A), (B), (C) and (D) being such that previously described, according to the following sequence of steps:
- part of the polymerization solvent and part of the initiator are poured into the reactor, and their mixture is heated to a polymerization temperature of between 60°C and 120°C,
- a first casting is then poured, containing the initiator and said at least one monomer (A) then left to react for a period T corresponding to a conversion rate of said monomers of 90% maximum,
- a second casting is then poured into the reactor, also containing the polymerization initiator as well as the monomer (B), the monomer (C) and the monomer (D), then left to react for a time T' at end of which the conversion rate of said monomers reaches a plateau,
- the reaction mixture is allowed to cool to room temperature.

By polymerization solvent is meant a solvent or a mixture of solvents. The polymerization solvent can be chosen in particular from ethyl acetate, butyl acetate, branched C ₈ -C ₁₆ alkanes such as C ₈ -C ₁₆ isoalkanes such as isododecane, isodecane , isohexadecane, and mixtures thereof.

Preferably, the polymerization solvent is isododecane.

Preferably, the polymerization temperature is from 85°C to 95°C.

Preferably, the polymerization temperature is 90°C.

Preferably, T' ranges from 3 to 6 hours.

In particular, the polymerization can be carried out in the presence of a radical initiator, in particular of the peroxide or azo type.

In particular, the radical initiator can be chosen from tert-Butyl peroxy-2-ethylhexanoate, such as Trigonox 21S marketed by AkzoNobel, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, such as as Trigonox 141 marketed by AkzoNobel, tert-butyl peroxypivalate, such as Trigonox 25C75 marketed by AkzoNobel, azobisisobutyronitrile (AIBN), 2,2′-azo-bis(2-amidinopropane) dihydrochloride (V50).

Preferably, the initiator is 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, such as Trigonox 141 marketed by AkzoNobel.

The monomers used in the context of this process, as well as their proportions, can be those described previously.

By way of non-limiting illustration of CP copolymers implemented according to the invention, mention may in particular be made of the copolymers comprising:
- a first sequence obtained by the copolymerization of isobornyl acrylate and isobornyl methacrylate in a mass ratio of 1/1, and
- a second sequence obtained by the copolymerization of isobutyl acrylate, acetoacetoxyethyl methacrylate and acrylic acid in an isobutyl acrylate/acetoacetoxyethyl methacrylate/acrylic acid mass ratio of 60/15/15,
wherein the first sequence/second sequence mass ratio is 70/30.

Cosmetic compositions according to the invention

As stated above, the present invention further relates to a composition, in particular cosmetic, for keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows and/or for the care, styling and/or coloring of keratin fibers and preferably the hair, comprising a CP copolymer as defined above.

As specified above, this composition according to the invention can in particular be presented in the variants of compositions called C1, C2 and C3.

Thus, a composition C1 may comprise, in addition to a fatty phase and a CP copolymer in accordance with the invention, at least one cosmetic active ingredient called "AC", chosen from a) coloring agents chosen from pigments, direct dyes, and their mixtures, b) active agents for caring for keratin materials, preferably the skin, c) UV filters and d) mixtures thereof.

According to a particular form of the invention, a composition C1 consists of a fatty phase and a CP copolymer in accordance with the invention, optionally at least one so-called “AC” cosmetic active ingredient chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b) active agents for caring for keratin materials, preferably the skin, c) UV filters and d) mixtures thereof and optionally at least one cosmetically acceptable compound other than an AC cosmetic active agent.

A composition C2 comprises, in addition to a fatty phase and a copolymer CP in accordance with the invention, at least one crosslinking agent called "R" as defined below, and optionally at least cosmetic active agent AC.

According to a particular form of the invention, a composition C2 is devoid of cosmetic active ingredient called “AC” in particular as defined below.

According to another particular form of the invention, a composition C2 consists of a fatty phase and a copolymer CP in accordance with the invention, at least one crosslinking agent, called "R" as defined below and optionally a cosmetically acceptable compound different from an AC cosmetic active ingredient.

A composition C3 comprises, in addition to a fatty phase and a copolymer CP in accordance with the invention, at least one crosslinking agent, called “R” as defined below, and at least one cosmetic active agent AC.

Cross-linking agent

Within the meaning of the invention, the term "crosslinking agent", also called "R", denotes a compound capable of establishing at least one covalent bond with an acetoacetate function of the (co)polymer CP contained in a composition according to the invention and thus to crosslink this (co)polymer.

Within the meaning of the present invention, it is understood that the terms “crosslinking agent” and “crosslinking agent” are equivalent.

In a particular embodiment, a composition according to the invention is devoid of such a crosslinking agent R.

Thus, a composition C1 as described above comprises a copolymer CP and a fatty phase in accordance with the invention and is devoid of crosslinking agent R.

In another particular embodiment, compositions according to the invention such as compositions C2 and C3 are obtained by mixing a composition C1 with at least one crosslinking agent R or a composition containing such a crosslinking agent and called “CR” composition.

As emerges from the above, a CR composition contains at least one crosslinking agent. In particular, a CR composition does not contain a CP copolymer. A CR composition can, on the other hand, comprise a fatty phase, an aqueous phase or can be in the form of a direct or inverse emulsion. A CR composition can also comprise a so-called “AC” cosmetic active ingredient, chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b) active ingredients for caring for keratin materials, preferably the skin, c) UV screening agents and d) mixtures thereof and in particular at least one coloring agent, more particularly at least one pigment.

More particularly, a composition C3 can be obtained either:
- by mixing a composition C1 with at least one crosslinking agent R or a composition containing such a crosslinking agent and called CR, and at least one cosmetic active ingredient AC, said AC being considered via a separate composition called "CAC", and/or via composition C1 and/or CR, or
- by mixing a composition C2 with at least one cosmetic active ingredient AC or a composition CAC, distinct from C2, containing said one cosmetic active ingredient AC.

As regards a CAC composition, it contains at least one cosmetic active ingredient chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b) active ingredients for caring for keratin materials, preferably the skin , c) UV filters and d) mixtures thereof. In particular, a CAC composition does not contain a CP copolymer. A CAC composition also does not contain crosslinking agent R. A CAC composition can, on the other hand, comprise a fatty phase, an aqueous phase or can be in the form of a direct or inverse emulsion.

According to another particular embodiment, a composition C3 can be obtained by mixing a composition C1 according to the invention with a composition CR comprising at least one crosslinking agent R, said composition C1 and/or CR possibly each additionally containing at least one AC cosmetic active ingredient.

When a composition according to the invention contains at least one crosslinking agent, said crosslinking agent and said CP copolymer are preferably present in a mass ratio ranging from 5 to 40%.

More specifically, a crosslinking agent R suitable for the invention can be chosen from compounds containing amine, thiol, alcohol, acrylate and/or carbonyl functions such as ketone and/or aldehyde functions, or a mixture thereof.

Thus, according to a particular embodiment, the crosslinking agent R is chosen from (poly)amino, (poly)thiolated and/or (poly)hydroxylated, (poly)carbonylated, (poly)acrylates and mixtures thereof, and preferably chosen from (poly)amino and (poly)thiolated compounds and in particular as detailed below.

By (poly)amino, (poly)thiolated and/or (poly)hydroxylated, (poly)carbonyl and (poly)acrylate compounds is meant the compounds comprising respectively at least one amine, thiol and/or hydroxyl, carbonyl function such a ketone or aldehyde or acrylate function.

(Poly)amine crosslinking agents

According to a preferred embodiment, the crosslinking agent R is chosen from (poly)amino compounds.

The (poly)amino compound can in particular be chosen from polyamino compounds having several primary amine and/or secondary amine groups or even from amino alkoxysilanes, and more particularly from amino alkoxysilane compounds, diamino compounds, triamino compounds, and their mixtures.

The (poly)amine compound can be a compound comprising from 2 to 20 carbon atoms, in particular a non-polymeric compound.

By "non-polymeric compound" is meant a compound which is not directly obtained by a polymerization reaction of monomers.

As (poly)amino 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, and spermidine.

The amino compound can also be chosen from amino alkoxysilanes, such as those of formula R′ ₁ Si(OR′ ₂ )z(R′ ₃ )x in which:
- R' ₁ is a C ₁ -C ₆ hydrocarbon chain, linear or branched, saturated or unsaturated, cyclic or acyclic substituted by a group chosen from amine groups NH ₂ or NHR with R representing a C ₁ -C ₄ alkyl , an aryl or an aryloxy substituted by an amino group or by a C ₁ -C ₄ aminoalkyl group; R' ₁ can be interrupted in its chain by a heteroatom (O, S, NH) or a carbonyl group (CO), R' ₁ being linked to the silicon atom directly via a carbon atom,
- R' ₂ and R' ₃ , identical or different, represent an alkyl group, linear or branched, comprising from 1 to 6 carbon atoms,
- z denotes an integer ranging from 1 to 3, and
- x denotes an integer ranging from 0 to 2,
with z + x = 3.

In particular, R' ₁ is an acyclic chain. Preferably, R' ₁ is a C ₁ -C ₆ hydrocarbon chain, linear or branched, saturated or unsaturated, substituted by an amine group NH ₂ or NHR, with R representing a C ₁ -C ₆ alkyl, a cycloalkyl in C ₃ -C ₆ or C ₆ aromatic. More preferably, R′ ₁ is a saturated linear C ₁ -C ₆ hydrocarbon chain substituted by an NH ₂ amine group. Even more preferentially, R′ ₁ is a saturated linear C ₂ -C ₄ hydrocarbon chain substituted by an NH ₂ amine group.

In particular, R′ ₂ represents an alkyl group comprising from 1 to 4 carbon atoms, preferably R′ ₂ represents a linear alkyl group comprising from 1 to 4 carbon atoms, and more preferably R′ ₂ represents the ethyl group.

In particular, R' ₃ represents an alkyl group comprising from 1 to 4 carbon atoms, preferably R' ₃ represents a linear alkyl group comprising from 1 to 4 carbon atoms, and more preferably R' ₃ represents the methyl group or ethyl.

Preferably, z is equal to 3.

According to a particular embodiment, the amino alkoxysilane is chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3 -(m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane and N-(2-aminoethylaminomethyl)phenethyltrimethoxysilane.

Preferably, the amino alkoxysilane is chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and more preferably amino alkoxysilane is 3-aminopropyl triethoxysilane (APTES).

According to a preferred embodiment, the (poly)amino compound is chosen from 3-aminopropyltriethoxysilane (APTES), 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, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine and lysine.

Preferably, the (poly)amine compound is chosen from ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 3-aminopropyltriethoxysilane (APTES), and more preferably, the (poly)amine compound is ethylenediamine or 3-aminopropyltriethoxysilane (APTES).

The (poly)amino compound can also be chosen from amino polymers, in particular having a weight-average molecular weight ranging from 500 g.mol^{- 1}at 1000000 g.mol^-1, preferably ranging from 500 g.mol^-1 at 500000 g.mol^-1, and preferably ranging from 500 g.mol^-1at 100000 g.mol^-1.

As amino polymer, mention may in particular be made of poly(alkylene (C ₂ -C ₅ ) imines), and preferably polyethyleneimines and polypropyleneimines, in particular poly(ethylene imines), in particular that sold under the reference 46,852-3 by Aldrich Chemical; poly(allylamine), in particular that sold under the reference 47,913-6 by the company Aldrich Chemical; polyvinylamines and their copolymers in particular with vinylamides, in particular vinylamine/vinylformamide copolymers such as those marketed under the name ^Lupamin® 9030 by the company BASF; polyamino acids having NH ₂ groups such as for example polylysine, in particular that sold by the company JNC Corporation (formerly Chisso); amino dextran, in particular that sold by the company CarboMer Inc; polyvinyl amino alcohol, in particular that sold by the company CarboMer Inc, copolymers based on acrylamidopropylamine; chitosans such as for example poly(D-Glucosamine) sold under the reference Kionutrime ^CSG® by the company Kytozyme; polydimethylsiloxanes comprising primary amine groups at the end of the chain or on the side chains, for example terminal or side aminopropyl groups, such as for example those of formula (X) or (XI) or (XII):

in which the value of n is such that the weight-average molecular weight of the polydimethylsiloxane ranges from 500 g.mol ^-1 to 55,000 g.mol ^-1 . As examples of compounds of formula (X), mention may be made of those sold under the names “DMS-A11”, “DMS-A12”, “DMS-A15”, “DMS-A21”, “DMS-A31”, “DMS -A32” and “DMS-A35” by the company Gelest.

in which the ^{values of n and m are such that the weight-average molecular weight of the polydimethylsiloxane ranges from 1000 g.mol -1 to} 55000 g.mol ^-1 . As examples of polydimethylsiloxanes of formula (XI), mention may be made of those sold under the names “AMS-132”, “AMS-152”, “AMS-162”, “AMS-163”, “AMS-191” and “AMS -1203” by the company Gelest.

in which the value of n is such that the weight-average molecular weight of the polydimethylsiloxane ranges from 500 to 3000 g.mol ⁻¹ . As examples of polydimethylsiloxanes (XII), mention may be made of those sold under the names “MCR-A11” and “MCR-A12” by the company Gelest.

As amino polymer, the amodimethicones of formula (XIII) may also be mentioned:

in which R, R' and R'', which are identical or different, each represent a hydroxyl or C ₁ -C ₄ alkyl group; A represents a C ₃ alkylene group, and m and n are such that ^{the weight-average molecular mass of the compound of formula (XIII) ranges from 5000 g.mol -1 to} 500000 g.mol ^-1 .

As amino polymer, mention may also be made of 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 for example those sold under the names Jeffamine D-230, D-400, D-2000, D-4000, ED-600 , ED-9000, ED-2003.

As amino polymer, mention may also be made of polytetrahydrofuran (or polytetramethylene glycol) α, ω-diamine, polybutadienes α, ω-diamine and polyamidoamine dendrimers (PAMAM) with terminal amine functions.

As amino polymer, mention may also be made of poly(meth)acrylates or poly(meth)acrylamides carrying lateral primary or secondary amine functions, such as poly(3-aminopropyl)methacrylamide, poly(2-aminoethyl) methacrylate.

As amino polymer, chitosans and polydimethylsiloxanes comprising primary amine groups at the end of the chain or on the side chains are preferably used.

Preferably, the polyamino compounds are chosen from chitosans and polydimethylsiloxanes comprising primary amine groups at the end of the chain or on the side chains, and APTES.

Thus, according to a preferred embodiment, a composition C2 or C3 according to the invention comprises a crosslinking agent R chosen from (poly)amino compounds, in particular chosen from chitosans, aminoalkoxysilanes, polydimethylsiloxanes comprising primary amine groups in chain end or on side chains, amodimethicones, polyglucosamines, and mixtures thereof.

More preferably, a C2 or C3 composition according to the invention comprises a crosslinking agent R chosen from chitosans, aminoalkoxysilanes and polydimethylsiloxanes comprising primary amine groups at the end of the chain or on the side chains, and even more preferably chosen from poly (D-Glucosamine), 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N - (2-aminoethyl)-3-aminopropyltriethoxysilane, and polydimethylsiloxanes comprising at the end of the chain groups aminopropyl terminals, and even more preferably is 3-aminopropyl triethoxysilane (APTES).

Cross-linking agents (poly)thiolated and/or (poly)hydroxylated

According to a preferred embodiment, the crosslinking agent is chosen from (poly)thiolated and/or (poly)hydroxylated compounds.

The (poly)thiolated and/or (poly)hydroxylated compound may in particular be organic or inorganic, preferably organic.

The (poly)thiolated and/or (poly)hydroxylated compound of the invention is chosen from fat-soluble or non-lipid-soluble compounds, preferably the (poly)thiolated and/or (poly)hydroxylated compound is fat-soluble.

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

In a preferred embodiment, the (poly)thiolated and/or (poly)hydroxylated compound is silicone, that is to say it comprises one or more hydroxy groups, or one or more thiol groups or one or more hydroxy groups and one or more thiol groups, it also comprises at least one siloxane chain.

In a particular embodiment, the (poly)thiolated and/or (poly)hydroxylated compound is inorganic. Mention may be made, for example, of polythiol silicones and polythiol silicas.

The (poly)thiolated and/or (poly)hydroxylated compound used in a composition according to the invention may in particular be chosen from nonpolymeric (poly)thiolated and/or (poly)hydroxylated compounds.

By “non-polymeric” compounds, within the meaning of the present invention, is meant compounds which are not directly obtained by a polymerization reaction of monomers.

According to one embodiment of the invention, the (poly)thiolated and/or (poly)hydroxylated compound is organic, non-polymeric and of formula (XIV) below as well as its solvates such as its hydrates:

in which :
- p and q, identical or different, represent an integer, it being understood that the sum p + q is greater than or equal to 2, preferably the sum p + q is inclusively between 2 and 10, preferably between 2 and 5;
- L denotes a multivalent (at least divalent) group, in particular comprising between 1 and 500 carbon and/or silicon atoms, more particularly between 2 and 40 carbon and/or silicon atoms, even more particularly between 3 and 30 carbon and/or silicon atoms, preferably between 6 and 20 carbon atoms, linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated;
L being optionally interrupted and/or terminated by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their associations such as –O-, –O-C(X)-, -N(R )-C(X)-, -Si(R_vs)(R_d)-O- with R representing a hydrogen atom or a group (C₁-VS₆) alkyl such as methyl; and or
L being 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' and X'', identical or different, represent an oxygen or sulfur atom, or an N(R_b);
- a, and b being 0 or 1, preferably the sum of a+b is 1;
-R_Toand R_b, identical or different, represent a hydrogen atom, or a group (C₁-VS₆)alkyl, or aryl(C₁-VS₄)alkyl such as benzyl, preferably R_Toand R_brepresent a hydrogen atom;
-R_vsand R_d, identical or different, represent a group (C₁-VS₆)alkyl, aryl(C₁-VS₄)alkyl or (C₁-VS₆)alkoxy.

According to one embodiment of the invention, in formula (XIV) above, q is equal to 0 and p is an integer greater than or equal to 2, preferably p is an integer comprised from 2 to 10, preferably from 2 to 5.

According to a particular embodiment of the invention, the (poly)thiolated and/or (poly)hydroxylated compound is chosen from polyhydroxylated compounds. In particular, polyhydroxylated compounds comprising from 2 to 20 carbon atoms, in particular nonpolymeric polyhydroxylated compound(s).

The (poly)thiolated and/or (poly)hydroxylated compound used according to the invention may be chosen from hydroxyalkoxysiloxane or thioalkoxysiloxane compounds, it being understood that these compounds may also comprise one or more primary or secondary amine groups.

A polyhydroxy compound used according to the invention is an organic compound comprising at least 2 hydroxy functions. This compound may include other non-reactive chemical functions such as esters, amides, ketones, urethanes. It is possible to use a mixture of distinct polyhydroxy compounds.

According to another variant, the polyhydroxy compound used according to the invention is an inorganic compound comprising at least 2 hydroxy functions. This compound may 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).

According to another embodiment, the thiolated and/or hydroxylated compound is chosen from polyhydroxylated, polythiolated, and polymeric polyhydroxylated and polythiolated compounds.

According to one embodiment of the invention, the polyhydroxylated compound is a non-polymeric organic compound of formula (XIVa) below:

in which :
- p denotes an integer greater than or equal to 2, preferably comprised inclusively between 2 and 10, preferably between 2 and 5;
- L is as defined above, preferably L denotes a multivalent (at least divalent) radical comprising between 8 and 30 carbon and/or silicon atoms, preferably between 10 and 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.

The polyhydroxy compound is preferably a diol compound.

Preferably, L denotes a multivalent C ₈ -C ₁₈ radical, in particular linear.

Preferably, the polyhydroxylated compound is a fat-soluble polyol, in particular a C ₈ -C ₁₈ diol, in particular linear. Advantageously, the C ₈ -C ₁₈ chain is a hydrocarbon chain, that is to say formed from carbon and hydrogen.

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

As polyol of formula (XIVa), 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.

According to a particular embodiment of the invention, the thiolated and/or hydroxylated compound is chosen from polythiolated compounds also called “ polymercapto ”.

