FR3109313A1 - PROCESS FOR TREATMENT OF KERATINIC MATERIALS USING AN ACRYLIC ANHYDRIDE POLYMER IN OILY DISPERSION AND A HYDROXYL AND / OR THIOLE COMPOUND - Google Patents

Abstract

Title: PROCESS FOR TREATMENT OF KERATINIC MATERIALS IMPLEMENTING AN ACRYLIC POLYMER OF ANHYDRIDE IN OILY DISPERSION AND OF A HYDROXYL AND / OR THIOLE COMPOUND The present invention relates to a process for treating keratin materials, preferably keratin fibers, in particular human fibers such as the hair, or human skin, in particular of the lips and preferably in at least two stages, firstly implementing the application to said materials of an oily dispersion A) comprising i) particles of copolymers d alkyl acrylates and acrylic anhydrides, ii) stabilizers, iii) one or more hydrocarbon oils; then in a second step the application to said materials of a composition (B) comprising iv) one or more hydroxylated and / or thiolated compounds, it being understood that the process of the invention uses v) one or more active ( s) cosmetic (s) chosen from a) pigments, b) active agents for caring for keratin materials, preferably the skin, and c) UV filters and d) mixtures thereof; the ingredients a) to d) possibly being in composition (A), and / or in composition (B), and / or in another composition (C). The process of the invention makes it possible to obtain a treatment of said keratin materials resistant in particular to sweat, to shower gels, to water and to fatty substances, in particular vegetable or animal edible oils, and more particularly vegetable oils such as olive, sunflower, walnut, hazelnut oil, etc. The process for treating keratin materials of the present application is also suitable for making up the skin or the lips, such as foundations and lipsticks. .

Description

METHOD FOR THE TREATMENT OF KERATIN MATERIALS USING AN ACRYLIC POLYMER OF ANHYDRIDE IN OILY DISPERSION AND A HYDROXYL AND/OR THIOLE COMPOUND

The present invention relates to a method for treating keratin materials, preferably keratin fibers, in particular human fibers such as the hair, or human skin, in particular the lips, said method preferably consisting of at least two steps implementing in a first time the application to said materials of an oily dispersion A) comprising i) particles of copolymers of alkyl acrylates and acrylic anhydrides, ii) stabilizing agents, iii) one or more hydrocarbon oils; then in a second step the application to said materials of a composition (B) comprising iv) one or more hydroxylated and/or thiolated compounds, it being understood that the process of the invention implements v) one or more active ( s) cosmetic(s) chosen from a) pigments, b) active agents for caring for keratin materials, preferably the skin or the hair, and c) UV filters as well as d) mixtures thereof; the ingredients a) to d) possibly being in composition (A), and/or in composition (B), and/or in another composition (C).

During the aging process, different signs appear on the skin, very characteristic of this aging, resulting in particular in a modification of the structure and functions of the skin. The main clinical signs of skin aging are in particular the appearance of fine lines and deep wrinkles, which increase with age.

It is known to treat these signs of aging by using cosmetic or dermatological compositions containing active agents capable of combating aging, such as α-hydroxy acids, β-hydroxy acids and retinoids. These active ingredients act on wrinkles by eliminating dead skin cells and accelerating the cell renewal process. However, these active agents have the drawback of only being effective for the treatment of wrinkles after a certain number of applications repeated over time. However, it is increasingly sought to obtain an immediate effect leading rapidly to a smoothing of wrinkles and/or fine lines and to the disappearance of signs of fatigue.

It is known to treat these signs of aging by using cosmetic or dermatological compositions containing active agents capable of combating aging, such as α-hydroxy acids, β-hydroxy acids and retinoids. These active ingredients act on wrinkles by eliminating dead skin cells and accelerating the cell renewal process. However, these active agents have the drawback of only being effective for the treatment of wrinkles after a certain number of applications repeated over time. However, it is increasingly sought to obtain an immediate effect leading rapidly to a smoothing of wrinkles and/or fine lines and to the disappearance of signs of fatigue.

Cosmetic products often require the use of a film-forming polymer with good cosmetic properties to obtain a deposit of the product on keratin materials. In particular, it is necessary that the film-forming deposit does not transfer during contact with the fingers, the clothes, as well as good resistance in contact with water, in particular rain or during the shower or even the perspiration as well as sebum, fats from foods, especially edible oils.