The polythiolated compounds used according to the invention can be water-soluble or fat-soluble, preferably they are fat-soluble.

According to a particular embodiment of the invention, the thiolated and/or hydroxylated compound is chosen from polythiolated compounds, in particular polythiolated compounds comprising from 2 to 20 carbon atoms.

According to a preferred embodiment, the thiolated and/or hydroxylated compound is thiolated, non-polymeric and of formula (XIV) defined above, in which p is 0 and q is an integer greater than or equal to 2, preferably p is an integer comprised inclusively between 2 and 10, preferably between 2 and 5.

In particular, a polythiolated compound suitable for the invention is a non-polymeric organic compound of formula (XIVb):

in which L is as defined in formula (XIVa) above and q represents an integer greater than or equal to 2, preferably comprised inclusively between 2 and 10, preferably between 2 and 5.

The polythiolated compounds suitable for the invention are preferably dithiol compounds.

Preferably, L denotes a multivalent C ₈ -C ₁₈ radical, in particular linear. Preferably, the fat-soluble polythiol is a C ₈ -C ₁₈ dithiol, in particular linear. Advantageously, the C ₈ -C ₁₈ chain is a hydrocarbon chain, that is to say formed from carbon and hydrogen. In particular, the liposoluble polythiol is a linear C ₈ -C ₁₆ , in particular C ₁₀ -C ₁₄ , diol.

As polyol of formula (XIVb), 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 another embodiment of the invention, the thiolated and/or hydroxylated compound is thiolated and hydroxylated, nonpolymeric and of formula (XIV) as defined above, in which q and p are integers greater than or equal to 1, preferably the sum p+q is an integer comprised from 2 to 10, preferably from 2 to 5, and preferably q>p.

According to yet another particular embodiment of the invention, the thiolated and/or hydroxylated compound is chosen from (poly)hydroxylated and (poly)thiolated compounds, in particular (poly)hydroxylated and (poly)thiolated compounds comprising 2 to 20 carbon atoms, and in particular non-polymeric (poly)hydroxylated and (poly)thiolated compounds.

According to another particular embodiment of the invention, the thiolated and/or hydroxylated compound is chosen from hydroxylated and/or thiolated alkoxysiloxanes, such as those of formula (XV) below:

in which :
● R' ₁ is a C ₁ -C ₁₂ hydrocarbon chain, linear or branched, saturated or unsaturated, cyclic or acyclic, substituted by one or more groups chosen from the groups:
- hydroxy or thiol, preferably thiol,
- aryl, aryloxy, arylthio, arylamino, the aryl group being substituted by one or more hydroxy, thiol, hydroxy(C ₁ -C ₆ )alkyl or thiol(C ₁ -C ₆ )alkyl groups, preferably thiol(C ₁ - C ₆ )alkyl, and
- R' ₁ is optionally interrupted in its hydrocarbon chain by one or more heteroatoms such as O, S, N, a carbonyl group (CO), or their combination such as ester –C(O)-O-, or amide –C (O)-N(H)-, R' ₁ being bonded to the silicon atom directly via a carbon atom,
● R' ₂ and R' ₃ , identical or different, represent an alkyl group, linear or branched, comprising from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atom(s) such as methyl,
● z denotes an integer ranging from 1 to 3, and
● x denotes an integer ranging from 0 to 2, with z + x =3.

Preferably, R′ ₂ represents an alkyl group comprising from 1 to 4 carbon atoms.

Preferably, R′ ₂ represents a linear alkyl group comprising from 1 to 4 carbon atoms.

Preferably, R′ ₂ represents the ethyl group.

Preferably, R′ ₃ represents an alkyl group comprising from 1 to 4 carbon atoms.

Preferably, R′ ₃ represents a linear alkyl group comprising from 1 to 4 carbon atoms.

Preferably, R′ ₃ represents the methyl or ethyl group.

Preferably, R′ ₁ is an acyclic chain.

Preferably, R' ₁ is a C ₁ -C ₆ hydrocarbon chain, linear or branched, saturated or unsaturated, substituted by one or more hydroxy or thiol groups, preferably thiol.

Preferably, R′ ₁ is a saturated linear C ₁ -C ₆ hydrocarbon-based chain substituted by a hydroxy or thiol group, preferably thiol.

More preferentially, R′ ₁ is a saturated linear C ₂ -C ₄ hydrocarbon chain substituted by a hydroxy or thiol group, preferably thiol.

Preferably, R' ₁ is a saturated linear C ₁ -C ₆ hydrocarbon chain substituted by a hydroxy or thiol group, preferably thiol, R' ₂ represents an alkyl group comprising from 1 to 4 carbon atoms, R' ₃ represents an alkyl group comprising from 1 to 4 carbon atoms.

Preferably z is equal to 3.

According to an even more particular embodiment of the invention, the alkoxysiloxanes (XV) are chosen from those of the following formula (XV'):

in which :
● p is 0 or 1;
● X represents an oxygen or sulfur atom, preferably sulfur;
● R ¹ represents a (C ₁ -C ₆ )alkyl radical;
● R ² and R ³ , identical or different, preferably identical, are chosen from:
- a (C ₁ -C ₆ )alkoxy group, in particular C ₁ -C ₄ ;
- a (C ₁ -C ₆ )alkyl group;
● R ⁴ represents a hydrogen atom, or a (C ₁ -C ₆ )alkyl group such as methyl;
● L ¹ represents a divalent, saturated, C ₁ -C ₂₀ linear or branched hydrocarbon radical.

According to an even more specific embodiment of the invention, the alkoxysiloxanes (XV) are chosen from those of the following formula (XV''):

in which :
● q is 0 or 1;
● X represents an oxygen or sulfur atom, preferably sulfur;
● R′ ¹ denotes a (C ₁ -C ₆ )alkyl radical;
● R′ ² and R′ ³ , identical or different, preferably identical, are chosen from:
- a (C ₁ -C ₆ )alkoxy group, in particular C ₁ -C ₄ ;
- a (C ₁ -C ₆ )alkyl radical;
● R ⁵ represents a hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted by an amino, thiol or hydroxy group;
● R ⁴ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, in particular methyl;
● L ² represents a divalent hydrocarbon-based, linear or branched saturated C ₁ -C ₂₀ group, optionally interrupted by a heteroatom such as –NH-, optionally substituted by one or more hydroxy, thiol or amino groups.

Preferably, the alkoxysilane of formula (XV) is chosen from 4-(trimethoxysilyl)-1-butanol, 3-(trimethoxysilyl)-1-propanol, 3-(triethoxysilyl)-1-propanol, 11- (trimethoxysilyl)-1-undecanethiol, 4-(trimethoxysilyl)-2-butanethiol, 2-(triethoxysilyl)-ethanethiol, 3-(triethoxysilyl)-1-propanethiol, 2-(trimethoxysilyl)-ethanethiol, 3 -(trimethoxysilyl)-1-propanethiol and 3-(dimethoxymethylsilyl)-1-propanethiol.

More preferably, the alkoxysilane of formula (XV) is chosen from 2-(triethoxysilyl)-ethanethiol (18236-15-2) and 3-(triethoxysilyl)-1-propanethiol (14814-09-6).

According to another embodiment, the thiol compound is a particle carrying at least two thiol groups. It is for example a silica functionalized by radicals, in particular of the alkyl type, substituted by thiol functions.

According to this embodiment, the thiolated compound can designate the particles marketed under the name ^SiliaMetS® Thiol by the company Silicycle or under the name SP-THIO-SILICA by the company Suprasciences.

The thiolated compound can be chosen from polythiol silicas prepared according to the procedure described in. J. Mater. Chem., 2007, 17, 3726-3732; J. Am. Chem. Soc., 2005, 127 (23), pp 8492–8498; 10.1109/ICBBE.2010.5517542; Chemical Engineering Journal, 2011, 171 (3), 1004-1011; Minerals Engineering, 2012, 35, 20-26; Colloids and Surfaces A: Physicochemical and Engineering Aspects, 380, (1–3), 229-233), Advanced Science, Engineering and Medicine, Volume 5, Number 9, September 2013, pp. 984-987(4).

The particle bearing at least two thiol groups can also be obtained by reacting a silica particle such as the ^Sunsphere® particles marketed by Asahi Glass with mercapto alkylalkoxysilanes such as 3-mercaptopropyltriethoxysilane.

Preferably, the thiolated compound is a particle carrying at least two thiol groups obtained by reacting a Sunsphere ^® silica particle marketed by Asahi Glass, preferably a 5 μm Sunsphere particle with 3-mercaptopropyltriethoxysilane according to the publication, Journal of Chromatography A, Volume 1217, Issue 47, 19 November 2010, Pages 7448–7454.

According to a second embodiment, the polythiolated particles can be present in the form of latex carrying thiol groups such as those described in Colloids and Surfaces A: Physiochemical and Engineering Aspects 153, 1999, 421-427.

According to another embodiment, the thiolated compound is a particle coated with compound(s) bearing at least two thiol functions.

The (poly)thiolated and/or (poly)hydroxylated compound used in a composition according to the invention may in particular be chosen from polymeric (poly)thiolated and/or (poly)hydroxylated compounds.

The polymeric (poly)thiol and/or (poly)hydroxyl compounds can be homopolymers, copolymers, star, combe, brush and dendritics with hydroxy and/or thiol units. Polymers can be of natural origin such as polysaccharides, polypeptides, or synthetic such as acrylics, polyesters, polyglycols. The hydroxy and thiol units can be present as terminal or pendent groups.

Examples include the polymers described in the following scientific 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; EP 1 247 515 A2; US 3,676,440; and EP 1,572,778.

The thiolated and/or hydroxylated polymers which may be suitable for the invention are preferably organic or silicone, more preferably of formula (XVI):

in which :
● p and q, identical or different, represent an integer, it being understood that the sum p + q is greater than or equal to 3;
● 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- and -(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 of 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, the thiolated and/or hydroxylated compound is chosen from (poly)hydroxylated polymers also called “ polyol ”.

According to another embodiment of the invention, the (poly)hydroxylated polymer(s) are chosen from those of formula (XVI′):

in which :
● p denotes an integer greater than or equal to 2, and
● POLY denotes a carbon 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 (XVI′), is generally between 500 and 400,000 g.mol ⁻¹ , preferably between 500 and 150,000 g.mol ⁻¹ .

Preferably, the (poly)hydroxylated polymers (XVI′) can be polymer (di)ols, in particular polyolefin (poly)ols, polydi(C ₁ -C ₆ )alkylsiloxane (poly)ols, polyesters (poly) ols, more 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 weight (Mn) of less than 7000 g.mol ^-1 , preferably between 1000 and 5000 g.mol ^-1 . 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.

More particularly, the compounds of formula (XVI') are chosen from the polyolefins (poly)ols of formula (XVII) below:

in which :
• ALK4 and ALK5, 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 ALK4 represents a group ( linear C ₁ -C ₆ alkylene such as n-butylene, and ALK5 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 a hydroxy or thiol group, more preferably hydroxy; And
• n and m, identical or different, represent an integer, with n + m representing an integer greater than or equal to 1.

The (poly)ols of formula (XVII) can in particular be chosen from polyolefins with hydroxy ends.

Among the polyolefins with hydroxy ends, 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 (XVII'):

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

The (poly)ols of formula (XVII) may in particular be chosen from polydialkylsiloxane (di)ols, particularly from those of formula (XVIII) below:

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, (C ₁ -C ₆ )alkoxy groups 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 than 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 is between 500 and 55,000 g.mol ^-1 ; particularly n is an integer comprised from 1 to 100, preferably comprised from 5 to 50, and preferentially comprised 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 group (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-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 polydialkylsiloxane (di)ols of formula (XVIII) are chosen from polydimethylsiloxanes, in particular the polydiols of formula (XVIII') below:

in which :
● L ⁴ and L ⁵ are as defined previously, preferably represent a divalent group chosen from –R ₂ –, –O–R ₂ –, –R ₂ –O–, –R ₂ –O–R' ₂ –, preferably –R ₂ –O–R' ₂ –, with R ₂ and R' ₂ , identical or different, representing a (C ₂ -C ₆ )alkylene group, linear or branched, such as ethylene or propylene, and
● n represents an integer comprised inclusively between 1 and 100, preferably between 5 and 50, and preferably between 10 and 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 (XVIII'') below 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 (poly)ols of formula (XVII) are chosen from the polyhydroxylated compounds of formula (XIX) below:

in which :
-R₁, identical or different, independently represents a hydroxy group; an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 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 designates an alkoxy radical having from 1 to 2 carbon atoms;
- R'₂ and R''₂ independently represent an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, in particular from 1 to 2 carbon atoms such as a methyl;
- a denotes an integer ranging from 0 to 10, b denotes an integer ranging from 0 to 500, with a + b ≥ 4.

Among the compounds of formula (XIX), 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 the reference 481939 (Mn ~550 g.mol ^-1 , ~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 (XIX) used in the context of the invention are chosen from the compounds of formula (XIX) 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 and R'' 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 another embodiment of the invention, the polythiol compound is a thiolated polymeric compound.

The modes of preparation of the thiolated polymers used according to the invention are known to those skilled in the art, several modes are reported below in a non-limiting manner.

The thiolated polymers used according to 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 used 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 comprising at least one double bond.

The thiolated polymers used 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 used 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 as procysteine:

- N-acetyl homocysteine-thiolactone:

- γ-thiobutyrolactone:

- imino thiolane:

According to one embodiment of the invention, the thiolated polymers used according to the invention are polymers that are soluble in cosmetic media, particularly in aqueous or aqueous-alcoholic media. They are more preferably obtained from amino polymers and their ammonium salts or polyhydroxylated polymers.

According to another embodiment of the invention, the thiolated polymers implemented according to the invention are polymers soluble in lipophilic media.

According to one embodiment of the invention, the polythiol compound is a polymeric compound of formula (XX):

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 average molecular weight by molar weight of the polythiol polymer compounds, such as those of formula (XX), is generally between 500 and 400,000 g.mol ^-1 , preferably between 500 and 150,000 g.mol ^-1 .

According to a particular embodiment of the invention, the polythiolated compounds are chosen from the polyorganosiloxanes of formula (XX'):

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, 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 is between 500 and 55,000 g.mol ^-1 ; particularly n is an integer comprised from 1 to 100, preferably comprised from 5 to 50, and preferentially comprised from 10 to 30, and
● L ⁴ and L ⁵ , are as defined above in formula (XII), in particular represent a covalent bond, a (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy, oxy-( C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-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, preferably a group (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene , or (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene.

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

in which :
● L ⁴ and L 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, preferably L ⁴ and L ⁵ represent represent a group (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene, or (C ₁ -C ₆ )alkylene -oxy(C ₁ -C ₆ )alkylene, more preferably a divalent group chosen from –R ₂ –, –O–R ₂ –, –R ₂ –O–, –R ₂ –O–R ₂ –, preferably – R ₂ –O–R ₂ –, with R ₂ representing a linear or branched, preferably linear (C ₂ -C ₆ )alkylene group, such as ethylene or n-propylene;
● n represents an integer comprised from 1 to 100, preferably from 5 to 50, and preferably 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 by polydimethylsiloxane in which the thiol functions are located at the chain ends by thio-n-propyl groups, 80 -120 marketed by Gelest under the name DMS – SM 21, of formula (XX'''):

Preferably, the polythiolated compounds are chosen from those of formula (XXI):

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 than 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, 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 55000 g.mol ^-1 .

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

in which the values of n and m are such that the weight-average molecular weight of the silicone is between 1000 and 55000 g.mol ^-1 .

Examples of silicone of formula (XXI′) include those sold by Genesee Polymers under the names GP-367, GP-71-SS, GP-800 and GP-710.

Preferably, the silicone of formula (XXI') is the compound GP-367 marketed by the company Genesee Polymers.

The polythiol silicones are in particular polydimethylsiloxanes comprising at least two thiol groups such as, for example, the products SMS-022, SMS-042 and SMS-992 sold by the company Gelest at 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 another embodiment, the thiolated compound is a particle bearing at least two thiol groups, such as a silica functionalized by radicals, for example of the alkyl type, substituted by thiol functions, or a particle covered with compound(s). ) carrying at least two thiol functions (coating), said particle possibly being a sphere, a fiber, a rod (rod) or an amorphous structure.

According to a particular embodiment of the invention, the hydroxylated and/or thiolated compound is chosen from polymer compounds of the hyperbranched polymer and dendrimer type.

“ Hyperbranched polymers ” are molecular constructions having a branched structure, generally 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 which associate following 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 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 the junction points of the branches of the same generations 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 ", starburst 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 another variant of the invention, the thiolated compound used according to the invention designates a non-polymeric organic compound and can be represented by the formula (XXII):

in which :
- n denotes an integer greater than or equal to 2, preferably between 2 and 10, preferably between 2 and 5, and
- W denotes a linear or branched or (hetero)cyclic, saturated multivalent (at least divalent) C ₂ -C ₈₀ radical, an aromatic radical, a heteroaromatic cyclic radical, W possibly also containing one or more heteroatoms such as O, N , S and/or one or more functions chosen from esters, ketones, amides, ureas, preferably esters or ketones, and/or be substituted by one or more linear or branched C ₁ -C ₁₀ alkyl groups, C ₁ alkoxy -C ₁₀ linear or branched, 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 (XXII) is generally between 90 and 1500 g.mol ^-1 .

According to a first embodiment, the compound containing a thiol unit of formula (XXII) is such that n=2 and W denotes a linear or branched, preferably C ₂ -C ₁₂ saturated divalent C ₂ -C ₂₀ hydrocarbon radical.

According to this embodiment, the compound with a thiol unit denotes, for example, 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 another embodiment, the compound with a thiol unit of formula (XXII) is such that n=3 and W denotes a trivalent saturated hydrocarbon radical C ₃ -C ₂₀ linear or branched, preferably C ₂ -C ₁₂ linear or branched .

According to this other embodiment, the compound with a thiol unit can be chosen, for example, from 1,1,1-tris(mercaptomethyl)ethane, 2-ethyl-2-mercaptomethyl-1,3-propanedithiol, 1,2 ,3-propanetrithiol.

According to a third embodiment, the compound with a thiol unit of formula (XXII) is such that n=2 or 3 and W denotes a divalent or trivalent saturated C ₃ -C ₂₀ linear or branched hydrocarbon radical, 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 embodiment, the compound with a thiol unit can be chosen, for example, from: C ₂ -C ₁₂ bis mercaptoalkyl ethers and sulfides 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) such as 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 and 1,2,3-tris(2-mercaptoethylthio)propane.

Preferably, according to this embodiment, the compound (XXII) is chosen from 1,2-bis(2-mercaptoethylthio)propanethiol, 1,2,3-tris(2-mercaptoethylthio)propane and tetrakis(2 -mercaptoethylthiomethyl) methane.

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

According to this fourth embodiment, the compound with a thiol unit can be chosen from: esters of polyols (glycols, triols, tetraols, pentaols, hexaols) and of C ₁ -C ₆ 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 (β-mercaptopropionate), dipentaerylthritol hexakis (β-mercaptoproprionate), trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3- mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutanate), and dipentaerythritol hex-3-mercaptopropionate.

Preferably, according to this fourth embodiment, the compound with a thiol unit is chosen from trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3 -mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutanate), and dipentaerythritol hex-3-mercaptopropionate.

Particularly preferably, the compound with a thiol unit is pentaerythritol tetrakis(3-mercaptopropionate).

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

According to this fifth embodiment, the compound with a thiol unit can be chosen from tetrakis(2-mercaptoethylthiomethyl)methane, bis-(2-mercaptoethylthio-3-mercaptopropane)sulphide.

According to a sixth embodiment, the compound with a thiol unit of formula (XXII) is 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 alkyl radicals C ₁ -C ₁₀ linear or branched.

According to this sixth embodiment, the compound with a thiol unit can be chosen, for example, 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 embodiment, the compound with a thiol unit of formula (XXII) is such that n=3 and W denotes a cyclic radical of substituted isocyanurate type.

According to this seventh embodiment, the compound with a thiol unit can be chosen from polythiols of the isocyanurate class described in patents US Pat. No. 3,676,440 and US Pat.

According to this seventh embodiment, the compound with a thiol unit is preferably tris((mercaptopropionyloxy)-ethyl)isocyanurate.

According to an eighth embodiment, the compound with a thiol unit of formula (XXII) is 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 the C ₁ -alkyl type. C ₁₀ , C ₁ -C ₁₀ alkoxy, it being understood that when the W radical is substituted, the thiol functions may be carried by the substituent(s).

According to this eighth embodiment, the compound with a thiol unit can be chosen, for example, from the following compounds:
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, and
3,4-thiophenedithiol.

According to this eighth embodiment, the compound (XXII) is chosen from 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(2-mercaptoethyl)benzene, 1,2 ,4-tris(2-mercaptoethyl)benzene, 1,3,5-tris(2-mercaptoethyl)benzene, 1,2,3-tris(2-mercaptoethyleneoxy)benzene, 1,2,4-tris( 2-mercaptoethyleneoxy)benzene, 1,3,5-tris(2-mercaptoethyleneoxy)benzene, 1,2,3,4-tetramercaptobenzene, 1,2,3,5-tetramercaptobenzene, 1,2,4, 5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl) benzene, 1,2,3,5-tetrakis(mercaptomethyl) benzene, 1,2,4,5-tetrakis(mercaptomethyl) benzene, 1,2,3,4-tetrakis(2-mercaptoethyl)benzene, 1,2,3,5-tetrakis(2-mercaptoethyl)benzene, 1,2,4,5-tetrakis(2-mercaptoethyl)benzene, 1,2,3,4-tetrakis(2-mercaptoethyleneoxy)benzene, 1,2,3,5-tetrakis(2-mercaptoethyleneoxy)benzene e, 1,2,4,5-tetrakis(2-mercaptoethyleneoxy)benzene, 1,2,3-tris(2-mercaptoethylthio)benzene, 1,2,4-tris(2-mercaptoethylthio)benzene, 1,3,5-tris(2-mercaptoethylthio) benzene, 1,2,3,4-tetrakis(2-mercaptoethylthio) benzene, 1,2,3,5-tetrakis(2-mercaptoethylthio) benzene, 1 ,2,4,5-tetrakis(2-mercaptoethylthio)benzene, and 3,4-thiophenedithiol.

According to a ninth embodiment, the compound with a thiol unit of formula (XXII) is 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 radical W is substituted, the thiol functions may be carried by the substituent(s).

According to another particular embodiment of the invention, the thiolated and/or hydroxylated compound is chosen from triglyceride derivatives of hydroxylated and/or thiolated thiolated fatty acids, such as those of formula (XXIII):

in which :
● R ¹ , R ² and R ³ , identical or different, represent a hydrogen atom, a hydroxy group, or a thiol, preferably a thiol;
● 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 hydroxy or thiol groups, preferably thiol;
● 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, preferably identical, represents a heteroatom such as O, S, and N, preferably O.

Preferably, the compounds of formula (XXIII) 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 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; and or
● X ¹ , X ² and X ³ are identical and represent a -C(O)-O- or -OC(O)- group.

According to this embodiment, the compound with a thiol unit can be chosen, for example, from: triglycerides of fatty acids or vegetable oils modified with thiol groups by chemical reaction, such as, for example, thiolated soybean oils and hydroxylated soybean oils and thiolated, in particular the ^{polymercaptan®} products from Chevron Phillips, such as polymercaptan 407 (mercapto hydroxy soybean oil) and polymercaptan 358 (mercaptanised soybean oil) of the following formula (XXIV):

More preferably, the triglyceride derivatives of hydroxylated and/or thiolated thiolated fatty acids of formula (XXIII) are such as those of formula (XXIV) above.

According to a particular embodiment of the invention, the thiolated and/or hydroxylated compound is chosen from polyhydroxylated, polythiolated, or (poly)hydroxylated and (poly)thiolated compounds having several hydroxy and/or thiol groups, and having a weight average molecular weight ranging from 500 to 1,000,000 g.mol ^-1 , preferably ranging from 500 to 500,000 g.mol ^-1 , and preferentially ranging from 500 to 100,000 g.mol ^-1 .

According to this variant, the compounds of formula (XXII) for which n denotes an integer greater than or equal to 3, preferably between 3 and 10 and more preferably between 3 and 5, will be preferred.

Preferably, according to this variant, the compounds of formula (XXII) are chosen from the compounds of the second embodiment, or from the compounds of the third embodiment, or from the compounds of the fourth 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 embodiment, or from the compounds of the seventh embodiment such as in particular tris((mercaptopropionyloxy)-ethyl)isocyanurate.

Particularly preferably, according to this variant, the compounds of formula (XXII) are chosen from trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis( 3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutanate), dipentaerythritol hex-3-mercaptopropionate, and tris((mercaptopropionyloxy)-ethyl)isocyanurate.

According to another variant, the compound with a thiol unit according to the invention designates a polymeric compound and can be represented by the formula (XXV):

in which :
- n denotes an integer greater than or equal to 5, preferably comprised from 5 to 5000, preferably from 5 to 1000, and
- POL designates 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 (XXV) is generally between 500 and 400,000 g.mol ^-1 , preferably between 500 and 150,000 g.mol ^-1 .

In a particular embodiment, POL denotes a multivalent radical of the homopolymer or copolymer type.

In a particular embodiment, POL designates a polymeric radical of the star, comb, brush or dendritic type.

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 thiolated compound of formula (XXV) is such that POL denotes a hydrocarbon-based polymeric 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 compounds with a thiol unit of formula (XXV) such as poly(vinylmercaptan), poly(4-mercaptostyrene), poly(vinylbenzylmercaptan), poly(4-mercaptostyrene)-co-poly(methylmethacrylate), as well as polymers containing amide functions such as thiolated poly(hexamethylene adipamide).

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

The thiolated compounds of formula (XXV) also designate the compounds of formula (XXV) such that POL designates a so-called dendrimer, branched or hyperbranched polymer radical and the thiol groups are terminal. Examples include the polymers described in 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 (XXV) according to the scheme below:

The structure of the thiolated polymer (XXV) obtained is given below:

The compound with a thiol unit of formula (XXV) 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, mention may be made of compounds containing functional thiol groups of formula (XXVI) below:

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 thiolated polymers according to the invention are chosen from hyperbranched polymers, and in particular polyethyleneimine, comprising at least one group chosen from the groups of formula (XXVI) as defined above.

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 , identical or different, represent: the hydrogen atom ; a C ₁ -C ₆ alkyl radical, linear, branched or cyclic, saturated or unsaturated; an amino radical (-NH ₂ ); a carboxylic acid radical (-COOH); a C ₁ -C ₁₀ alkylamino radical; a C ₁ -C ₁₀ acylamino radical;
● R'' ¹ , R'' ² , R'' ³ and R'' ⁴ , 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 mode of the invention, the thiolated polymers are hyperbranched polymers and the dendrimers comprising functional groups of formula (XXVI) 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 represent 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 group of formula (XXVI) then corresponding to the following formula (XXVII):

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

Preferably, in formulas (XXVI) and (XXVII), X 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 (XXVIII):

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' is 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, and/or 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 , and (C ₁ -C ₈ )alkyl amino-carbonyl;
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 from 3 to 10000.

Preferably, the degree of grafting of thiol functions is greater than or equal to 1%.

Advantageously, poly N-α- and N-ε- lysine and ornithine corresponding to formula (XXVIII) have: 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 (XXVIII).

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 of between 30×10 ⁴ and 50×10 ⁴ g.mol ⁻¹ .

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(β-mercaptopropionate) type polymers can also be used according to 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 such as Pluracol P201 marketed by the company Wyandotte Chemical Corp. and β-mercaptopropionic acid.

According to a particular embodiment of the invention, the hydroxylated and/or thiolated polymers are polyethoxylated of formula (XXIX) as well as their optical isomers, and their acid or base salts, as well as their solvates such as hydrates:

in which :
● R ₁ , R ₂ and R ₃ , identical or different, preferably identical represent a hydroxy(C ₁ -C ₆ )alkyl or thio(C ₁ -C ₆ )alkyl group, preferably 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, represents 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 (XXII) 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 no. 345352-19-4).

According to a preferred embodiment, the crosslinking agent R is a (poly)thiolated and/or (poly)hydroxylated compound, in particular chosen from nonpolymeric (poly)thiolated and/or (poly)hydroxylated compounds such as the compounds polyhydroxylated (liposoluble polyol), polythiolated compounds (dithiol compounds), hydroxylated and/or thiolated alkoxysiloxanes, silicas functionalized by radicals, in particular of the alkyl type, substituted by thiol functions, latices bearing thiol groups, coated particles of compound(s) carrying at least two thiol functions and polymeric (poly)thiol and/or (poly)hydroxyl compounds such as homopolymers, copolymers, star, combe, brush and dendritics with hydroxy and/or thiol units, preferably organic or silicone.

Preferably, the polymeric (poly)thiol and/or (poly)hydroxyl compounds are chosen from polymer (di)ols, in particular polyolefin (poly)ols, polydi(C ₁ -C ₆ )alkylsiloxane (poly)ols , polyester (poly)ols, triglyceride derivatives of hydroxylated and/or thiolated thiolated fatty acids, amino thiols derived from dendrimers or from polyethyleneimines (PEI) and silicone thiols.

Preferably, the polymeric (poly)thiol and/or (poly)hydroxyl compounds are chosen from polydimethylsiloxane diols such as polydimethylsiloxanes with terminal hydroxy functions; thiolated poly(C ₁ -C ₄ )alkylsiloxanes such as polydimethylsiloxanes containing at least two thiol groups; and fatty acid triglycerides or vegetable oils modified with thiol groups by chemical reaction.

Preferably, the (poly)thiolated and/or (poly)hydroxylated compounds used according to the invention are chosen from fat-soluble polyols, dithiol compounds, hydroxylated and/or thiolated alkoxysiloxanes, silicas functionalized with radicals, in particular of the alkyl type, substituted by thiol functions, latices bearing thiol groups, particles coated with compound(s) bearing at least two thiol functions, polyolefins (poly)ols, polydi(C ₁ -C ₆ )alkylsiloxane ( poly)ols, polyesters (poly)ols, amino thiols derived from dendrimers or polyethyleneimines (PEI), silicone thiols, polydimethylsiloxane diols, thiolated poly(C ₁ -C ₄ )alkylsiloxanes and fatty acid triglycerides or vegetable oils modified with thiol groups by chemical reaction.

Preferably, the (poly)thiolated and/or (poly)hydroxylated compounds used according to the invention are chosen from polydimethylsiloxanes comprising at least two thiol groups.

Cross-linking agents (poly)carbonyls

According to a particular embodiment, the crosslinking agent R is a (poly)carbonyl compound.

In particular, the (poly)carbonyl compound is chosen from terephthalaldehyde, 5,5-dimethyl-1,3-cyclohexanedione, phenylglyoxal, isophthalaldehyde, 4-acetylbenzaldehyde, 4,4-diformyltriphenylamine, 2-acetylbenzaldehyde, 3-(2-furoyl)quinoline-2-carboxaldehyde, 3-(2-furoyl)quinoline-2-carboxaldehyde, 3-acetylbenzaldehyde, 9-(2-ethylhexyl)carbazole-3,6-dicarboxaldehyde, phthaldialdehyde, 1,3-cyclohexanedione, 4,4'-biphenyldicarboxaldehyde, benzene-1,3,5-tricarboxaldehyde, and oxidized inulin.

Cross-linking agents (poly)acrylates

According to a particular embodiment, the crosslinking agent R can be a (poly)acrylate compound.

More particularly, the (poly)acrylate compound can be chosen from 1,3-butanedioldiacrylate, 1,4-butanedioldiacrylate, di(trimethylolpropane)tetraacrylate, glycerol 1,3-diglycerolate diacrylate, glycerol propoxylate (1PO/OH ) triacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol ethoxylate diacrylate, hydroxypivalyl hydroxypivalate, neopentyl glycol diacrylate, neopentyl glycol propoxylate (1PO/OH) diacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, poly(propylene glycol) diacrylate, tricyclo[5.2.1.0 ^2,6 ]decanedimethanol diacrylate, trimethylolpropane ethoxylate (1EO/OH) methyl ether diacrylate, trimethylolpropane propoxylate triacrylate, trimethylolpropane triacrylate, tri(propylene glycol) diacrylate, tris[2-(acryloyloxy)ethyl]isocyanurate, N,N'-methylene bis-acrylamide, trimethylol propane triacrylate, methylene-bis-acrylamide, or mixtures of these compounds.

According to a preferred embodiment, the crosslinking agent is chosen from (poly)amino, (poly)thiolated and/or (poly)hydroxylated, (poly)carbonyl, (poly)acrylate compounds, and mixtures thereof, and preferably chosen from (poly)amine and (poly)thiolated compounds, with in particular said (poly)amine being chosen from chitosans, aminoalkoxysilanes and polydimethylsiloxanes comprising primary amine groups at the end of the chain or on the side chains, and even more preferably chosen from poly(D-Glucosamine), 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N -(2-aminoethyl)-3-aminopropyltriethoxysilane and polydimethylsiloxanes comprising at the end chain of aminopropyl terminal groups, and even more preferably is 3-aminopropyl triethoxysilane (APTES) and in particular said (poly)thiolated compound, being chosen from polydiorganosiloxanes with thiol functions, friends nosilicones with thiol functions, alkoxysilanes with thiol functions, organic polythiols, natural products modified by thiol groups, amino thiols derived from dendrimers or from polyethyleneimines (PEI) and silicone thiols, preferably the (poly)thiolated compound being chosen from polydimethylsiloxanes terminated with mercaptopropyl groups and dimethicone/mercaptopropyl methicone copolymers.

Fat phase

The compositions C1, C2 or C3 according to the invention contain a fatty phase, in particular a fatty phase comprising a hydrocarbon oil, preferably isododecane.

In a preferred embodiment, the hydrocarbon oil, preferably isododecane, is predominantly present in the fatty phase of a composition according to the invention, relative to all of the constituents of said fatty phase.

The CR and CAC compositions can also contain a fatty phase suitable for the invention.

Hydrocarbon oil

As stated previously, a composition C1, C2 or C3 according to the invention or CR or CAC suitable for the invention may comprise at least one hydrocarbon-based oil, in particular non-volatile.

By “ oil ”, is meant a non-aqueous compound, immiscible with water, liquid at ambient temperature (20° C.) and atmospheric pressure (760 mm Hg).

The term "hydrocarbon oil" means 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 alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

In particular, a composition in accordance with the invention may comprise at least one hydrocarbon-based oil chosen from:
- C ₈ -C ₁₄ hydrocarbon-based oils, 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 of Isopars or Permetyls,
linear alkanes, for example such as n-dodecane (C ₁₂ ) and n-tetradecane (C ₁₄ ) sold by Sasol respectively under the references Parafol 12-97 and Parafol 14-97 , as well as their mixtures, the undecane mixture -tridecane, the mixtures of n-undecane (C ₁₁ ) and n-tridecane (C ₁₃ ) obtained in Examples 1 and 2 of application WO2008/155059 from Cognis, and mixtures thereof, and
short chain esters (having 3 to 8 carbon atoms in total), such as ethyl acetate, methyl acetate, propyl acetate and 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 caprylic/capric acid triglycerides such as those sold by Stéarineries Dubois,
- synthetic ethers having 10 to 40 carbon atoms,
- linear or branched hydrocarbons, of mineral or synthetic origin, in particular petroleum jelly, polydecenes, hydrogenated polyisobutene, in particular Parleam ^® , squalane, paraffin oils, and mixtures thereof,
- synthetic esters such as the oils of formula R ₁ COOR ₂ in which R ₁ represents the residue of a linear or branched fatty acid containing from 1 to 40 carbon atoms and R ₂ represents a hydrocarbon chain in particular branched containing from 1 to 40 carbon atoms provided that the sum of the numbers of carbon atoms in R ₁ and R ₂ is greater than or equal to 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, isostearate of isostearyl, 2-hexyl-decyl laurate, 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 from 12 to 26 carbon atoms, such as octyl dodecanol, isostearyl alcohol, oleic alcohol, 2-hexyldecanol, 2-butyloctanol, and 2-undecylpentadecanol.

Preferably, the hydrocarbon oil present in a composition according to the present invention is apolar, it is formed solely of carbon and hydrogen atoms.

Preferably, the hydrocarbon-based oil is chosen from C ₈ -C ₁₄ hydrocarbon-based oils and mixtures thereof and in a particularly preferred manner, the hydrocarbon-based oil is isododecane.

According to a preferred embodiment, the compositions C1, C2 and/or C3 according to the invention comprise at least one hydrocarbon-based oil, preferably chosen from C ₈ -C ₁₄ hydrocarbon-based oils and mixtures thereof, and more preferably is at least isododecane.

According to a particular embodiment, the compositions C1, C2 and/or C3 according to the invention contain a fatty phase comprising isododecane, in particular a fatty phase mainly comprising isododecane with respect to all the constituents of said fatty phase such as an isododecane/octyldodecanol mixture or an isododecane/isononyl isononanoate mixture.

Preferably, a composition according to the invention comprises from 15% to 90% by weight, and preferably from 40% to 85% by weight, of hydrocarbon oil(s) relative to the total weight of the composition.

Non-volatile oil distinct from ' hydrocarbon oil

According to a preferred embodiment, a composition C1, C2 or C3 according to the invention may also comprise at least one non-volatile oil distinct from said hydrocarbon-based oil described above.

Thus, a composition according to the invention may comprise one or more silicone oils, fluorinated or not, or mixtures thereof. In particular, it may be an oil chosen from:
- linear or branched hydrocarbons, in particular polydecenes, hydrogenated polyisobutene, in particular Parléam;
- fatty alcohols having 12 to 26 carbon atoms such as octyldodecanol, 2-butyloctanol, 2-hexyldecanol, 2-undecylpentadecanol, oleic alcohol;
- partially hydrocarbon and/or silicone fluorinated oils;
- silicone oils such as non-volatile, linear or cyclic polymethylsiloxanes (PDMS), liquid or pasty at room temperature such as cyclomethicones, dimethicones, optionally comprising a phenyl group, such as phenyl trimethicones, phenyltrimethylsiloxydiphenyl siloxanes, diphenylmethyldimethyl-trisiloxanes, diphenyl dimethicones, phenyl dimethicones, polymethylphenyl siloxanes;
- and mixtures thereof.

The term “ silicone oil ” means an oil comprising at least one silicon atom, and in particular at least one Si—O group.

The term " fluorinated oil " means an oil comprising at least one fluorine atom.

These oils may be present in a content ranging from 0.01% to 60%, and better still from 0.1% to 50% by weight, relative to the total weight of the composition.

Preferably, the non-volatile oil distinct from said hydrocarbon-based oil is chosen from non-volatile hydrocarbon-based oils, more preferably chosen from fatty alcohols having from 12 to 26 carbon atoms, synthetic esters and mixtures thereof.

A composition according to the invention advantageously comprises at least one non-volatile oil distinct from said hydrocarbon oil, preferably ranging from 0.01% to 60% by weight, and preferably from 0.1% to 50% by weight, of non-volatile oil distinct from said hydrocarbon oil, relative to the total weight of the composition.

Other oils

According to a particular embodiment, a composition C1, C2 or C3 according to the invention may also comprise at least one oil distinct from the oils mentioned above.

Thus, a composition according to the invention may comprise hydrocarbon oils, silicone oils, fluorinated or not, or mixtures thereof, distinct from the oils mentioned above.

The oils may be volatile or non-volatile.

They can be of animal, vegetable, mineral or synthetic origin.

The oils may optionally comprise oxygen, nitrogen, sulfur and/or phosphorus atoms, for example, in the form of hydroxyl or acid radicals.

Aqueous phase

According to a particular embodiment, the compositions C1, C2 and/or C3 according to the invention can also comprise an aqueous phase.

According to a particular embodiment, the CR compositions containing at least one crosslinking agent and/or CAC containing at least one cosmetic active agent according to the invention can also comprise an aqueous phase and/or consist of an aqueous phase.