After application, the deposit must also be as invisible to the eye as possible, must not be unsightly or sticky, and must not powder.

It is known to use dispersions of polymer particles of nanometric size, in organic media such as hydrocarbon oils. The polymers are used in particular as a film-forming agent in make-up products such as mascaras, eyeliners, eye shadows or lipsticks. Document EP-A-749747 describes in the examples dispersions in hydrocarbon oils (paraffin oil, isododecane) of acrylic polymers stabilized with polystyrene/copoly(ethylene-propylene) diblock copolymers. The film obtained after application of the dispersion to the skin is not very shiny. Document FR 1362795 also describes the use of dispersions of surface-stabilized polymer particles containing hydrocarbon oils for making up the lips and eyelashes. Document WO-A-2010/046229 describes dispersions in isododecane of acrylic polymers stabilized by stabilizing polymers. Document FR 1362795 describes the use of a dispersion of surface-stabilized polymer particles containing hydrocarbon oils for making up the lips and eyelashes. In addition, the shiny effect, especially on the lips, is not always satisfactory.

Thus, the object of the present invention is to provide a method for treating keratin materials, in particular the skin, preferably human, and more preferably the face, which has good resistance to external aggressions, and in time, said treatment consisting, for example, of a tightening effect, of care, of protection against Ultraviolet (UV) rays and/or of make-up such as make-up of the face and in particular of the lips.

In the field of hair, there is also a need for film-forming materials which can be deposited on the surface of the hair without weighing it down or sticking the keratin fibers together, the appearance of which must remain as natural as possible. Thus, in the field of dyeing keratin fibres, it is already known to dye keratin fibers by various techniques using direct dyes for non-permanent dyes or dye precursors for permanent dyes.

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

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

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

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

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

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

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

The colors obtained by this method of coloring have the disadvantage of being eliminated from the first shampoo.

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

It is also known from patent 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.

It is also known to use, in other cosmetic fields, dispersions of polymer particles of nanometric size, in organic media such as hydrocarbon oils. The polymers are used in particular as a film-forming agent in make-up products such as mascaras, eyeliners, eye shadows or lipsticks. Document EP-A-749747 describes in the examples dispersions in hydrocarbon oils (paraffin oil, isododecane) of acrylic polymers stabilized with polystyrene/copoly(ethylene-propylene) diblock copolymers. The film obtained after application of the dispersion to the skin is not very shiny. Document FR 1362795 also describes the use of dispersions of surface-stabilized polymer particles containing hydrocarbon oils for making up the lips and eyelashes. Document WO-A-2010/046229 describes dispersions in isododecane of acrylic polymers stabilized by stabilizing polymers. In prepared by radical polymerization controlled by reversible chain transfer.

Document FR 1 362 795 describes the use of a dispersion of surface-stabilized polymer particles containing hydrocarbon oils for making up the lips and eyelashes.

Thus, the object of the present invention is also to provide a method for treating keratin fibers having good resistance to attacks such as brushing, not bleeding, resistant to sweat, light and bad weather, resistant to shampoos and to the various aggressions that said fibers may undergo without degradation of said fibers and while retaining perfectly individualized keratin fibers.

1. une ou plusieurs particule(s) constituée(s) d’un ou plusieurs copolymère(s) éthylénique :

1. de (C₁-C₄)(alkyl)acrylate de (C₁-C₄)alkyle, de préférence le (méth)acrylate de (C₁-C₄)alkyle et
2. de composé anhydride à insaturation éthylénique, de préférence d’anhydride maléique; et

1. un ou plusieurs agents stabilisants constitué(s) de polymères éthyléniques choisis parmi :

1. les polymères de monomères (C₁-C₆)(alkyl)acrylate de (C₃-C₁₂)cycloalkyle ; et
2. copolymères de (C₁-C₆)(alkyl)acrylate de (C₃-C₁₂)cycloalkyle et (C₁-C₄)(alkyl)acrylate de (C₁-C₄)alkyle ; et

1. une ou plusieurs huile(s) hydrocarbonée(s) ;

et ’application sur lesdites matières d’une composition (B) distincte de (A), anhydre ou non, de préférence anhydre, comprenant :