The aqueous phase of a composition according to the invention C1, C2 or C3 or of a composition CR or CAC suitable for the invention comprises water and optionally a water-miscible solvent.

A water suitable for the invention can be a floral water, such as cornflower water and/or a mineral water such as VITTEL water, LUCAS water or LA ROCHE POSAY water, a thermal and/or spring water.

By “ water - miscible solvent ”, is meant in the present invention a compound that is liquid at room temperature and miscible with water (miscibility in water greater than 50% by weight at 25° C. and atmospheric pressure).

The water-miscible solvents that can be used in the composition of the invention can also be volatile.

Among the water-miscible solvents which can be used in the composition in accordance with the invention, mention may in particular be made of lower monoalcohols having from 1 to 5 carbon atoms, such as ethanol and isopropanol, glycols having 2 with 8 carbon atoms such as ethylene glycol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, C ₃ and C ₄ ketones and C ₂ -C ₄ aldehydes.

According to one embodiment variant, the aqueous phase of a composition according to the invention may comprise at least one C ₂ -C ₃₂ polyol.

By “ polyol ”, it is necessary to understand, within the meaning of the present invention, any organic molecule comprising at least two free hydroxyl groups.

Preferably, a polyol in accordance with the present invention is present in liquid form at room temperature.

A polyol suitable for the invention may be a compound of the alkyl type, linear, branched or cyclic, saturated or unsaturated, carrying on the alkyl chain at least two –OH functions, in particular at least three –OH functions, and more particularly minus four –OH functions.

The polyols which are advantageously suitable for the formulation of a composition according to the present invention are those having in particular from 2 to 32 carbon atoms, preferably 3 to 16 carbon atoms.

Advantageously, the polyol can be chosen, for example, from ethylene glycol, pentaerythritol, trimethylolpropane, propylene glycol, 1,3-propanediol, pentane-1,2-diol, caprylyl glycol (octane-1,2- diol), butylene glycol, isoprene glycol, pentylene glycol, hexylene glycol, glycerol, polyglycerols, such as glycerol oligomers such as diglycerol, polyethylene glycols, and mixtures thereof.

Preferably, a composition according to the invention is an anhydrous composition.

By anhydrous composition is meant a composition containing less than 2% by weight of water, or even less than 0.5% of water, and in particular free of water. If necessary, such small amounts of water can in particular be introduced by ingredients of the composition which can contain residual amounts.

Cosmetic Active

A composition according to the invention, in particular C1 or C2 or a composition suitable for the invention as CR, may comprise one or more cosmetic active ingredient(s) called “AC”, chosen from:
a) coloring agents chosen from pigments, direct dyes, and mixtures thereof,
b) active ingredients for the care of keratin materials, preferably the skin,
c) UV filters,
and d) mixtures thereof.

The AC cosmetic active(s) optionally present in composition C1 can be introduced with the copolymer CP and/or with a separate CAC composition.

The cosmetic active agent(s) AC optionally present in a composition C2 can be introduced with the crosslinking agent R and/or a composition CR, and/or with a composition C1 and/or with a composition CAC.

A C3 composition according to the invention or a CAC composition suitable for the invention comprises one or more AC cosmetic active ingredient(s) chosen from a) coloring agents from pigments, direct dyes, and mixtures thereof , b) active ingredients for caring for keratin materials, preferably the skin, c) UV filters, and d) mixtures thereof.

A C3 composition according to the invention or a CAC composition suitable for the invention comprises one or more AC cosmetic active ingredient(s) chosen from a) coloring matter chosen from pigments, direct dyes, and their mixtures, b) active ingredients for the care of keratin materials, in particular the skin, c) UV filters, and mixtures thereof.

According to a particular embodiment, the at least one cosmetic agent is chosen from dyestuffs, in particular chosen from pigments, direct dyes and mixtures thereof.

The AC cosmetic active agents present in a C3 composition can be introduced therein in different ways depending on the protocol chosen to prepare this composition.

They can thus be introduced with at least one of the ingredients of composition C3, for example with the (co)polymer in composition C1 and/or with the crosslinking agent R or a separate composition CR containing at least this crosslinking agent and/ or with a CAC composition.

In the variant where composition C3 is obtained from a composition C1, they may be present in this composition C1 and/or be implemented with a composition CAC. In the variant where composition C3 is obtained from a composition C2, this or these ACs may be present in this composition C2 and/or be implemented with a composition CAC.

Of course, in each of these variants, one or more CAs, identical or different, can be present in the compositions considered for preparing C3.

Similarly, the same AC cosmetic active ingredient may be present in a C1 composition and/or in a C2 composition and/or in a CR composition and/or in a distinct CAC composition, it being understood that when several distinct cosmetic active ingredients are used, these can be introduced for all or part indifferently in C1 and/or in C2 and/or in CR and/or in a distinct composition CAC.

If several cosmetic active agents are present in a composition C3, these may be present simultaneously in a composition C1 and/or in a composition C2 and/or in a composition CR and/or in a separate composition CAC.

According to another variant, if several cosmetic active agents are present in a composition C3, each of them can be present separately in a composition C1 and/or in a composition C2 and/or in a composition CR and/or in a separate composition CAC .

According to a particular embodiment, the at least one cosmetic agent is chosen from dyestuffs, preferably chosen from pigments, direct dyes and mixtures thereof.

Of course, those skilled in the art will take care to choose this or these optional AC cosmetic active agents, and/or their quantity, in such a way that the advantageous properties of the corresponding composition according to the invention are not, or substantially not, altered by the proposed addition.

Dyestuffs

A composition according to the invention as C1 or C2, or suitable for the invention as CR, may also comprise at least one coloring matter, whether particulate or not, water-soluble or not, and preferably in an amount of at least 0.01% by weight relative to the total weight of the composition under consideration.

A composition according to the invention C3, or suitable for the invention as CAC, further comprises at least one coloring matter, whether particulate or not, water-soluble or not, and preferably in an amount of at least 0.01% by weight relative to the total weight of the composition under consideration.

For obvious reasons, this quantity is likely to vary significantly with regard to the intensity of the desired color effect and the color intensity provided by the dyestuffs considered and its adjustment is clearly within the competence of the person skilled in the art. art.

Preferably, a composition C3 according to the invention comprises at least one dyestuff chosen from pigments, direct dyes, and mixtures thereof.

Preferably, a CAC composition suitable for the invention comprises at least one dyestuff chosen from pigments, direct dyes, and mixtures thereof, preferably at least one pigment.

When a composition C1, C2, CR according to the invention comprises at least one AC cosmetic active, said cosmetic active preferably comprises at least one coloring material chosen from pigments, direct dyes and mixtures thereof and more preferably at least one pigment .

Preferably, a composition C3 according to the invention comprises at least one pigment.

Pigment s

By “ pigment ”, within the meaning of the invention, is meant any compound capable of imparting color to keratin materials. These compounds have a solubility in water at 25° C. and at atmospheric pressure (760 mmHg) of less than 0.05% by weight, and preferably less than 0.01% by weight.

A composition C1 or C2 according to the invention or a composition CR suitable for the invention may comprise at least one cosmetic active agent AC, said cosmetic active agent preferably comprising one or more pigment(s).

A C3 composition according to the invention or a CAC composition suitable for the invention comprises at least one AC cosmetic active, said cosmetic active preferably comprising one or more pigment(s).

Mention may in particular be made, as pigments suitable for the invention, of the organic and/or inorganic pigments known to 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.

These pigments can be synthetic or natural.

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

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

A pigment suitable for the invention can be chosen from mineral pigments.

By " mineral pigment " is meant any pigment which 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 manganese violet, ultramarine blue, chromium hydrate, ferric blue and the oxides or dioxides of titanium, zirconium or cerium, as well as the oxides of zinc, iron or chromium.

It may also be a pigment having a structure which may for example be of the sericite/brown iron oxide/titanium dioxide/silica type. Such a pigment is marketed for example under the reference Coverleaf NS or JS by the company Chemicals And Catalysts and has a contrast ratio close to 30. It can also be pigments having a structure which can be, for example, of the type silica microspheres containing iron oxide. An example of a pigment having this structure is that marketed by the Miyoshi company under the reference PC Ball PC-LL-100 P, this pigment consisting of silica microspheres containing yellow iron oxide.

Advantageously, the pigments can be iron oxides and/or titanium dioxides.

A pigment suitable for the invention can be chosen from organic pigments.

By " organic pigment " is meant any pigment which meets the definition of the Ullmann encyclopedia in the organic pigment chapter.

Mention may be made, among the organic pigments useful in the present invention, of the compounds nitroso, nitro, azo, xanthene, pyrene, quinoline, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, of the metal complex type, isoindolinone, isoindoline, quinacridone, perinone , perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone.

In particular, the white or colored organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 74100, 74160, the yellow pigments coded in the Color Index under the references CI 61565, 61570, 74260, orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, 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, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole, phenolic derivatives as described in patent FR 2,679,771.

By way of example, mention may also be made of organic pigment pigment pastes such as the products sold by the company HOECHST under the name:
- YELLOW COSMENYL IOG: Pigment YELLOW 3 (CI 11710);
- COSMENYL YELLOW G: Pigment YELLOW 1 (CI 11680);
- ORANGE COSMENYL GR: Pigment ORANGE 43 (CI 71105);
- COSMENYL RED R: Pigment RED 4 (CI 12085);
- CARMIN COSMENYL FB: Pigment RED 5 (CI 12490);
- VIOLET COSMENYL RL: Pigment VIOLET 23 (CI 51319);
- COSMENYL BLUE A2R: Pigment BLUE 15.1 (CI 74160);
- GREEN COSMENYL GG: Pigment GREEN 7 (CI 74260);
- COSMENYL BLACK R: Pigment BLACK 7 (CI 77266).

The pigments in accordance with the invention can also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments can 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.

The organic pigment can also be a lake. 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 dyes adsorbed on organic substrates, mention may be made of carminic acid. Mention may also be made of the dyes 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 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 42 053), D & C Blue 1 ( CI 42 090), FDC Red 4, D & C Red 6, D & C Red 22, D & C Red 28, D & C Red 30, D & C Orange 4, D & C Yellow 8, D & C Green 5 , D & C Red 17, D & C Green 6, D & C Yellow 11, D & C Violet 2, Sudan red, carotenes (β-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein) , palm oil, Sudan brown, quinoline yellow, annatto, curcumin, betanin (beetroot), carmine, coppery chlorophyllin, methylene blue, anthocyanins (enocianine, black carrot, hibiscus, elderberry ), caramel, riboflavin, beet juice and l and caramel.

As examples of lacquers, mention may be made of the product known under the following name: D & C Red 7 (CI 15 850:1).

The pigment may also be a special effect pigment. By special effect pigments, we mean pigments that 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 or photochromic pigments, and those with a higher refractive index such as nacres, interference pigments or glitter.

By " nacres ", it is necessary to understand colored particles of any shape, iridescent or not, in particular produced by certain molluscs in their shell or else synthesized, and which have a color effect by optical interference.

As examples of special effect pigments, mention may be made of pearlescent pigments such as mica covered with titanium, or bismuth oxychloride, colored pearlescent pigments such as mica covered with titanium and iron oxides, mica covered with iron oxide, mica covered with titanium and in particular with ferric blue or chromium oxide, mica covered with titanium and an organic pigment as defined previously as well as pearlescent pigments based on bismuth oxychloride. It can also be particles of mica on the surface of which are superimposed at least two successive layers of metal oxides and/or organic coloring matter.

As pearlescent pigments, mention may be made of Cellini nacres marketed by BASF (Mica-TiO ₂ -lacquer), Prestige marketed by Eckart (Mica-TiO ₂ ), Prestige Bronze marketed by Eckart (Mica-Fe ₂ O ₃ ) Colorona marketed by Merck (Mica-TiO ₂ -Fe ₂ O ₃ ).

Mention may also be made of the gold-colored nacres marketed by the company BASF under the name of Brillant gold 212G (Timica), Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne) ; the mother-of-pearl bronzes marketed in particular by the company MERCK under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona) and by the company BASF under the name Super bronze (Cloisonne); the orange nacres sold in particular by the company BASF 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); the brown nacres in particular marketed by the company BASF under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); mother-of-pearl with a copper sheen in particular marketed by the company BASF under the name Copper 340A (Timica); 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 BASF under the name Yellow (4502) (Chromalite); nacres of a red tint with a gold sheen in particular marketed by the company BASF under the name Sunstone G012 (Gemtone); the pink nacres in particular marketed by the company BASF under the name Tan opale G005 (Gemtone); black mother-of-pearl with a gold sheen in particular marketed by the company BASF 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), white mother-of-pearl with sheen silver in particular marketed by the company MERCK under the name Xirona Silver and the pinkish-orange-golden-green nacres in particular marketed by the company MERCK under the name Indian summer (Xirona) and mixtures thereof.

Still by way of example of nacres, mention may also be made of particles comprising a borosilicate substrate coated with titanium oxide.

Particles with a glass substrate coated with titanium oxide are in particular sold under the name METASHINE MC1080RY by the company TOYAL.

Finally, as examples of nacres, mention may also be made of polyethylene terephthalate flakes, in particular those marketed by the company Meadowbrook Inventions under the name Silver 1P 0.004X0.004 (silver flakes). One can also consider multilayer pigments based on synthetic substrates such as alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum.

Advantageously, the nacres in accordance with the invention are micas covered with titanium dioxide or iron oxide as well as bismuth oxychloride.

The special effect pigments can also be chosen from reflective particles, that is to say in particular particles whose size, structure, in particular the thickness of the layer or layers which constitute it and their physical and chemical natures, and the surface finish, allow them to reflect incident light. This reflection may, where appropriate, have sufficient intensity to create on the surface of the composition or mixture, when the latter is applied to the support to be made up, highlights visible to the naked eye, that is i.e. brighter points that contrast with their surroundings by seeming to shine.

The reflective particles can be selected so as not to significantly alter the coloring effect generated by the coloring agents associated with them and more particularly so as to optimize this effect in terms of color rendering. They may more particularly have a yellow, pink, red, bronze, orange, brown, gold and/or copper color or reflection.

These particles can have various shapes, in particular be in the form of platelets or globular, in particular spherical.

The reflective particles, whatever their shape, may or may not have a multilayer structure and, in the case of a multilayer structure, for example at least one layer of uniform thickness, in particular of a reflective material.

When the reflective particles do not have a multilayer structure, they may be composed for example of metal oxides, in particular titanium or iron oxides obtained by synthesis.

When the reflective particles have a multilayer structure, these may for example comprise a natural or synthetic substrate, in particular a synthetic substrate at least partially coated with at least one layer of a reflective material, in particular of at least one metal or metallic material . The substrate can be monomaterial, multimaterial, organic and/or inorganic.

More particularly, the substrate of the reflective particles can be chosen from glasses, ceramics, graphite, metal oxides, aluminas, silicas, silicates, in particular aluminosilicates and borosilicates, synthetic mica and their mixtures, this list not being limiting.

The reflective material may comprise a layer of metal or of a metallic material.

By way of illustration of these particles, mention may be made of aluminum particles, such as those marketed under the names Starbrite 1200 EAC ^® by the company Siberline and Metalure ^® by the company Eckart and glass particles covered with a metallic layer in particular those described in the documents JP-A-09188830, JP-A-10158450, JP-A-10158541, JP-A-07258460 and JP-A-05017710.

Still as an example of reflective particles comprising a mineral substrate coated with a layer of metal, mention may also be made of particles comprising a borosilicate substrate coated with silver.

Particles with a glass substrate coated with silver, in the form of platelets, are sold under the name MICROGLASS METASHINE REFSX 2025 PS by the company TOYAL. Particles with a glass substrate coated with a nickel/chrome/molybdenum alloy are sold under the name CRYSTAL STAR GF 550, GF 2525 by this same company.

It is also possible to use particles comprising a metal substrate such as silver, aluminum, iron, chromium, nickel, molybdenum, gold, copper, zinc, tin, magnesium, steel, bronze, titanium, said substrate being coated with at least one layer of at least one metal oxide such as titanium oxide, aluminum oxide, iron oxide, cerium, chromium oxide, silicon oxides and mixtures thereof.

Mention may be made, by way of example, of the aluminum, bronze or copper powders coated with SiO ₂ marketed under the name VISIONAIRE by the company ECKART.

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 that 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 used in the composition according to the present invention is generally between 10 nm and 200 μm, preferably between 20 nm and 80 μm, and more preferably between 30 nm and 50 μm.

The pigments can be dispersed in the composition using a dispersing agent.

The dispersing agent serves to protect the dispersed particles against their agglomeration or flocculation. This dispersing agent may be a surfactant, an oligomer, a polymer or a mixture of several of them, bearing 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 dispersants also have at least one functional group that is compatible or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of C ₈ to C ₂₀ fatty acid and of polyol such as glycerol, diglycerin, such as poly(12-hydroxystearic acid stearate) are used. ) 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 else the 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 composition 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 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; sodium, potassium, magnesium, iron, titanium, zinc or aluminum salts of fatty acids, for example aluminum stearate or laurate, aluminum dimyristate and aluminum salt of hydrogenated tallow glutamate; metal alkoxides; polyethylene; (meth)acrylic polymers, for example polymethylmethacrylates; polymers and copolymers containing acrylate units; alkanoamines; silicone compounds, for example silicones, in particular polydimethylsiloxanes; fluorinated organic compounds, for example perfluoroalkyl ethers, perfluoroalkyl phosphates, hexafluoropropylene polyoxides, perfluoropolyethers; fluoro-silicone compounds such as perfluoroalkylsilanes, amino acids; N-acylated amino acids or their salts; lecithin, isopropyl trisostearyl titanate, isostearyl sebacate; and their mixtures.

The term alkyl mentioned in the compounds mentioned above denotes in particular an alkyl group having from 1 to 30 carbon atoms, preferably having from 5 to 16 carbon atoms.

The surface-treated pigments useful in the composition 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 treatments of the pigments are chosen from the following treatments:
- a PEG-Silicone treatment, for example the AQ surface treatment marketed by LCW;
- a Methicone treatment, for example the SI surface treatment marketed by LCW;
- a Dimethicone treatment, for example the Covasil 3.05 surface treatment marketed by LCW;
- a Dimethicone/Trimethylsiloxysilicate treatment, for example the Covasil 4.05 surface treatment marketed by LCW;
- a Magnesium Myristate treatment, for example the MM surface treatment marketed by LCW;
- an Aluminum Dimyristate treatment, for example the MI surface treatment marketed by Miyoshi;
- a Perfluoropolymethylisopropyl ether treatment, for example the FHC surface treatment marketed by LCW;
- an Isostearyl Sebacate treatment, for example the HS surface treatment marketed by Miyoshi;
- a Perfluoroalkyl Phosphate treatment, for example the PF surface treatment marketed by Daito;
- an acrylate/dimethicone copolymer and perfluoalkyl phosphate treatment, for example the FSA surface treatment marketed by Daito;
- a polymethylhydrogen siloxane/perfluoroalkyl phosphate treatment, for example the FS01 surface treatment marketed by Daito;
- an Acrylate/Dimethicone Copolymer treatment, for example the ASC surface treatment marketed by Daito;
- an Isopropyl Titanium Triisostearate treatment, for example the ITT surface treatment marketed by Daito;
- an Acrylate copolymer treatment, for example the APD surface treatment marketed by Daito;
- a Perfluoroalkyl Phosphate/Isopropyl Titanium Triisostearate treatment, for example the PF+ITT surface treatment marketed by Daito.

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

The term "sub-micron" means pigments whose particle size has been micronized by the micronization method and whose average particle size is less than one micrometer (μm), in particular the average particle size is between 0.1 to 0.9 μm, and preferably from 0.2 to 0.6 μm.

According to one embodiment, the dispersing agent and the pigment(s) are present in a dispersant/pigment mass ratio comprised from 1:4 to 4:1, particularly from 1.5:3.5 to 3.5:1, or better of 1.75:3 and 3:1.

The dispersing agent(s) can therefore have a silicone skeleton, such as silicone polyether and dispersants of the amino-silicone type, different from the alkoxysilanes previously described. Suitable dispersing agents include:
- amino-silicones, that is to say 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, by Genesee Polymers,
- silicone acrylates such as those marketed under the names and references Tego ^® RC 902, Tego ^® RC 922, Tego ^® RC 1041, and Tego ^® RC 1043 by the company Evonik,
- polydimethylsiloxane (PDMS) silicones with carboxylic groups such as those marketed under the names and references X-22162 and X-22370 by the company Shin-Etsu, silicone epoxies such as those marketed under the names and references 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 company.

According to one particular embodiment, the dispersing agent(s) are of the amino-silicone type, different from the alkoxysilanes previously described and are cationic.

Preferably, the pigment(s) is (are) chosen from inorganic, mixed inorganic-organic or organic pigments.

According to a particular embodiment, the pigment(s) according to the invention are organic pigments, preferably organic pigments surface-treated with an organic agent chosen from silicone compounds.

According to another embodiment of the invention, the pigment or pigments according to the invention are mineral pigments.

A composition C1 or C2 according to the invention or a composition CR suitable for the invention may comprise at least one cosmetic active agent AC, said cosmetic active agent preferably comprising one or more direct dye(s).

A C3 composition according to the invention or a CAC composition suitable for the invention comprises at least one AC cosmetic active, said cosmetic active preferably comprising one or more direct dye(s).

By " direct dye " is meant natural and/or synthetic dyes, different from oxidation dyes. These are dyes that will diffuse superficially on the fiber. They can be ionic or nonionic, preferably cationic or nonionic.

Among the direct dyes suitable for the invention, mention may be made of azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines and styryls; carbonyl dyes; azine dyes; nitro(hetero)aryl dyes; tri(hetero)arylmethane dyes; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.

The direct dyes are preferably cationic direct dyes. Mention may be made of the cationic hydrazono dyes of formulas (A) and (B) below and the cationic azo dyes of formulas (C) and (D) below:

in which :
- Het ⁺ represents a cationic heteroaryl radical, preferentially with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally substituted preferentially by at least one (C ₁ -C ₈ )alkyl group such as methyl;
- Ar ⁺ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge, preferably ammonium, particularly tri(C ₁ -C ₈ )alkyl-ammonium such as trimethylammonium;
- Ar represents an aryl group, in particular phenyl, optionally substituted, preferably by one or more electron-donating groups such as optionally substituted (C ₁ -C ₈ )alkyl, optionally substituted (C ₁ -C ₈ )alkoxy, (di)(C ₁ -C ₈ )(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group, aryl(C ₁ -C ₈ )alkylamino, and N-(C ₁ -C ₈ )alkyl-N-aryl(C ₁ - C ₈ ) alkylamino optionally substituted or else Ar represents a julolidine group;
- Ar'' represents an optionally substituted (hetero)aryl group such as phenyl or pyrazolyl optionally substituted, preferably by one or more (C ₁ -C ₈ )alkyl, hydroxyl, (di)(C ₁ -C ₈ )(alkyl )amino, (C ₁ -C ₈ )alkoxy or phenyl;
- Ra and Rb, identical or different, representing a hydrogen atom or a (C ₁ -C ₈ )alkyl group optionally substituted, preferably by a hydroxyl group;
or else the substituent Ra with a substituent of Het+ and/or Rb with a substituent of Ar form together with the atoms which carry them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group optionally substituted by a hydroxyl group;
- Q - represents an organic or inorganic anionic counterion such as a halide or an alkyl sulphate.

Particular mention may be made of direct dyes with cationic charge, endocyclic azo and hydrazono of formula (A) to (D) as defined previously. More particularly, the cationic direct dyes with an endocyclic cationic charge described in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferably the following direct dyes of formulas (E) and (F):

in which :
- R ¹ represents a (C ₁ -C ₄ )alkyl group such as methyl;
- R ² and R ³ , which are identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl; And
- R ⁴ represents a hydrogen atom or an electron-donating group such as (C ₁ -C ₈ )alkyl optionally substituted, (C ₁ -C ₈ )alkoxy optionally substituted, (di)(C ₁ -C ₈ )(alkyl) amino optionally substituted on the alkyl group(s) by a hydroxyl group; particularly R ⁴ is a hydrogen atom;
- Z represents a CH group or a nitrogen atom, preferably CH;
- Q - is an anionic counter ion as defined above, particularly a halide such as chloride or an alkyl sulphate such as methyl sulphate or mesytyl.

In particular, the dyes of formula (E) and (F) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives with Q- an anionic counterion as defined previously, particularly halide such as chloride or a alkyl sulfate such as methyl or mesyl sulfate.

The direct dyes can be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly called “acid” direct dyes for their affinity with alkaline substances.

By " anionic direct dyes " is meant any direct dye comprising in its structure at least one CO ₂ R' or SO ₃ R' substituent with R' designating a hydrogen atom or a cation originating from a metal or an amine , or an ammonium ion.

The anionic direct dyes can be chosen from acid nitro direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and acid natural dyes.

As direct anionic dyes suitable for the invention, mention may be made of the dyes of formulas (G), (G'), (H), (H'), (J), (J'), (K), ( K'), (L), (M), (N) and (O) following:

a) the anionic azo dyes of formulas (G) and (G') below:

in which R ₇ , R ₈ , R ₉ , R ₁₀ , R′ ₇ , R′ ₈ , R′ ₉ and R′ ₁₀ , which are identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;
- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO--, M+ with M+ as defined above;
- R''-S(O) ₂ -, with R'' representing a hydrogen atom, an alkyl group, an aryl group, (di) (alkyl) amino, aryl (alkyl) amino; preferably a phenylamino or phenyl group;
- R'''-S(O) ₂ -X'- with R''' representing an optionally substituted alkyl or aryl group, X' being as defined above;
- (di)(alkyl)amino;
- aryl(alkyl)amino optionally substituted by one or more groups chosen from i) nitro; ii) nitroso; iii) (O) ₂ S(O-)-, M+ and iv) alkoxy with M+ as defined above;
- optionally substituted heteroaryl; preferentially a benzothiazolyl group;
- cycloalkyl; in particular cyclohexyl;
- Ar-N=N- with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl, (O) ₂ S(O-)-, M+ or phenylamino groups;
- or else two contiguous groups R ₇ with R ₈ or R ₈ with R ₉ or R ₉ with R ₁₀ together form a fused benzo A'group; and R' ₇ with R' ₈ or R' ₈ with R' ₉ or R' ₉ with R' ₁₀ together form a fused group benzo B'; with A' and B' optionally substituted with one or more groups chosen from nitro; nitroso; (O) ₂ S(O-)-, M+; hydroxy; mercapto; (di)(alkyl)amino; R°-C(X)-X'-;R°-X'-C(X)-;R°-X'-C(X)-X''-;
Ar-N=N- and optionally substituted aryl(alkyl)amino; with M+, R°, X, X', X'' and Ar as defined previously;
and in which:
- W represents a sigma σ bond, an oxygen or sulfur atom, or a divalent radical –NR- with R as defined above, or methylene -C(Ra)(Rb)- with identical or different Ra and Rb, representing a hydrogen atom or an aryl group, or else Ra and Rb form together with the carbon atom which carries them a cycloalkyl spiro; preferentially W represents a sulfur atom or Ra and Rb together form a cyclohexyl;
it being understood that the formulas (G) and (G') comprise at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical (O)CO--, M+ on one of the rings A, A ', B, B' or C; preferentially sodium sulfonate.

Examples of dyes of formula (G) include: Acid Red 1, Acid Red 4, Acid Red 13, Acid Red 14, Acid Red 18, Acid Red 27, Acid Red 28, Acid Red 32, Acid Red 33, Acid Red 35, Acid Red 37, Acid Red 40, Acid Red 41, Acid Red 42, Acid Red 44, Pigment Red 57, Acid Red 68, Acid Red 73, Acid Red 135, Acid Red 138, Acid Red 184, Food Red 1, Food Red 13, Acid Orange 6, Acid Orange 7, Acid Orange 10, Acid Orange 19, Acid Orange 20, Acid Orange 24, Yellow 6, Acid Yellow 9, Acid Yellow 36, Acid Yellow 199, Food Yellow 3 ; Acid Violet 7, Acid Violet 14, Acid Blue 113, Acid Blue 117, Acid Black 1, Acid Brown 4, Acid Brown 20, Acid Black 26, Acid Black 52, Food Black 1, Food Black 2, Food Yellow 3 or sunset yellow ; and by way of example of dyes of formula (G′), mention may be made of: Acid Red 111, Acid Red 134, Acid Yellow 38.

b) the anionic azo pyrrazolone dyes of formula (H) and (H') below:

in which :
- R ₁₁ , R ₁₂ and R ₁₃ , which are identical or different, represent a hydrogen or halogen atom, an alkyl group or -(O) ₂ S(O-), M+ with M+ as defined previously;
- R ₁₄ represents a hydrogen atom, an alkyl group or a -C(O)O- group, M+ with M+ as defined previously;
- R ₁₅ represents a hydrogen atom;
- R ₁₆ represents an oxo group in which case R' ₁₆ is absent, or else R ₁₅ with R ₁₆ together form a double bond;
- R ₁₇ and R ₁₈ , identical or different, represent a hydrogen atom, or a group chosen from:
- (O) ₂ S(O-)-, M+ with M+ as defined above;
- Ar-OS(O) ₂ - with Ar representing an optionally substituted aryl group; preferably a phenyl optionally substituted by one or more alkyl groups;
- R ₁₉ and R ₂₀ together form either a double bond or a benzo group D', optionally substituted;
- R′ ₁₆ , R′ ₁₉ and R′ ₂₀ , which are identical or different, represent a hydrogen atom or an alkyl or hydroxy group;
- R ₂₁ represents a hydrogen atom, an alkyl or alkoxy group;
- R _a and R _b which are identical or different, are as defined above, preferably R _a represents a hydrogen atom and R _b represents an aryl group;
- Y represents either a hydroxy group or an oxo group;

represents a single bond when Y is an oxo group; and represents a double bond when Y represents a hydroxy group;
it being understood that the formulas (H) and (H') comprise at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+ on one of the rings D or E ; preferentially sodium sulfonate.

By way of example of dyes of formula (H), mention may be made of: Acid Red 195, Acid Yellow 23, Acid Yellow 27, Acid Yellow 76, and by way of example of dyes of formula (H'), mention may be made of: Acid Yellow 17.

c) the anthraquinone dyes of formulas (J) and (J') below:

in which R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ and R ₂₇ , which are identical or different, represent a hydrogen atom, a halogen atom, or a group chosen from:
- alkyl;
- hydroxy, mercapto;
- alkoxy, alkylthio;
- optionally substituted aryloxy or arylthio, preferentially substituted by one or more groups chosen from alkyl and (O) ₂ S(O-)-, M+ with M+ as defined previously;
- aryl(alkyl)amino optionally substituted by one or more groups chosen from alkyl and (O) ₂ S(O-)-, M+ with M+ as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- (O) ₂ S(O-)-, M+ with M+ as defined above;
and in which:
Z' represents a hydrogen atom or an NR ₂₈ R ₂₉ group with R ₂₈ and R ₂₉ , which are identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- polyhydroxyalkyl such as hydroxyethyl;
- aryl optionally substituted by one or more particularly i) alkyl groups such as methyl, n-dodecyl, n-butyl; ii) (O) ₂ S(O-)-, M+ with M+ as defined above; iii) R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R°, X, X' and X'' as defined above, preferably R° represents an alkyl group;
- cycloalkyl; in particular cyclohexyl;
Z represents a group chosen from hydroxy and NR′ ₂₈ R′ ₂₉ with R′ ₂₈ and R′ ₂₉ , which are identical or different, represent the same atoms or groups as R ₂₈ and R ₂₉ as defined above;
it being understood that the formulas (J) and (J') comprise at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferentially sodium sulphonate.

Examples of dyes of formula (J) include: Acid Blue 25, Acid Blue 43, Acid Blue 62, Acid Blue 78, Acid Blue 129, Acid Blue 138, Acid Blue 140, Acid Blue 251, Acid Green 25, Acid Green 41, Acid Violet 42, Acid Violet 43, Mordant Red 3, EXT violet #2; and by way of example of dyes of formula (J′), mention may be made of: Acid Black 48.

d) nitro dyes of formulas (K) and (K') below:

in which R ₃₀ , R ₃₁ and R ₃₂ , which are identical or different, represent a hydrogen or halogen atom, or a group chosen from:
- alkyl;
- alkoxy optionally substituted by one or more hydroxy groups, alkylthio optionally substituted by one or more hydroxy groups;
- hydroxy, mercapto;
- nitro, nitroso;
- polyhaloalkyl;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R°, X, X' and X '' as previously defined;
- (O) ₂ S(O-)-, M+ with M+ as defined previously;
- (O)CO--, M+ with M+ as defined previously;
- (di)(alkyl)amino;
- (di)(hydroxyalkyl)amino;
- heterocycloalkyl such as piperidino, piperazino or morpholino; particularly R ₃₀ , R ₃₁ and R ₃₂ represent a hydrogen atom;
and in which:
- Rc and Rd, identical or different, represent a hydrogen atom or an alkyl group;
- W is as defined previously; W particularly represents an –NH– group;
- ALK represents a divalent linear or branched, C ₁ -C ₆ alkylene group; particularly ALK represents a -CH ₂ -CH ₂ - group;
- n is 1 or 2;
- p represents an integer comprised inclusively between 1 and 5;
- q represents an integer comprised inclusively between 1 and 4;
- u is 0 or 1;
- when n is 1, J represents a nitro or nitroso group; especially nitro;
- when n is 2, J represents an oxygen or sulfur atom, or a divalent radical –S(O) _m – with m representing an integer 1 or 2; preferably J represents a –SO ₂ – radical;
- M' represents a hydrogen atom or a cationic counterion;

present or absent represents a benzo group optionally substituted by one or more R ₃₀ groups as defined previously;
it being understood that the formulas (K) and (K') comprise at least one sulfonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferentially sodium sulphonate.

By way of example of dyes of formula (K), mention may be made of: Acid Brown 13, Acid Orange 3; as examples of dyes of formula (K'), mention may be made of: Acid Yellow 1, Sodium salt of 2,4-dinitro-1-naphthol-7-sulfonic acid, 2-piperidino 5-nitro benzene acid sulfonic acid, 2(4'-N,N(2''-hydroxyethyl)amino-2'-nitro)aniline ethane sulfonic acid, 4-β-hydroxyethylamino-3-nitrobenzene sulfonic acid; EXT D&C yellow 7.

e) triarylmethane dyes of formula (L) below:

in which :
- R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ , which are identical or different, represent a hydrogen atom or a group chosen from alkyl, optionally substituted aryl and optionally substituted arylalkyl; particularly an alkyl and benzyl group optionally substituted by an (O) _m S(O-)-, M+ group with M+ and m as defined above;
- R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ , identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- (di)(alkyl)amino;
- hydroxy, mercapto;
- nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;
- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO--, M+ with M+ as defined previously;
- or else two contiguous groups R ₄₁ with R ₄₂ or R ₄₂ with R ₄₃ or R ₄₃ with R ₄₄ together form a fused benzo group: I'; with I' optionally substituted by one or more groups chosen from nitro; nitroso; (O) ₂ S(O-)-, M+; hydroxy; mercapto; (di)(alkyl)amino; R°-C(X)-X'-;R°-X'-C(X)-; ix) R°-X'-C(X)-X''-; with M+, R°, X, X', X'' as defined above;
in particular R ₃₇ to R ₄₀ represent a hydrogen atom, and R ₄₁ to R ₄₄ , which are identical or different, represent a hydroxy or (O) ₂ S(O-)-, M+ group; and when R ₄₃ with R ₄₄ together form a benzo group, it is preferentially substituted by an (O) ₂ S(O-)- group;
it being understood that at least one of the rings G, H, I or I' comprises at least one sulphonate radical (O) ₂ S(O-)- or a carboxylate radical -C(O)O-; preferentially sulfonate.

By way of example of dyes of formula (L), mention may be made of: Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 9, Acid Violet 49, Acid green 3, Acid green 5, Acid Green 50.

f) dyes derived from xanthene of formula (M) below:

in which R ₄₅ , R ₄₆ , R ₄₇ and R ₄₈ , which are identical or different, represent a hydrogen atom or a halogen atom and R ₄₉ , R ₅₀ , R ₅₁ and R ₅₂ , which are identical or different, represent a hydrogen, halogen, or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;
- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO--, M+ with M+ as defined previously;
particularly R ₅₃ R ₅₄ , R ₅₅ and R ₄₈ represent a hydrogen or halogen atom;
and in which:
- G represents an oxygen or sulfur atom or an NRe group with Re as defined previously; particularly G represents an oxygen atom;
- L represents an alcoholate O-, M+; an S-, M+ thioalcoholate or an NRf group, with Rf representing a hydrogen atom or an alkyl group, and M+ as defined above; M+ is particularly sodium or potassium;
- L' represents an oxygen or sulfur atom or an ammonium group: N+RfRg, with Rf and Rg, identical or different, representing a hydrogen atom, an optionally substituted alkyl or aryl group; L' represents in particular an oxygen atom or a phenylamino group optionally substituted by one or more alkyl groups or (O) _m S(O-)-, M+ with m and M+ as defined previously;
- Q and Q', identical or different, represent an oxygen or sulfur atom; particularly Q and Q' represent an oxygen atom;
- M+ is as defined previously.

By way of example of dyes of formula (M), mention may be made of: Acid Yellow 73, Acid Red 51, Acid Red 52, Acid Red 87, Acid Red 92, Acid Red 95, Acid Violet 9.

g) dyes derived from indole of formula (N):

in which R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ and R ₆₀ , identical or different, represent a hydrogen atom or a group chosen from:
- alkyl;
- alkoxy, alkylthio;
- hydroxy, mercapto;
- nitro, nitroso;
- R°-C(X)-X'-, R°-X'-C(X)-, R°-X'-C(X)-X''- with R° representing a hydrogen atom, an alkyl or aryl group; X, X' and X'', identical or different, representing an oxygen, sulfur or NR atom with R representing a hydrogen atom or an alkyl group;
- (O) ₂ S(O-)-, M+ with M+ representing a hydrogen atom or a cationic counterion;
- (O)CO--, M+ with M+ as defined previously;
and in which:
- G represents an oxygen or sulfur atom or an NRe group with Re as defined above; particularly G represents an oxygen atom;
- Ri and Rh, identical or different, represent a hydrogen atom or an alkyl group;
it being understood that formula (N) comprises at least one sulphonate radical (O) ₂ S(O-)-, M+ or a carboxylate radical -C(O)O-, M+; preferentially sodium sulphonate.

Examples of dyes of formula (N) include: Acid Blue 74.

h) dyes derived from quinoline of formula (O) below:

in which :
- R ₆₁ represents a hydrogen or halogen atom or an alkyl group;
- R ₆₂ , R ₆₃ , and R ₆₄ , identical or different, represent a hydrogen atom or a (O) ₂ S(O-)- group, M+ with M+ representing a hydrogen atom or a cationic counterion ;
or else R ₆₁ with R ₆₂ , or R ₆₁ with R ₆₄ , together form a benzo group optionally substituted by one or more (O) ₂ S(O-)- groups, M+ with M+ representing a hydrogen atom or a counter -cationic ion;
it being understood that formula (XVII) comprises at least one sulphonate radical (O) ₂ S(O-)-, M+, preferably sodium sulphonate.

Examples of dyes of formula (O) include: Acid Yellow 2, Acid Yellow 3 and Acid Yellow 5.

Among the natural direct dyes that can be used according to the invention, mention may be made of lawsone, juglone, alizarin, purpurin, carminic acid, kermesic acid, purpurogalline, protocatechaldehyde, indigo, isatin , curcumin, spinulosin, apigenidine, orceins. It is also possible to use extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna.

Preferably, the direct dyes are chosen from anionic direct dyes.

The dyestuffs, preferably the pigments, can be present in concentrations ranging from 0.01 to 30% by weight, preferably from 0.02 to 20% by weight, more particularly from 0.05 to 15% with respect to the total weight of the composition containing them.