1. un ou plusieurs composé(s) hydroxylé(s) et/ou thiolé(s) polymérique(s) ou non, de préférence organique(s) et/ou siliconé(s) ;

étant entendu que :

• le procédé met de l’invention en œuvre v) un ou plusieurs actif(s) cosmétique(s) choisi(s) parmi a) les agents colorants choisis parmi les pigments, les colorants directs et leur mélanges, b) les actifs de soin des matières kératiniques de préférence de la peau ou des cheveux et c) les filtres UV ainsi que d) leur mélanges les ingrédients a) à d) pouvant se trouver dans la composition (A), et/ou dans la composition (B), et/ou dans une autre composition (C) ; et

les compositions (A), (B) et (C) peuvent être appliquée ensemble ou séparément.The technical problems have been solved by the method of the invention, which is a method for treating keratin materials, preferably α) keratin fibers, in particular human fibers such as the hair, or β) human skin, in particular the lips, comprising the application to said materials of an oily dispersion (A), preferably anhydrous, comprising:

1. one or more particle(s) consisting of one or more ethylenic copolymer(s):

1. of (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl, preferably (meth)acrylate of (C ₁ -C ₄ )alkyl and
2. an ethylenically unsaturated anhydride compound, preferably maleic anhydride; And

1. one or more stabilizing agents consisting of ethylenic polymers chosen from:

1. polymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl monomers; And
2. copolymers of (C ₁ -C ₆ )(alkyl)acrylate, (C ₃ -C ₁₂ )cycloalkyl and (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl; And

1. one or more hydrocarbon oil(s);

and the application to said materials of a composition (B) distinct from (A), anhydrous or not, preferably anhydrous, comprising:

1. one or more hydroxylated and/or thiolated compound(s), polymer(s) or not, preferably organic(s) and/or silicone(s);

Being heard that :

• the process implements the invention v) one or more cosmetic active ingredient(s) chosen from a) coloring agents chosen from pigments, direct dyes and mixtures thereof, b) care active ingredients keratin materials, preferably skin or hair, and c) UV screening agents and d) mixtures thereof, the ingredients a) to d) which may be found in composition (A), and/or in composition (B), and/or in another composition (C); And

the compositions (A), (B) and (C) can be applied together or separately.

1. l’application sur lesdites matières d’une dispersion huileuse (A), de préférence anhydre, comprenant :

1. une ou plusieurs particule(s) constituée(s) d’un ou plusieurs copolymère(s) éthylénique :

1. de (C₁-C₄)(alkyl)acrylate de (C₁-C₄)alkyle, de préférence le (méth)acrylate de (C₁-C₄)alkyle et
2. de composé anhydride à insaturation éthylénique, de préférence d’anhydride maléique; et

1. un ou plusieurs agents stabilisants constitué(s) de polymères éthyléniques choisis parmi :

1. les polymères de monomères (C₁-C₆)(alkyl)acrylate de (C₃-C₁₂)cycloalkyle ; et
2. copolymères de (C₁-C₆)(alkyl)acrylate de (C₃-C₁₂)cycloalkyle et (C₁-C₄)(alkyl)acrylate de (C₁-C₄)alkyle ; et

1. une ou plusieurs huile(s) hydrocarbonée(s) ; suivie de

1. l’application sur lesdites matières d’une composition (B), distincte de (A), anhydre ou non, de préférence anhydre, comprenant :

1. un ou plusieurs composé(s) hydroxylé(s) et/ou thiolé(s), de préférence thiolé(s), polymérique(s) ou non, de préférence polymérique(s), de préférence siliconé(s) ;

étant entendu que le procédé de l’invention met en œuvre v) un ou plusieurs actif(s) cosmétique(s) choisi(s) parmi a) les agents colorants choisis parmi les pigments, les colorants directs et leur mélanges , b) les actifs de soin des matières kératiniques notamment de la peau ou des cheveux et c) les filtres UV ainsi que d) leur mélanges, les ingrédients a) à d) pouvant se trouver dans la composition (A), et/ou dans la composition (B), et/ou dans une autre composition (C).More preferably, the process of the invention relates to a process for treating keratin materials, preferably α) keratin fibres, in particular human fibers such as the hair, or β) human skin, in particular the lips, comprising:

1. the application to said materials of an oily dispersion (A), preferably anhydrous, comprising:

1. one or more particle(s) consisting of one or more ethylenic copolymer(s):

1. of (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl, preferably (meth)acrylate of (C ₁ -C ₄ )alkyl and
2. an ethylenically unsaturated anhydride compound, preferably maleic anhydride; And

1. one or more stabilizing agents consisting of ethylenic polymers chosen from:

1. polymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl monomers; And
2. copolymers of (C ₁ -C ₆ )(alkyl)acrylate, (C ₃ -C ₁₂ )cycloalkyl and (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl; And

1. one or more hydrocarbon oil(s); followed by

1. the application to said materials of a composition (B), distinct from (A), anhydrous or not, preferably anhydrous, comprising:

1. one or more hydroxylated and/or thiolated compound(s), preferably thiolated(s), polymeric or not, preferably polymeric(s), preferably silicone(s);

it being understood that the process of the invention implements v) one or more cosmetic active ingredient(s) chosen from a) coloring agents chosen from pigments, direct dyes and mixtures thereof, b) active ingredients for caring for keratin materials, in particular the skin or the hair, and c) UV filters as well as d) mixtures thereof, the ingredients a) to d) possibly being in composition (A), and/or in composition ( B), and/or in another composition (C).

This process for treating keratin materials, in particular the skin, in at least two successive steps using, in a first step, the oily dispersion (A) as defined above, then, in a following step, a composition (B) comprising one or more amine compounds as defined above and optionally a composition (C), makes it possible to obtain a treatment of said keratinous materials resistant in particular to sweat, shower gels, water and fatty substances, in particular vegetable or animal edible oils, and more particularly vegetable oils such as olive oil, sunflower oil, walnut oil, hazelnut oil, etc.

The process for treating keratin materials of the present application is also suitable for making up the skin, including the lips, such as foundations and lipsticks.

The present patent application also relates to a process, in particular cosmetic, for caring for or making up the skin, the lips of which, more particularly the skin of the face, in particular the wrinkled skin, comprising the topical application to the skin including the lips, in particular cosmetic compositions, (A) and (B) and optionally (C), as described above.

The invention also relates to a process, in particular cosmetic, for caring for the skin, more particularly the skin of the face, in particular the wrinkled skin, comprising the topical application to the skin of the compositions, in particular cosmetics, (A) , and (B) and optionally (C), as previously described.

The method of the present patent application is in particular intended to smooth the human skin of the face and/or the body and/or to reduce or erase the signs of skin aging, in particular to reduce or erase wrinkles and/or fine lines. skin.

A subject of the invention is also the cosmetic use as a tightening agent for the skin, in particular for wrinkled skin, of compositions, in particular cosmetics, (A), and (B) and optionally (C), such as previously described.

The term “ tensioning agent ” is understood to mean compounds capable of having an apparent tensioning effect, that is to say of smoothing the skin and reducing, or even causing the disappearance, very quickly or even immediately, of wrinkles and fine lines.

The tightening effect can be characterized by an in vitro shrinkage test.

The present patent application also relates to a process, in particular cosmetic, for coloring keratin materials, in particular human keratin fibers such as the hair, comprising the topical application to the keratin materials of the compositions, in particular cosmetics, (A) and (B ) and optionally (C), as described above, it being understood that said coloring process uses v) one or more cosmetic active ingredient(s) chosen from a) coloring agents chosen from pigments, direct dyes and mixtures thereof, preferably pigments,

This process for treating keratin fibres, in particular human keratin fibers such as the hair, in at least two successive steps using, during a first step, the oily dispersion (A) as defined above and then during a following step a composition (B) comprising one or more hydroxylated compound(s) and/or thiolated compound(s) as defined above and optionally a composition (C), makes it possible to obtain a treatment of said fibers which is resistant in particular to shampoo(s) (s) and water. When said process is a coloring process as described above, that is to say using v) one or more cosmetic active ingredient(s) chosen from a) pigments, it appears that the colors obtained on fibers after treatment are intense, chromatic, and/or a good rise in color. The colors remain particularly chromatic even after several successive shampoos.