The direct dye(s) may be present in concentrations ranging from 0.001 to 10% by weight of the total weight of the composition, preferably from 0.005 to 5% by weight of the total weight of the composition which contains them.

Preferably, the cosmetic active agent(s) AC, in particular the dyestuff(s) and more particularly the pigment(s) are introduced into the compositions C1 under consideration to prepare the compositions C3.

Skincare assets

A composition according to the invention C1, C2, or suitable for the invention, CR, may comprise, as cosmetic active ingredient, at least one care active ingredient, and preferably in the amount of at least 0.01% by weight relative to the total weight of the composition under consideration.

According to a particular form of the invention, a composition according to the invention C3, or suitable for the invention, CAC, comprises, as cosmetic active ingredient, at least one care active ingredient, and preferably at a rate of at least 0.01% by weight relative to the total weight of the composition under consideration.

In particular, the care active may be at least one hydrophilic active and/or one lipophilic active, and preferably a hydrophilic active.

The term “hydrophilic active” means a water-soluble or water-dispersible active capable of forming hydrogen bonds.

The cosmetic care active(s) may in particular be chosen from:
- vitamins and their derivatives, in particular their esters, in particular tocopherol (vitamin E) and its esters (such as tocopherol acetate), ascorbic acid (vitamin C) and its derivatives;
- humectants, in particular urea, hydroxyureas, glycerol, polyglycerols, glycerolglucoside, diglycerolglucoside, polyglycerylglucosides, and xylitylgiucoside, and in particular glycerol;
- C-glycoside compounds;
- antioxidant compounds;
- anti-ageing active agents, in particular hyaluronic acid compounds, and in particular sodium hyaluronate, retinol and its derivatives, salicylic acid compounds and in particular n-octanoyl-5-salycilic acid (acid capryloyl salicylic), caffeine, adenosine, c-beta-d-xylopyranoside-2-hydroxy-propane and 3-hydroxy-2-pentylcyclopentylacetic acid sodium salt;
- skin care agents selected from allantoin, panthenol and protein hydrolysates;
- venotonics, in particular polyphenols, and in particular escin, ruscus, diosmin, hesperidin, resveratrol, and
- their mixtures.

Preferably, the at least one care active ingredient comprises at least one skin care active ingredient.

Preferably, the at least one care active comprises at least one moisturizing agent (also called humectant) and preferably comprises at least glycerin.

According to a particular form of the invention, a composition according to the invention C1, C2, or suitable for the invention, CR, may comprise, as cosmetic active ingredient, at least one care active ingredient, and preferably at least a moisturizing agent (also called humectant).

According to a particular form of the invention, a composition according to the invention C3, or suitable for the invention, CAC, comprises, as cosmetic active ingredient, at least one care active ingredient, and preferably at least one moisturizing agent (also called humectant).

Preferably, the care active is a moisturizing agent, and in particular is glycerin (glycerol).

The care active(s) may in particular be present, in the composition under consideration, in a content ranging from 0.01% to 30% by weight, relative to the weight of the composition, and preferably from 0.02% to 25% in weight.

Preferably, the care active(s), in particular glycerin, are introduced into the compositions C1.

UV filters

A composition according to the invention C1 or C2, or suitable for the invention, CR, may comprise, as cosmetic active ingredient, at least one UV filter.

A composition according to the invention C3, or suitable for the invention, CAC, comprises, as cosmetic active ingredient, at least one UV filter.

The UV filter is a UV filter usually used in cosmetics. It can be chosen from the positive list contained in Annex VI of Regulation (EC) No. 1223/2009, which specifies the list of UV filters authorized in cosmetics.

The UV filters suitable for the invention can be of different types.

They can be organic lipophilic, hydrophilic or insoluble.

By "lipophilic UV filter" is meant any cosmetic or dermatological filter capable of being completely dissolved in the molecular state in a liquid fatty phase or else of being dissolved in colloidal form (for example in micellar form) in a fatty phase. liquid.

By "hydrophilic UV filter" is meant any cosmetic or dermatological filter capable of being completely dissolved in the molecular state in a liquid aqueous phase or else of being dissolved in colloidal form (for example in micellar form) in an aqueous phase. liquid.

By "insoluble UV filter" is meant any cosmetic or dermatological filter which is neither defined as a lipophilic UV filter nor as a hydrophilic UV filter, and which is in the form of particles in the aqueous or liquid fatty phase.

The UV filters of the composition according to the invention can provide UVA and/or UVB photoprotection.

According to a preferred embodiment, the compositions according to the invention, preferably cosmetic, can comprise at least one organic and/or mineral UV filter (filters of UV radiation from sunlight).

In particular, a composition according to the invention C1 or C2, or suitable for the invention, CR, may comprise, as cosmetic active ingredient, at least one UV filter chosen from hydrophilic organic UV filters, organic UV filters lipophilic filters, insoluble organic UV filters, mineral filters, and mixtures thereof.

In particular, a composition according to the invention C3, or suitable for the invention, CAC, may comprise, as cosmetic active ingredient, at least one UV filter chosen from hydrophilic organic UV filters, lipophilic organic UV filters, insoluble organic UV filters, mineral filters, and mixtures thereof.

In particular, these compositions may comprise one or more UV screening agents chosen from bis-resorcinyltriazine derivatives, dibenzoylmethane derivatives, benzylidenecamphor derivatives, and mixtures thereof.

The organic UV filters can also be chosen from anthranilics; cinnamic derivatives; salicylic derivatives; benzophenone derivatives; phenyl benzotriazole derivatives; benzalmalonate derivatives, in particular those cited in US Pat. No. 5,624,663; phenyl benzimidazole derivatives; imidazolines; derivatives of 4,4-diarylbutadienes; bis-benzoazolyl derivatives, as described in patents EP 6,693,23 and US 2,463,264; derivatives of p-aminobenzoic acid (PABA); methylene bis-(hydroxyphenyl benzotriazole) derivatives, as described in applications US Pat. No. 5,237,071, US Pat. benzoxazole derivatives, as described in patent applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 10162844; screening polymers and screening silicones such as those described in particular in application WO 93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE 19855649; 4,4-diarylbutadienes as described in applications EP 0 967 200, DE 19746654, DE 19755649, EP 1 008 586, EP 1 133 980 and EP 133 981; derivatives of other merocyanins such as those described in applications WO 04006878, WO 05058269 and WO 06032741 and mixtures thereof.

According to a particular embodiment, the concentration of organic UV screening agents in the compositions according to the invention varies from 1% to 50%, preferably from 1% to 40% by weight, and again for example ranges from 5% to 35% by weight, relative to the total weight of the composition.

The compositions according to the invention can also comprise mineral UV filters which are generally pigments. The pigments can be coated or uncoated.

Coated pigments are pigments which have undergone one or more surface treatments of a chemical, electronic, mechanochemical and/or mechanical nature with compounds as described for example in Cosmetics & Toiletries, February 1990, Vol. 105, p. 53-64, such as amino acids, beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins, sodium, potassium, zinc, iron or aluminum salts of fatty acids, metal alkoxides (titanium or aluminum), polyethylene, silicones, proteins (collagen, elastin), alkanolamines, silicon oxides, metal oxides or sodium hexametaphosphate.

In a known manner, silicones are organosilicon polymers or oligomers with a linear or cyclic, branched or cross-linked structure, of variable molecular weight, obtained by polymerization and/or polycondensation of suitably functionalized silanes, and consisting essentially of a repetition main units in which the silicon atoms are interconnected by oxygen atoms (siloxane bond), optionally substituted hydrocarbon radicals being directly bonded via a carbon atom on said silicon atoms.

The term “ silicones ” also encompasses the silanes necessary for their preparation, in particular the alkyl silanes.

The silicones used for coating the pigments suitable for the present invention are preferably chosen from the group containing alkyl silanes, polydialkylsiloxanes and polyalkylhydrogenosiloxanes. More preferably still, the silicones are chosen from the group containing octyl trimethyl silane, polydimethylsiloxanes and polymethylhydrogenosiloxanes.

Of course, the metal oxide pigments, before their treatment with silicones, may have been treated with other surfactants, in particular with cerium oxide, alumina, silica, compounds of aluminum, silicon compounds, or mixtures thereof.

Thus, the mineral UV filters can be chosen from coated or uncoated pigments, and in particular from coated titanium oxide pigments, titanium oxides treated with a silicone, uncoated titanium oxide pigments, pigments pigments, coated zinc oxide pigments, uncoated cerium oxide pigments, uncoated iron oxide pigments, coated iron oxide pigments, and mixtures thereof.

Mention may also be made of mixtures of metal oxides, in particular titanium dioxide and cerium dioxide, including the equal weight mixture of silica-coated titanium dioxide and cerium dioxide, sold by the company Ikeda under the name "Sunveil A ", as well as the mixture of titanium dioxide and zinc dioxide coated with alumina, silica and silicone such as the product "M 261" sold by the company Kemira or coated with alumina, silica and glycerine such than the “M 211” product sold by Kemira.

The pigments can be introduced into the compositions according to the invention as such or in the form of a pigment paste, that is to say mixed with a dispersant, as described for example in document GB 2206339.

According to a particular embodiment, the compositions according to the invention are devoid of mineral UV filters.

According to a particular embodiment, the amount of mineral UV screening agent(s), present in the compositions according to the invention, can range from 0.01% to 20% by weight, relative to the total weight of the composition. It ranges for example from 1% to 15% by weight, relative to the total weight of the composition.

According to a particular embodiment, the composition according to the invention also comprises one or more organic UV filters and one or more mineral UV filters.

According to a particular embodiment, the compositions according to the invention comprise a combination of UV filters as described in patent FR 2 977 490, application WO 2013/004777 or application US 2014/0134120.

Preferably, the water-soluble UV screening agent(s) are introduced into a composition according to the invention and in particular into a composition C3, by being mixed with the composition C1 if considered to prepare a composition C3 and/or with the composition CR containing at least one cross-linking agent.

Preferably, the fat-soluble UV screening agent(s) are introduced into a composition according to the invention and in particular into a composition C3, via a separate composition CAC.

According to another preferred embodiment, the inorganic or insoluble UV screening agent(s) are present in composition C1.

Expenses

A composition according to the invention may also comprise one or more fillers, in particular in a content ranging from 0.01% to 30% by weight, relative to the total weight of the composition, preferably ranging from 0.01% to 20 % by weight relative to its total weight.

By “fillers”, is meant particles of any shape, colorless or white, mineral or synthetic, insoluble in the medium of the composition regardless of the temperature at which the composition is manufactured.

These fillers can in particular be used to modify the rheology or the texture of the composition.

By way of illustration of these fillers, mention may be made of talc, mica, silica, kaolin, poly-β-alanine and polyethylene powders, tetrafluoroethylene polymer powders (Teflon®), lauroyl-lysine, starch, boron nitride, polymeric hollow microspheres such as those of polyvinylidene chloride/acrylonitrile such as Expancel® (Nobel Industrie), acrylic acid copolymers, silicone resin microbeads (Tospearls® from Toshiba, for example), elastomeric polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate and hydro-carbonate, hydroxyapatite, barium sulphate, aluminum oxides, polyurethane powders, composite fillers, hollow silica microspheres, and glass or ceramic microcapsules. It is also possible to use particles, which have the shape of portions of hollow spheres, as described in patent applications JP-2003 128 788 and JP-2000 191 789.

other assets

According to a preferred embodiment, a composition C1 or C2 or C3 according to the invention or CR or CAC suitable for the invention comprises at least one additional cosmetic active ingredient.

A composition according to the invention may also contain ingredients commonly used in cosmetics, such as thickeners, gelling agents, trace elements, softeners, sequestrants, perfumes, basifying or acidifying agents, dispersing agents, preservatives, surfactants, anti-hair loss agents, anti-dandruff agents, propellants, polar additives, film-forming polymers different from the CP copolymers of the invention, or mixtures thereof.

Of course, those skilled in the art will take care to choose this or these optional additional compounds and/or their quantity in such a way that the advantageous properties of a composition according to the invention are not, or substantially not, altered by the addition considered.

By way of non-limiting illustration of a composition C1, mention may be made of the compositions comprising in the isododecane at least one block copolymer comprising:
- a first sequence obtained by the copolymerization of isobornyl acrylate and isobornyl methacrylate in a mass ratio of 1/1, and
- a second sequence obtained by the copolymerization of isobutyl acrylate, acetoacetoxyethyl methacrylate and acrylic acid in an isobutyl acrylate/acetoacetoxyethyl methacrylate/acrylic acid mass ratio of 60/15/15,
in which the first sequence/second sequence mass ratio is 70/30,
preferably, a non-volatile oil distinct from isododecane chosen from 2-octyl-1-dodecanol and isononyl isononanoate, and preferably at least one pigment.

By way of non-limiting illustration of compositions C2 or C3, mention may be made of the compositions comprising in the isododecane at least one block copolymer comprising:
- a first sequence obtained by the copolymerization of isobornyl acrylate and isobornyl methacrylate in a mass ratio of 1/1, and
- a second sequence obtained by the copolymerization of isobutyl acrylate, acetoacetoxyethyl methacrylate and acrylic acid in a mass ratio of isobutyl acrylate/acetoacetoxyethyl methacrylate/acrylic acid 60/15/15,
in which the first sequence/second sequence mass ratio is 70/30,
a cross-linking agent chosen from 3-aminopropyl triethoxysilane (APTES), poly(D-Glucosamine), [4-6% (mercaptopropyl) methylsiloxane]-dimethylsiloxane copolymer, poly(dimethylsiloxane) with bis(3-aminopropyl) endings ( PDMS-diNH ₂ ) and bis-cetearyl amodimethicone, preferably a non-volatile oil distinct from isododecane chosen from 2-octyl-1-dodecanol and isononyl isononanoate and preferably at least one pigment.

Composition

A composition C1, C2 or C3 can be in the form of a make-up product, in particular colored, for the skin, in particular a foundation, optionally having care properties, a blush, a blush or eyeshadow, concealer, eyeliner; a lip makeup product such as a lipstick, optionally having care properties, a lip gloss, lip pencils; a make-up product for appendages such as the nails, the eyelashes, in particular in the form of a mascara bar, the eyebrows and the hair, a temporary tattoo product for the skin of the body.

According to a particular embodiment, a composition C1, C2 or C3 according to the invention is in the form:
- or a colored product for the lips;
- or a skincare product, optionally colored, in particular a cream or a fluid having moisturizing and/or filling and/or tightening effect properties; Or
or a hair product, in particular a hair coloring product or even a hair styling product in particular devoid of coloring material, such as a lacquer, or a so-called “styling” product of the mousse or gel type.

Process d ' application of the compositions according to ' invention

The compositions C1, C2 and C3 according to the invention can be applied directly as such to the target keratin material or even be formed directly on the surface of this keratin material.

There are thus distinguished according to the invention three modes of implementation called “1-gesture application mode”, “2-gesture application mode” and “3-gesture application mode”.

The term "1-step method of application" means the direct application to the target keratin material of a single composition in accordance with the invention, namely a composition C1 according to the invention or a composition C2 or C3 according to the invention comprising at least one fatty phase, at least one copolymer CP and at least one crosslinking agent R as described above.

The term "mode of application 2 gestures", the successive application, on the target keratin material, of two different compositions, at least one of which according to the invention. Thus, this 2-step mode of application covers the sequential application to a target keratin material, α) of a composition C1 optionally containing at least one cosmetic active ingredient AC, and β) of a second composition chosen from a composition CR containing at least one crosslinking agent R and optionally at least one cosmetic active agent AC, as defined above, AC preferably being a dyestuff.

According to this mode of application, step α) is preferably followed by step β).

“3-step mode of application” means the sequential application to a target keratin material, α) of a CAC composition comprising one or more cosmetic active ingredient(s), β) of a composition C1 and γ) of a composition CR comprising at least one crosslinking agent R as defined above.

According to this mode of application, step γ) preferably constitutes the last step of said process and more preferably step α) is followed by step β) itself followed by step γ).

In the 2- or 3-step application modes, the composition C1 is conventionally qualified as a “base coat” and the composition which is superimposed on it, generally the composition CR, is qualified as a “top coat”.

These 3 modes of application are detailed and illustrated below.

“1 gesture” application mode

According to one embodiment, a single composition C1 is applied to the keratin materials.

According to another embodiment, a single composition C2 or C3 is applied to the keratin materials.

According to this embodiment, a composition C1 is mixed with at least one crosslinking agent R or a composition CR and optionally with at least one cosmetic active agent AC or a distinct composition CAC before application to the keratin material.

Advantageously, the system remains fluid for a long enough time to allow application to keratin materials such as, for example, the skin or the hair.

According to one particular embodiment, composition C2 is prepared just before application to the keratin materials, for example by mixing a composition C1 and a crosslinking agent R or by mixing a composition C1 and a composition CR containing at least one crosslinker R.

According to a particular embodiment, the resulting composition C2 or C3 is applied to dry keratin materials.

According to a particular embodiment, the keratin materials can be dried after application of the resulting composition C2 or C3.

After application of the composition, a persistent and non-sticky deposit is advantageously obtained. The deposit obtained is also resistant to food oils, water and shampoos.

“2 gestures” application mode

According to a particular embodiment, a composition according to the invention can be implemented according to a so-called “2-step” mode of application.

According to such an embodiment, one applies sequentially to the keratin materials i) a composition C1 according to the invention and ii) a crosslinking agent R or a composition CR comprising at least one crosslinking agent R, CR and R as described below. above.

Preferably, step ii) is subsequent to step i).

According to one particular embodiment, the compositions are applied to dry keratin materials.

According to another particular embodiment, the keratin materials can be dried after application of the compositions, in particular after application of each composition.

After application of the two compositions, a persistent and non-sticky deposit is advantageously obtained. The deposit obtained is also resistant to food oils, water and shampoos.

“3 gestures” application mode

According to a particular embodiment, a composition according to the invention can be implemented according to a so-called “3-step” mode of application.

According to this embodiment, the keratinous materials are applied sequentially to i) a composition CAC containing at least one cosmetic active agent AC, in particular at least one coloring material, preferably at least one pigment, ii) a composition C1 comprising at least one copolymer CP as defined previously and iii) a crosslinking agent R or a composition CR comprising at least one crosslinking agent R, CR and R as described above, and distinct from the composition CAC.

Preferably step iii) is subsequent to step ii).

According to such an embodiment, preferably, a CAC composition comprising at least AC cosmetic active ingredient, in particular at least one dyestuff, and preferably at least one pigment, is applied to the keratin materials.

Successively, a composition C1 as described above, comprising at least one copolymer CP and at least one fatty phase, preferably isododecane, as described above, is applied to the composition CAC.

Successively, a composition CR comprising at least one crosslinking agent R, as described above and distinct from said composition CAC, is applied to the compositions CAC and C1.

According to one particular embodiment, the compositions CAC, C1 and CR are prepared just before application to the keratin materials.

According to one particular embodiment, the compositions are applied to dry keratin materials.

According to one particular embodiment, the keratin materials can be dried after application of the compositions, in particular after application of each composition.

Thus, the compositions C1, C2, C3 and optionally the compositions CAC and CR can be applied to dry or wet keratin fibers, having undergone rinsing or not, as well as to all types of fibers, light or dark, natural or colored, permed, bleached or straightened.

According to a particular embodiment of the invention, the fibers are washed before application of one of the compositions C1, C2, C3 and optionally of a CAC and/or CR composition. The application to the fibers can be implemented by any conventional means, in particular by means of a comb, a brush, a brush, a sponge or the fingers.

According to one embodiment, the compositions C1, C2, C3 and optionally the compositions CAC and CR are applied to the keratin fibers according to an exposure time of between 1 minute and 10 hours, in particular between 1 minute and 1 hour.

After application of composition C1, C2 or C3 and optionally of one or more CAC and/or CR compositions, the keratin fibers may optionally undergo rinsing.

The keratin fibers are then optionally dried or left to dry, for example at a temperature greater than or equal to 30°C.

According to a particular embodiment, the fibers can be dried at a temperature greater than or equal to 40°C. According to a particular embodiment, the fibers can be dried at a temperature above 40°C and below 100°C.

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 can be implemented with a drying device such as a helmet, a hair dryer, a climazon, etc.

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

After the drying step, a shaping step can be implemented with, for example, a straightening iron, the temperature for the shaping step is between 110 and 220°C, preferably between 140 and 200°C.

After the drying step, a final rinse and/or shampoo can optionally be carried out.

Such an implementation advantageously makes it possible to obtain persistent, non-sticky deposits that are resistant to fatty materials such as edible oils or sebum, and to water as well as to shampoos.

In addition, a 3-step application advantageously improves cosmeticity and brings shine and volume to keratin materials.

More particularly, according to one of its aspects, the present invention relates to a process, in particular cosmetic, for keratin materials, in particular for caring for and/or making up the skin, the lips, the eyelashes and/or the eyebrows and/ or for caring for, styling and/or coloring keratin fibers and preferably the hair, comprising a step of applying to said keratin materials a composition C1 according to the invention, said composition containing at least one CP copolymer as than defined above, at least one fatty phase i) and optionally at least one cosmetic active ingredient, called "AC", chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b) care active ingredients keratin materials, preferably skin, c) UV filters and d) mixtures thereof.

According to another of its aspects, the present invention relates to a particularly cosmetic process for keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows and/or for caring for , styling and/or coloring keratin fibers and preferably hair, comprising a step of applying to said keratin materials a composition C2 or C3 according to the invention, said compositions containing at least one CP copolymer, at least a crosslinking agent R and at least one fatty phase as defined above and optionally at least one cosmetic active agent AC as defined above, in particular at least one dyestuff and in particular at least one pigment.

According to another aspect, the present invention relates to a particularly cosmetic process for keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows and/or for caring for, styling and/or coloring the keratin fibers and preferably the hair, comprising at least the steps consisting in:
(a) bringing all or part of the surface of said keratin materials into contact with a composition C1 according to the invention, and preferably devoid of crosslinking agent and optionally containing at least one cosmetic active agent AC as defined previously; And
(b) bringing all or part of said surface into contact with a so-called “CR” composition distinct from said composition C1 and comprising at least one crosslinking agent R, in particular a crosslinking agent R as defined above, and preferably free of of CP copolymer as defined previously;
with steps (a) and (b) being able to be carried out, simultaneously or sequentially and it being understood that said method can optionally implement at least one cosmetic active ingredient, called “AC”, contained in composition C1 and/or in composition CR and/or optionally in a composition separate from C1 and CR, called "CAC", said AC being chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b) active ingredients for the care of keratin materials, preferably skin, c) UV filters and d) mixtures thereof.

Cosmetic treatment process

According to another of its aspects, the present invention relates to a process for making up the skin, in particular the lips, the eyelashes, the eyebrows, comprising a step of applying to the skin or the said lips or the eyelashes or the eyebrows, of a C3, in particular containing at least one dyestuff in particular as defined previously and more particularly at least one pigment.

According to another of its aspects, the present invention relates to a process for making up the skin, in particular the lips, eyelashes or eyebrows, comprising at least the sequential application:
- of a composition C1 as described above,
- a crosslinker R or a composition CR containing at least one crosslinker R,
it being understood that said composition C1 or composition CR contains at least one dyestuff as defined above, preferably at least one pigment. Preferably, composition C1 is applied before the crosslinking agent R or the composition CR containing at least one crosslinking agent R.

According to another of its aspects, the present invention relates to a process for making up the skin, in particular the lips, eyelashes or eyebrows, comprising at least three successive steps consisting in applying sequentially i) a CAC composition containing at least one coloring agent AC, ii) a composition C1, iii) a crosslinking agent R or a composition CR containing at least one crosslinking agent R, it being understood that said method uses at least one cosmetic active ingredient AC denoting a coloring material, in particular a pigment.

Preferably, composition C1 is applied before the crosslinking agent R or the composition CR containing at least one crosslinking agent R.

Preferably, said makeup process comprises at least the steps consisting of:
- apply to the skin, in particular the lips, the eyelashes or the eyebrows, a CAC composition containing at least one AC coloring matter, in particular at least one pigment and optionally at least one care active ingredient as defined above:
- apply, in contact with said CAC composition applied to the skin, the eyelashes or the eyebrows, a composition C1;
- Applying, in contact with said composition C1, applied in contact with said composition CAC, a crosslinking agent R or a composition CR comprising at least one crosslinking agent.

According to another of its aspects, the present invention relates to a care process, in particular non-therapeutic and cosmetic, for the skin, in particular the face or the lips, comprising a step of applying to the skin at least one composition C1, C2 or C3 according to the invention.

According to another of its aspects, the present invention relates to a care process, in particular non-therapeutic and cosmetic, for the skin, in particular the face or the lips, comprising a step of applying to the skin a composition C3, in particular containing at least one moisturizing cosmetic active ingredient, in particular glycerol, and optionally at least one coloring material as defined above.

According to another of its aspects, the present invention relates to a care process, in particular non-therapeutic and cosmetic, for the skin, in particular the face or the lips, comprising the sequential application:
- of a composition C1 as described above, and
- a crosslinker R or a composition CR containing at least one crosslinker R,
it being understood that said composition C1 and/or said composition CR contains at least one moisturizing cosmetic active agent such as glycerol and optionally at least one coloring material.

Preferably, composition C1 is applied before the crosslinking agent R or the composition CR containing at least one crosslinking agent R.

According to yet another of its aspects, the present invention relates to a care process, in particular non-therapeutic and cosmetic, for the skin, in particular the face or the lips, comprising at least the sequential application:
- a CAC composition containing at least one AC cosmetic active ingredient,
- of a composition C1,
- a crosslinking agent R or a composition CR comprising at least one crosslinking agent R,
it being understood that said method uses at least one cosmetic active agent AC designating a care active agent, in particular a moisturizing active agent, in particular glycerol and optionally at least one coloring material as defined previously.

Preferably, composition C1 is applied before the crosslinking agent R or the composition CR containing at least one crosslinking agent R.

Preferably, said method comprises at least the three successive steps consisting in:
- apply to said skin a CAC composition containing at least one AC cosmetic active ingredient, in particular at least one care active ingredient, preferably at least one moisturizing active ingredient such as glycerol, and optionally at least one coloring matter as defined above,
- apply, in contact with said CAC composition applied to the skin, a composition C1,
- apply, in contact with said composition C1, applied in contact with said composition CAC, a crosslinking agent R or a composition CR comprising at least one crosslinking agent R.

According to another of its aspects, the present invention relates to a process for dyeing keratin fibers, preferably human keratin fibers such as the hair, comprising a step of applying to said keratin fibers a composition C1, C2 or C3 according to the invention, said composition C1, C2 or C3 containing at least one dyestuff, in particular as defined above.

According to another of its aspects, the present invention relates to a process for dyeing keratin fibres, preferably human keratin fibers such as the hair, comprising a step of applying to said keratin fibers a composition C3 according to invention, said composition C3 containing at least one coloring agent, in particular as defined above.

According to another of its aspects, the present invention relates to a process for dyeing keratin fibers, preferably human keratin fibers such as the hair, comprising at least the sequential application:
- of a composition C1 as described above, and
- a crosslinker R or a composition CR containing at least one crosslinker R,
it being understood that said composition C1 and/or said composition CR contains at least one dyestuff as defined above, preferably at least one pigment.

Preferably, composition C1 is applied before the crosslinking agent R or the composition CR containing at least one crosslinking agent R.

According to another of its aspects, the present invention relates to a process for dyeing keratin fibres, preferably human keratin fibers such as the hair, comprising at least the three successive steps consisting in applying sequentially i) a CAC composition containing at at least one coloring matter AC, ii) a composition C1, iii) a crosslinking agent R or a composition CR containing at least one crosslinking agent R, it being understood that said method uses at least one cosmetic active ingredient AC designating a coloring matter, in particular a pigment.

Preferably, composition C1 is applied before the crosslinking agent R or the composition CR containing at least one crosslinking agent R.

Preferably, said coloring process comprises at least the steps consisting of:
- applying to said keratin fiber a CAC composition containing at least one AC coloring matter, in particular at least one pigment and optionally at least one care active ingredient as defined above,
- applying, in contact with said CAC composition applied to the keratin fibre, a composition C1,
- Applying, in contact with said composition C1, applied in contact with said composition CAC, a crosslinking agent R or a composition CR comprising at least one crosslinking agent.

According to another of its aspects, the present invention relates to a process for styling keratin fibers, in particular human keratin fibers and in particular the hair, comprising a step of applying to the keratin fibers a composition C1, C2 or C3 as previously defined according to the invention.

According to another of its aspects, the present invention relates to a process for styling keratin fibers, preferably human keratin fibers such as the hair, comprising a step of applying to said keratin fibers a composition C3 according to the invention. , said composition C3 optionally containing at least one cosmetic active agent AC, in particular a dyestuff as defined previously.

According to another of its aspects, the present invention relates to a method for styling keratin fibres, preferably human keratin fibers such as, comprising at least the sequential application:
- of a composition C1 as described previously and
- a crosslinking agent R or a composition CR containing at least one crosslinking agent R,
it being understood that said composition C1 or composition CR optionally contains at least one cosmetic active agent AC, in particular a dyestuff as defined above, preferably at least one pigment. Preferably, composition C1 is applied before the crosslinking agent R or the composition CR containing at least one crosslinking agent R.

According to another of its aspects, the present invention relates to a process for styling keratin fibres, preferably human keratin fibers such as the hair, comprising at least the three successive steps consisting in applying sequentially i) a CAC composition containing at at least one cosmetic active agent AC, ii) a composition C1, iii) a crosslinking agent R or a composition CR containing at least one crosslinking agent R.

Preferably, composition C1 is applied before the crosslinking agent R or the composition CR containing at least one crosslinking agent R.

In particular, said styling method comprises at least the steps consisting of:
- the application to said keratin fiber of a CAC composition containing at least one AC cosmetic active ingredient, in particular at least one coloring matter, in particular at least one pigment and optionally at least one care active ingredient as defined above,
- the application, in contact with said CAC composition applied to the keratin fibre, of a composition C1, and
- the application, in contact with said composition C1, applied in contact with said composition CAC, of a crosslinking agent R or of a composition CR comprising at least one crosslinking agent R.

set

According to yet another of its aspects, the present invention also relates to a kit, in particular cosmetic, for keratin materials, in particular for the care and/or makeup of the skin and/or the lips, the eyelashes, the eyebrows and/or for the care, styling and/or coloring of keratin fibers and preferably the hair, comprising:
- a first compartment containing at least one fatty phase as defined above and at least one copolymer CP, optionally at least one cosmetic active agent AC as defined above, and preferably devoid of crosslinking agent R;
- a second compartment distinct from the first and containing at least one crosslinking agent R, in particular as defined above, preferably devoid of copolymer CP; And
- optionally, a third compartment distinct from the first and second compartments and containing at least one AC cosmetic active ingredient, identical to or different from that/those possibly contained in the first and second compartments and as defined above;
it being understood that the first and/or second compartments may also contain one or more identical or different AC cosmetic active agents and that said AC cosmetic active agent is chosen from a) coloring agents chosen from pigments, direct dyes and mixtures thereof, b) active agents for caring for keratin materials, preferably the skin, in particular moisturizing agents such as glycerol, c) UV filters, and d) mixtures thereof.

Throughout the description, including the claims, the expression "comprising a" must be understood as being synonymous with "comprising at least one", unless otherwise specified.

The expressions “between … and …”, “comprises of … to …”, “formed from … to …”, and “ranging from … to …” must be understood as limits included, unless otherwise specified.

The invention is illustrated in more detail by the examples presented below. Unless otherwise indicated, the quantities indicated are expressed in percentage by mass.

Examples

Methods and Measures

1 . Styling application: Protocol of ' styling evaluation

The styling evaluation protocol is detailed below:

A 1g lock of 90% white natural hair is wrapped around a brush.

2 g of a solution containing the polymer at 10% in isododecane are sprayed on the wick. The lock is weighed before and after application. Approximately 0.5 g of the solution containing the polymer is actually deposited on the lock.

The wick is measured immediately after application and 24 hours later, after storage at room temperature.

A comparison is made with a wick on which only isododecane has been sprayed.

2 . Application coloring capillary

The hair color assessment protocol is detailed below:

The evaluations are carried out according to three different protocols: in 1, 2 or 3 step(s), each on locks of natural hair at 90% white.

a) 1-step protocol

The composition is prepared just before application.

It is applied to dry hair in a bath ratio of 0.5 g of formula per gram of hair.

The wick is dried with a hair dryer.

Shampoo resistance evaluations are conducted 24 hours after application of the composition.

The resistance to the shampoo(s) can then be evaluated visually and/or by measuring the colorimetric data of each of the locks with a spectrophotometer of the Minolta CM-3610d type.

b) 2-step protocol

A first composition, called “base coat”, is applied to dry hair according to a bath ratio of 0.5 g of composition per gram of hair.

The wick is dried with a hair dryer.

3 hours after the application of the “base coat”, a second composition, called “top coat”, is applied according to a bath ratio of 0.5 g of composition per gram of hair.

The wick is again dried with a hair dryer.

Shampoo resistance evaluations are conducted 24 hours after the application of the “top coat”.

The resistance to the shampoo(s) can then be evaluated visually and/or by measuring the colorimetric data of each of the locks with a spectrophotometer of the Minolta CM-3610d type.

c) 3-step protocol

A composition comprising a pigment in a cosmetic medium such as water or isododecane is applied to dry hair.

The wick is dried with a hair dryer.

Immediately after drying, a composition, called a “base coat”, is applied according to a bath ratio of 0.5 g of composition per gram of hair.

The wick is again dried with a hair dryer.

3 hours after the application of the “base coat”, a composition, called “top coat”, is applied according to a bath ratio of 0.5 g of composition per gram of hair.

The wick is once again dried with a hair dryer.

Shampoo resistance evaluations are conducted 24 hours after the application of the “top coat”.

The resistance to the shampoo(s) can then be evaluated visually and/or by measuring the colorimetric data of each of the locks with a spectrophotometer of the Minolta CM-3610d type (Illuminant D65).

The colored locks of hair are combed then moistened under a trickle of water at 35°C before being passed between the fingers 5 times then wrung out between two fingers. A standard shampoo (Garnier Ultra Doux®) is then applied evenly to the locks at the rate of 0.4 g of shampoo per gram of lock by gently kneading the locks lengthwise. 10 passes are made from root to tip. The locks impregnated with shampoo are rinsed under running water at 35°C by passing each lock between the fingers (15 passages) then wringing them out between two fingers before the next shampoo. Once the desired number of shampoos is achieved, the locks of hair are combed and then dried with a hair dryer.

3. Colorimetric evaluation

These evaluations were carried out by spectrocolorimetry by measuring the L*, a* and b* colorimetric data using a Minolta CM-3610d (Illuminant D65) type spectrophotometer.

In the L* system, a*, b*, L* represents lightness, a* represents the green/red color axis and b* the blue/yellow color axis. The higher the value of L, the lighter the color or the weaker the color intensity. Conversely, the lower the value of L, the darker and more intense the color. The higher the value of a*, the more the shade is red and the higher the value of b*, the more the shade is yellow.

Using this system, it is assessed on the one hand, if the rise in hair color obtained with a composition according to the invention is acceptable, and on the other hand if the subsequent hair coloring, that is to say say before shampoo is affected by successive shampoos. Thus, the rise in color, or capacity of the fibers to be colored, is evaluated by the variation in coloring between the locks of the colored keratin fibers and of the same keratin fibers before coloring.

The increase in color on the hair (ΔΕ), or the capacity of the fibers to be colored, is evaluated by the variation in coloring between the locks of the colored keratin fibers and the same fibers before coloring according to the following equation:

In this equation, L*, a* and b* represent the values measured after coloring the keratin fibers and L ₀ *, a ₀ * and b ₀ * represent the values measured before coloring the keratin fibers which are natural white hair to at least minus 90% (BN).

The higher the value of the rise in color ΔΕ, the more the fibers were colored and the coloring effective.

The persistence of the color, or the resistance of the color of the keratin fibers vis-à-vis external aggressions such as shampoos, is evaluated by the difference in rise ΔΕ before and after aggressions here successive shampoos, of said fibers. The lower the variation, the more the color persists.

4. Skin application

The composition, of the “base coat” type, containing a polymer with acetoacetate functions is produced using a Speed Mixer (2 minutes at 3500 revolutions per minute). This "base coat" is applied to a Bioskin-type vitro support (support simulating an elastomer skin) using a film puller (wet thickness 100 µm). The deposit is left to dry for 24 hours.

A composition, of the “top coat” type, containing an amine compound is then applied.

After 24 hours of drying, the deposits obtained are evaluated according to points 4 to 6 below.

5. Resistance to ' oil ' olive or ' water

0.5 mL of olive oil or water is applied to the deposit. After 5 minutes, the olive oil or water is removed by 15 passes with a cotton ball. The deterioration of the deposit resulting from its contact with olive oil or water is thus observed.

The resistance is evaluated according to the following scale:
+++: no attack on the deposit which is as it was originally,
++: a little transfer but the deposit is as it was originally,
+: the deposit is a little altered and a little transfer is observed.

6. Test d ' adhesion to the substrate

A piece of adhesive tape ( ^Scotch® Magic™ 810 from 3M; l=19 mm, L=5 cm) is applied to the deposit. A mass of approximately 1070 g is applied to the piece of tape for 30 seconds. The adhesive tape is then removed and applied to a slide to observe the amount of residual deposit on the adhesive tape. The adhesion of the film to the support is thus evaluated.

The adhesion of the deposit to the support is evaluated according to the following scale:
+++: no transfer of the repository which is as originally,
++: a little transfer but the deposit is as it was originally,
+: deposit transfer.

7. Fragmentation test

The Bioskin ^® plate on which the deposit is located is manually stretched 10 times.

The degree of fragmentation (or cracking) of the deposit is then observed in order to determine whether it is cohesive or not.

The fragmentation of the film is evaluated according to the following scale:
+++: no fragmentation, the repository is intact,
++: fragmentation is observed but no hole is formed in the deposit,
+: fragmentation is observed, accompanied by holes in the deposit.

Example AT : Preparation of copolymer 1: cop olympic e re pseudo-block with acetoacetate function

In a 1L controlled reactor, 150 mL of isododecane are maintained at 90°C.

A mixture composed of 150 g of isododecane, 1.8 g of Trigonox T141 initiator, 105 g of isobornyl acrylate and 105 g of isobornyl methacrylate is poured in 1 hour then left to react for 1 hour 30 minutes. at 90°C.

Then, a mixture composed of 60 g of isobutyl acrylate, 1.2 g of Trigonox T141 initiator, 15 g of acetoacetoxyethyl methacrylate and 15 g of acrylic acid is poured in 30 minutes.

The reaction medium is maintained for 3 hours at 90°C.

At the end of the reaction, 150 g of isododecane of isododecane are introduced. The next day, the reaction medium is stripped with 2×300 mL of isodecane. A dry extract of polymer at 54.12% in isododecane is obtained.

Example 1 : Compositions according to ' invention for application 1 step capillary

The composition of examples 1 according to the invention comprising copolymer 1, as prepared in example A above, is prepared from the contents indicated in the table below. The contents are expressed in percentage by weight, relative to the total weight of the composition.

Color build-up and hair color resistance to shampoo tests are carried out with the composition of Example 1, according to the one-step protocol, detailed in points 2 and 3 above in the “Methods and Measures” section. ".

The table below details the number of shampoos and reports the colorimetric values measured.

It appears from the table above that the treatment of keratin fibers with the composition of the invention of example 1 makes it possible to color said fibers intensely and chromatically with a very significant increase in color.

In addition, the composition according to the invention tested confers resistance to coloring even after 10 successive shampoos since no significant variation in the colorimetric parameters has been observed or measured.

It was also observed visually that the chromatic coloring (in particular in the reds) is unchanged between the coloring obtained just after application of the composition of example 1 according to the invention, and after 10 successive shampoos. This observation is confirmed by a small variation in the values of ΔE.