The process in accordance with the present invention makes it possible in particular to obtain, on keratin fibers, sheathings, in particular colored ones, having a visible coloring on all types of fibers, in particular on dark hair, in a remanent manner to shampoos while preserving the physical qualities of the keratin fiber. Such a sheathing is in particular resistant to the external aggressions that the hair may undergo, such as blow-drying and perspiration. In particular, it makes it possible to obtain a smooth and homogeneous deposit. Furthermore, it has surprisingly been observed that the keratin fibers remained perfectly individualized and could be styled without any problem.

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

• un «radical alkyle» est un groupe hydrocarboné saturé en C₁-C₈, linéaire ou ramifié, en particulier en C₁-C_6,de préférence en C₁-C₄tel que méthyle, éthyle, isopropyle, et t-butyle;
• un «radical alcoxy» est un groupe alkyle-oxy avec alkyle tel que défini précédemment de préférence alcoxy en C₁-C₄tel que méthoxy, éthoxy ;
• l’expression «éventuellement substitué» attribué au radical alkyle sous-entend que ledit radical alkyle peut être substitué par un ou plusieurs radicaux choisis parmi les radicaux i) hydroxy, ii) alcoxy en C₁-C₄, iii) acylamino, iv) amino éventuellement substitué par un ou deux radicaux alkyle, identiques ou différents, en C₁-C₄, lesdits radicaux alkyles pouvant former avec l’atome d’azote qui les portent un hétérocycle comprenant de 5 à 7 chaînons, comprenant éventuellement un autre hétéroatome différent ou non de l’azote ;
• lorsque le groupement alcoxy est éventuellement substitué, cela sous-entend que le groupe alkyle est éventuellement substitué tel que défini supra.
• un radical «cycloalkyle» est un groupe hydrocarboné cyclique saturé comprenant de 1 à 3 cycles, de préférence 1 ou 2 cycles, notamment 2 cycles et comprenant de 3 à 13 atomes de carbone, de préférence entre 5 et 10 atomes de carbone, tel que cyclopentyle, cyclohexyle, cycloheptyle, norbornyle, ou isobornyle le radical cycloalkyle pouvant être substitué par un ou plusieurs groupes (C₁-C₄)alkyle tel que méthyle, de préférence le radical cycloalkyle est un groupe isobornyle ;
• un radical «cyclique» est un groupe hydrocarboné cyclique, saturé ou insaturé, aromatique ou non aromatique, comprenant de 1 à 3 cycles, de préférence 1 cycle, et comprenant de 3 à 10 atomes de carbone tel que cyclohexyle ou phényle;
• un radical «hétéro cyclique» est un groupe hydrocarboné cyclique, saturé ou insaturé, aromatique ou non aromatique, comprenant de 1 à 3 cycles, de préférence 1 cycle, et comprenant de 3 à 10 atomes de carbone, et de 1 à 5 hétéroatomes choisis parmi O, S, et N tel que morpholinyle, pipérazinyle, pipéridinyle, furyle, pyridinyle, indolyle ;
• un radical «aryle» est un radical cyclique hydrocarboné, insaturé aromatique, comprenant de 6 à 12 atomes de carbones, mono ou bicyclique, fusionné ou non, de préférence le groupe aryle comprend 1 cycle et à 6 atomes de carbone tel que phényle ;
• un radical « aryloxy » est un radical aryle-oxy i.e. aryl-O- avec aryle tel que défini précédemment, de préférence phénoxy;
• un radical « aryl(C₁-C₄)alcoxy » est un radical aryl-(C₁-C₄)alkyle-O-, de préférence benzoxy ;
• un «groupe alkylène» représente un chaîne divalente en C₁-C₁₈; particulièrement en C₁-C₆, plus particulièrement en C₁-C₂lorsque la chaîne est linéaire ; éventuellement substituée par un ou plusieurs, identiques ou différents, groupements choisis parmi, (C₁-C₂)alcoxy, (di)(C₁-C₂) (alkyl)amino, R^a-Z^a-C(Z^b)-, et R^a-Z^a-S(O)_t- avec Z^a, Z^b, identiques ou différents, représentant un atome d’oxygène, de soufre, ou un groupe NR^a’, R^a, représentant un métal alcalin, un atome d’hydrogène, un groupement alkyle ou alors est absent si une autre partie de la molécule cationique et R^a’ représentant un atome d’hydrogène ou un groupement alkyle et t vaut 1 ou 2 ; de préférence le groupe« alkylène» est un groupe hydrocarboné saturé divalent en C₁-C₈, linéaire ou ramifié, en particulier en C₁-C_6,de préférence en C₁-C₄tel que méthylène, éthylène, ou propylène ;
• une «chaîne hydrocarbonée divalente en C ₁ -C ₃₀ , saturée ou insaturée, éventuellement substituée», représente une chaîne hydrocarbonée, particulièrement an C₁-C₈, comprenant éventuellement une ou plusieurs doubles liaisons π, conjuguée ou non, particulièrement la chaîne hydrocarbonée est saturée ; ladite chaîne est éventuellement substituée par un ou plusieurs, identiques ou différents, groupements choisis parmi, (C₁-C₂)alcoxy, (di)(C₁-C₂) (alkyl)amino, R^a-Z^a-C(Z^b)-, et R^a-Z^a-S(O)_t- avec Z^a, Z^b, identiques ou différents, représentant un atome d’oxygène, de soufre, ou un groupe NR^a’, R^a, représentant un métal alcalin, un atome d’hydrogène, un groupement alkyle ou alors est absent si une autre partie de la molécule cationique et R^a’ représentant un atome d’hydrogène ou un groupement alkyle et t vaut 1 ou 2 ;