In addition, it was also observed that the keratin fibers appear individualized after application of the compositions of example 1 according to the invention, with a respected volume and this even after 10 shampoos. Advantageously, the touch is also very pleasant.

Examples 2 - 4 : Compositions according to ' invention for hair application in 2 stage s

The compositions of examples 2 to 4 according to the invention comprising copolymer 1, as prepared in example A above, are prepared from the contents indicated in the table below. The contents are expressed in percentage by weight, relative to the total weight of the composition.

Color rise and shampoo resistance tests are carried out for the "base coat" and "top coat" combinations of the compositions of examples 2 to 4, according to the 2-step protocol, detailed in points 2 and 3 above. in the “Methods and measurements” section.

The table below details the number of shampoos and reports the colorimetric values measured.

It appears from the table above that the treatment of keratin fibers with the compositions of the invention of examples 2 to 4 makes it possible to color said fibers intensely and chromatically with a very significant increase in color.

In addition, the compositions according to the invention tested confer resistance to staining even after several successive shampoos for the composition of Example 2 since no significant variation in the colorimetric parameters was observed or measured.

It was also observed visually that the chromatic coloring (in particular in the reds) is unchanged between the coloring obtained just after application of the composition of example 2 according to the invention, and after 3 successive shampoos. This observation is confirmed by a small variation in the value of ΔE.

In addition, it was also observed that the keratin fibers appear individualized after application of the compositions of examples 2 to 4 according to the invention, with a respected volume and this even after several shampoos. Advantageously, the touch is also very pleasant.

Example 5 : Composition according to ' invention for application 3 step capillary

The composition of example 5 according to the invention comprising copolymer 1, as prepared in example A above, is prepared from the contents indicated in the table below. The contents are expressed as percentage by weight, relative to the total weight of the composition considered.

A color rise test is carried out for the "base coat", "top coat" and "Pigment" combination of example 5 according to the invention, according to the 3-step protocol, detailed in points 2 and 3 above. above in the “Methods and measurements” section.

It appears from the table above that the treatment of keratin fibers with the compositions of the invention of example 5 makes it possible to color said fibers intensely and chromatically with a very significant increase in color.

In addition, it was also observed that the keratin fibers appear individualized after application of the compositions of example 5 according to the invention, with a respected volume. Advantageously, the touch is also very pleasant.

Examples 6 - 10 : Compositions according to ' invention for application makeup

The compositions of examples 6 to 10 according to the invention comprising copolymer 1, as prepared in examples A, above, are prepared from the contents indicated in the table below. The contents are expressed in percentage by weight, relative to the total weight of the composition considered.

For each of examples 6 to 10 according to the invention, the evaluations are carried out according to points 4 to 7 of the “Methods and measurements” section above. These evaluations are carried out on successive deposits of the “base coat” (or C1) and then “top coat” (or CR) compositions and reported in the table below.

Resistance to ' water

The deposits made with the compositions of the “base coat” type then of the “top coat” type of Examples 6 to 10 according to the invention advantageously exhibit very good water resistance.

Deposits resistant to daily chemical attacks are therefore advantageously obtained thanks to the compositions according to the invention.

Resistance to ' oil

The deposits made with the compositions of the "base coat" type and then of the "top coat" type of examples 6 to 10 according to the invention, also advantageously have good resistance to oil, in particular, the compositions of examples 6 to 9 have very good oil resistance.

Deposits resistant to daily chemical attacks are therefore advantageously obtained thanks to the compositions according to the invention.

Adhesion to the support

The successive application of the composition of the “top coat” type on the composition of the “base coat” type, according to Examples 6 to 10, makes it possible to significantly improve the adhesion, in particular to the support of the final cosmetic product. The compositions of Examples 6, 7, 9 and 10 exhibit good adhesion to the substrate and the compositions of Example 8 exhibit very good adhesion to the substrate.

Fragmentation

The successive application of the “top coat” type composition on the “base coat” type composition, according to Examples 1 to 3, makes it possible to significantly improve the cohesion of the final cosmetic product. In particular, the compositions of Examples 9 and 10 exhibit very good cohesion.

Examples 11 - 12 : Compositions according to ' invention for application styling

The composition of examples 11 and 12 according to the invention comprising copolymer 1, as prepared in example A above, are prepared from the contents indicated in the table below. The contents are expressed as percentage by weight, relative to the total weight of the composition considered.

For examples 11 and 12 according to the invention, an evaluation is carried out according to point 1 of the “Methods and measurements” part above. A test was carried out according to the styling application protocol at point 1 compared to comparative examples not comprising any treatment of the locks or consisting in treating a lock only with water, isododecane or with (3- Aminopropyl) triethoxysilane (APTES) (from Sigma Aldrich) at 5% by weight in isododecane.

The wick lengths measured after application and 24 hours after application are given in the table below:

The compositions of Examples 11 and 12 allow corporization of the hair fiber. The curls obtained after treatment of the keratin fibers with these compositions are very marked, with curl heights, that is to say lock lengths after treatment, which are reduced by 30 to 70%, whereas the curls obtained with the Water, isododecane and/or APTES are not very marked with a very small loop radius. The compositions of Examples 11 and 12 according to the invention make it possible to maintain a very marked curl effect even after 24 hours, unlike locks treated with isododecane or APTES. A significant persistence of the curl effect was also observed for locks treated with the composition of example 12, without noting after 24 hours a difference in the height of the curled lock.

Claims (25)

Composition, called “C1”, in particular cosmetics for keratin materials, and in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows and/or for caring for, styling and/or or the coloring of keratin fibres, preferably the hair, comprising at least one fatty phase containing at least one block copolymer called “CP” comprising:
- at least one first block having a glass transition temperature (T _g ) greater than or equal to 40 ° C, and obtained from at least one monomer (A) of (alkyl) acrylate of formula (I):

in which :
• R ¹ represents hydrogen or a (C ₁ -C ₄ )alkyl group, linear or branched, preferably R ¹ represents a methyl group; And
• R ² represents a C ₄ to C ₁₂ cycloalkyl group; And
- at least one second sequence having a glass transition temperature (T _g ) less than or equal to 20°C, and obtained from at least:
(i) a monomer (B) of formula (II):

in which :
• R ^a represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, linear or branched, preferably a methyl group;
• R ^b and R ^c , identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group, linear or branched, preferably R ^b and R ^c represent a hydrogen atom;
• R ^d represents a (C ₁ -C ₄ )alkyl group, linear or branched, preferably R ^d represents a methyl group; And
• L represents a (C ₁ -C ₆ )alkylene group, linear or branched, or cycloalkylene, in particular L represents a (C ₁ -C ₄ )alkylene group, preferably L represents ethylene;
and preferably monomer (B) is acetoacetoxyethyl methacrylate;
(ii) an (alkyl)acrylate monomer (C) of formula (III):

in which :
• R ¹ represents a hydrogen atom or a radical (C ₁ -C ₄ )alkyl, linear or branched, preferably R ¹ represents a methyl group; And
• R ³ represents an unsubstituted (C ₁ -C ₄ )alkyl group, linear or branched, with the exception of the tert-butyl group, or a methoxyethyl group; And
(iii) a monomer (D) chosen from ethylenically unsaturated monomers comprising at least one carboxylic, phosphoric and/or sulphonic acid function, maleic anhydride and its derivatives, and itaconic anhydride and its derivatives. Composition according to the preceding claim, said block copolymer comprising from 60% to 80% by weight of the first block and from 20% to 40% by weight of the second block, and preferably comprising from 65% to 75% by weight of the first sequence and from 25% to 35% by weight of the second sequence, relative to its total weight. Composition according to any one of the preceding claims, the first block having a glass transition temperature (T _g ) greater than or equal to 60°C, in particular varying from 60°C to 150°C, more particularly varying from 60°C at 140°C, and preferably ranging from 80°C to 120°C. Composition according to any one of the preceding claims, the first sequence being obtained from:
a) at least one acrylate monomer (A1) of formula (V):

in which R ² represents a C ₄ to C ₁₂ cycloalkyl group, in particular R ² represents an (iso)bornyl group, and
b) at least one (alkyl)acrylate monomer (A2) of formula (VI):

in which R' ¹ represents a (C ₁ -C ₄ )alkyl group, linear or branched, preferably R' ¹ represents a methyl group and R ² represents a C ₄ to C ₁₂ cycloalkyl group;
and preferably the first block is obtained from isobornyl methacrylate and isobornyl acrylate. Composition according to the preceding claim, the first block being obtained from monomers (A1) and (A2) as defined in claim 4, in a mass ratio (A1)/(A2) varying from 30:70 to 70:30, in particular varying from 40:60 to 60:40, and preferably varying from 45:55 to 55:45. Composition according to any one of the preceding claims, the first block further comprising at least one additional monomer chosen from linear or branched C ₈ -C ₂₂ alkyl (meth)acrylates, in particular chosen from 2 -ethylhexyl, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, behenyl acrylate, behenyl methacrylate, stearyl acrylate and stearyl methacrylate. Composition according to any one of the preceding claims, the second block having a glass transition temperature (T _g ) less than or equal to 10°C, in particular less than or equal to 0°C, preferably varying from -100°C to 0°C, and more preferably varying from -30°C to 0°C. Composition according to any one of the preceding claims, the second sequence being obtained from:
(i) at least one monomer (B) as defined in claim 1, preferably acetoacetoxyethyl methacrylate,
(ii) at least one monomer (C) as defined in claim 1, preferably isobutyl acrylate, and
(iii) at least one monomer (D) as defined in claim 1, preferably acrylic acid. Composition according to any one of the preceding claims, the second block further comprising at least one additional silicone monomer of formula (IX):
(IX)
in which :
- R ₈ represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, linear or branched, preferably R ₈ represents a methyl group;
- R ₉ represents a divalent hydrocarbon group, saturated or unsaturated, preferably saturated, linear or branched, having from 1 to 10 carbon atoms, and optionally containing one or two ether bonds -O-;
- R ₁₀ represents a linear or branched alkyl group having from 1 to 10 carbon atoms; And
- n represents an integer from 1 to 300;
and preferably the second block further comprises at least one additional silicone monomer chosen from monomethacryloyloxypropyl polydimethylsiloxanes. A composition according to any preceding claim, wherein said block copolymer comprises:
- a first sequence obtained by the copolymerization of isobornyl acrylate and isobornyl methacrylate in a mass ratio of 1/1, and
- a second sequence obtained by the copolymerization of isobutyl acrylate, acetoacetoxyethyl methacrylate and acrylic acid in an isobutyl acrylate/acetoacetoxyethyl methacrylate/acrylic acid mass ratio of 60/15/15,
and wherein the first sequence/second sequence mass ratio is 70/30. Composition according to any one of the preceding claims, comprising from 1% to 60% by weight, preferably from 2% to 30% by weight of said block copolymer, relative to the total weight of the composition. Composition according to any one of the preceding claims, comprising at least one hydrocarbon-based oil, preferably chosen from C ₈ -C ₁₄ hydrocarbon-based oils and mixtures thereof, and more preferably comprising at least isododecane and optionally at least one oil not volatile distinct from said hydrocarbon-based oil, preferably chosen from non-volatile hydrocarbon-based oils, more preferably chosen from fatty alcohols having from 12 to 26 carbon atoms, synthetic esters and mixtures thereof. Composition according to any one of the preceding claims, containing at least in the isododecane a block copolymer comprising
- a first sequence obtained by the copolymerization of isobornyl acrylate and isobornyl methacrylate in a mass ratio of 1/1, and
- a second sequence obtained by the copolymerization of isobutyl acrylate, acetoacetoxyethyl methacrylate and acrylic acid in a mass ratio of isobutyl acrylate/acetoacetoxyethyl methacrylate/acrylic acid 60/15/15,
in which the first sequence/second sequence mass ratio is 70/30,
preferably a non-volatile oil distinct from isododecane chosen from 2-octyl-1-dodecanol and isononyl isononanoate, and preferably at least one pigment. Composition called "C2" according to any one of the preceding claims, comprising at least one crosslinking agent, called "R", and optionally at least one cosmetic active ingredient, called "AC", chosen from a) coloring agents chosen from pigments , direct dyes, and mixtures thereof, b) active ingredients for caring for keratin materials, preferably the skin, c) UV screening agents and d) mixtures thereof. Composition called "C3" according to the preceding claim, comprising at least one cosmetic active ingredient, called "AC", chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b) active ingredients for caring for keratins, preferably of the skin, c) UV filters and d) mixtures thereof. Composition according to Claim 14 or 15, in which the said crosslinking agent is chosen from (poly)amino, (poly)thiolated and/or (poly)hydroxylated, (poly)carbonyl and (poly)acrylate compounds, and mixtures thereof, and preferably chosen from (poly)amine and (poly)thiolated compounds, with in particular said (poly)amine being chosen from chitosans, aminoalkoxysilanes and polydimethylsiloxanes comprising primary amine groups at the end of the chain or on the side chains, and even more preferably chosen from poly(D-Glucosamine), 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N -(2-aminoethyl)-3-aminopropyltriethoxysilane and polydimethylsiloxanes comprising at the end of the chain of the aminopropyl terminal groups, and even more preferably is 3-aminopropyl triethoxysilane (APTES) and in particular said (poly)thiolated compound, being chosen from polydiorganosiloxanes containing thiol functions, aminosilicones with thiol functions, alkoxysilanes with thiol functions, organic polythiols, natural products modified with thiol groups, amino thiols derived from dendrimers or polyethyleneimines (PEI) and silicone thiols, preferably the compound ( poly)thiol being chosen from polydimethylsiloxanes terminated with mercaptopropyl groups and dimethicone/mercaptopropyl methicone copolymers. Composition according to any one of the preceding claims, characterized in that it comprises in the isododecane at least one block copolymer comprising
- a first sequence obtained by the copolymerization of isobornyl acrylate and isobornyl methacrylate in a mass ratio of 1/1, and
- a second sequence obtained by the copolymerization of isobutyl acrylate, acetoacetoxyethyl methacrylate and acrylic acid in a mass ratio of isobutyl acrylate/acetoacetoxyethyl methacrylate/acrylic acid 60/15/15,
in which the first sequence/second sequence mass ratio is 70/30,
a cross-linking agent chosen from 3-aminopropyl triethoxysilane (APTES), poly(D-Glucosamine), [4-6% (mercaptopropyl) methylsiloxane]-dimethylsiloxane copolymer, poly(dimethylsiloxane) with bis(3-aminopropyl) endings ( PDMS-diNH ₂ ) and bis-cetearyl amodimethicone, preferably a non-volatile oil distinct from isododecane chosen from 2-octyl-1-dodecanol and isononyl isononanoate and preferably at least one pigment. Composition according to any one of the preceding claims, which is in the form:
- or a colored product for the lips;
- or a skincare product, optionally colored, in particular a cream or a fluid having moisturizing and/or filling and/or tightening effect properties; Or
or a hair product, in particular a hair coloring product or even a hair styling product in particular devoid of coloring material, such as a lacquer, or a so-called “styling” product of the mousse or gel type. Process, in particular cosmetic, for keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows and/or for caring for, styling and/or coloring keratin fibers and preferably hair, consisting in applying to said keratin materials a composition C1 according to any one of Claims 1 to 13, optionally at least one crosslinking agent R, in particular according to Claim 16, and optionally at least one cosmetic active agent AC , chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b) active agents for caring for keratin materials, preferably the skin, c) UV screening agents and d) mixtures thereof. Process, in particular cosmetic for keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows and/or for caring for, styling and/or coloring keratin fibers and preferably hair, comprising at least the steps of:
(a) bringing all or part of the surface of said keratin materials into contact with a composition C1 according to any one of Claims 1 to 13, and preferably devoid of crosslinking agent; And
(b) bringing all or part of said surface into contact with a so-called “CR” composition distinct from said composition C1 and comprising at least one crosslinking agent R, in particular according to claim 16;
with steps (a) and (b) being able to be carried out, simultaneously or sequentially and it being understood that said method can optionally implement at least one cosmetic active ingredient, called “AC”, contained in composition C1 and/or in composition CR and/or optionally in a composition separate from C1 and CR, called "CAC", said AC being chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b) active ingredients for the care of keratin materials, preferably skin, c) UV filters and d) mixtures thereof. Process for making up the skin, in particular the lips, comprising a step of applying to the said skin at least one composition C1, C2 or C3 according to any one of Claims 1 to 18, and at least one coloring matter with in particular said method comprising at least the two successive steps consisting in applying sequentially to said skin i) at least one composition C1 according to any one of Claims 1 to 13, and ii) a crosslinking agent R or a composition CR containing at least a crosslinking agent R in particular according to claim 16, it being understood that said composition C1 and/or said composition CR contains at least one dyestuff or said method comprising at least the three successive steps consisting in applying sequentially to the skin i) a composition CAC containing at least one dyestuff, ii) a composition C1 according to any one of claims 1 to 13, and iii) a crosslinking agent R or a composition CR con containing at least one crosslinking agent R in particular according to claim 16 with said composition C1 and/or said composition CR containing, where appropriate, at least one dyestuff. Care process, in particular non-therapeutic and cosmetic, for the skin, in particular the face or the lips, comprising a step of applying to the said skin at least one composition C1, C2 or C3 according to any one of Claims 1 to 18 and at least one moisturizing cosmetic active; with in particular said method comprising at least the two successive steps consisting in applying sequentially to said skin: i) a composition C1 according to any one of Claims 1 to 13, and ii) a crosslinking agent R or a composition CR containing at least one cross-linking agent R in particular according to claim 16; it being understood that said composition C1 and/or said composition CR contains at least one moisturizing cosmetic active ingredient, in particular glycerol, and optionally at least one coloring material or said method comprising at least the three successive steps consisting in applying sequentially to the skin i) a CAC composition, ii) a composition C1 according to any one of claims 1 to 13, and iii) a crosslinking agent R or a composition CR containing at least one crosslinking agent R in particular according to claim 14 with said CAC composition and/or composition C1 and/or composition CR containing at least one moisturizing cosmetic active ingredient, in particular glycerol and optionally a coloring material. Process for styling keratin fibers, in particular human keratin fibers, in particular hair, comprising a step of applying to said fibers a composition C1, C2 or C3 according to any one of Claims 1 to 18. Process for dyeing keratin fibers, preferably human keratin fibers such as hair and eyebrows, comprising a step of applying to said keratin fibers a composition C1, C2, or C3 according to any one of Claims 1 to 18, and at least one coloring agent with in particular said method comprising at least the two successive steps consisting in applying sequentially to said fibers i) at least one composition C1 according to any one of Claims 1 to 13, and ii) a crosslinking agent R or a composition CR containing at least one crosslinking agent R in particular according to claim 16, it being understood that said composition C1 and/or said composition CR contains at least one dyestuff or said process comprising at least the three successive steps consisting in applying sequentially i) a composition CAC containing at least one dyestuff, ii) a composition C1 according to any one of rev indications 1 to 13, and iii) a crosslinking agent R or a composition CR containing at least one crosslinking agent R, in particular according to claim 16 with said composition C1 and/or said composition CR containing, where appropriate, at least one dyestuff. Kit, in particular cosmetics, for keratin materials, in particular for caring for and/or making up the skin, lips, eyelashes and/or eyebrows, and/or for caring for, styling and/or coloring the keratin fibers and preferably hair, comprising:
- a first compartment containing at least one composition C1 according to any one of claims 1 to 13, and preferably devoid of crosslinking agent R;
- a second compartment distinct from said first compartment and comprising at least one crosslinking agent R, in particular according to claim 16; And
- where applicable, a third compartment distinct from the first and second compartments containing at least one cosmetic active ingredient, called “AC”, identical to or different from that/those possibly contained in the first and/or second compartments;
it being understood that the first and/or second compartments may also contain one or more identical or different AC cosmetic active agents and that said AC active agent is chosen from a) coloring agents chosen from pigments, direct dyes, and mixtures thereof, b ) active ingredients for caring for keratin materials, preferably the skin, c) UV filters and d) mixtures thereof.