• les radicaux «aryle» ou «hétéroaryle» ou la partie aryle ou hétéroaryle d’un radical peuvent être substitués par au moins un substituant porté par un atome de carbone, choisi parmi :
  • un radical alkyle en C₁-C₈, éventuellement substitué par un ou plusieurs radicaux choisis parmi les radicaux hydroxy, alcoxy en C₁-C₂, (poly)-hydroxyalkoxy en C₂-C₄, acylamino, amino substitué par deux radicaux alkyle, identiques ou différents, en C₁-C₄, éventuellement porteurs d’au moins un groupement hydroxy ou, les deux radicaux pouvant former avec l’atome d’azote auquel ils sont rattachés, un hétérocycle comprenant de 5 à 7 chaînons, de préférence de 5 ou 6 chaînons, saturé ou insaturé éventuellement substitué comprenant éventuellement un autre hétéroatome identique ou différent de l’azote ;
  • un atome d’halogène;
  • un radical alcoxy en C₁-C₂;
  • un radical héterocycloalkyle à 5 ou 6 chaînons ;
  • un radical acylamino (-NR-COR’) dans lequel le radical R est un atome d’hydrogène, un radical alkyle en C₁-C₄et le radical R’ est un radical alkyle en C₁-C₂; un radical carbamoyle ((R)₂N-CO-) dans lequel les radicaux R, identiques ou non, représentent un atome d’hydrogène, un radical alkyle en C₁-C₄; un radical alkylsulfonylamino (R’SO₂-NR-) dans lequel le radical R représente un atome d’hydrogène, un radical alkyle en C₁-C₄et le radical R’ représente un radical alkyle en C₁-C₄, un radical phényle ; un radical aminosulfonyle ((R)₂N-SO₂-) dans lequel les radicaux R, identiques ou non, représentent un atome d’hydrogène, un radical alkyle en C₁-C₄,
  • un radical carboxylique sous forme acide ou salifiée (de préférence avec un métal alcalin ou un ammonium, substitué ou non) ;
  • un groupement cyano ;
  • un groupement polyhalogénoalkyle, préférentiellement le trifluorométhyle ;

la partie cyclique ou hétérocyclique d’un radical non aromatique peut être substituée par au moins un substituant choisi parmi les groupements :

• aloxy en C₁-C₄,
• alkyle en C₁-C₄,
• alkylcarbonylamino (RCO-NR’-) dans lequel le radical R’ est un atome d’hydrogène, un radical alkyle en C₁-C₄et le radical R est un radical alkyle en C₁-C₂,;
• alkylcarbonyloxy (RCO-O-) dans lequel le radical R est un radical alkyle en C₁-C₄, groupement amino éventuellement substitué par un ou deux groupements alkyle identiques ou différents en C₁-C₄, lesdits radicaux alkyle pouvant former avec l’atome d’azote auquel ils sont rattachés, un hétérocycle comprenant de 5 à 7 chaînons, saturé ou insaturé éventuellement substitué comprenant éventuellement au moins un autre hétéroatome différent ou non de l’azote ;
• alkoxycarbonyle (RG-CO-) dans lequel le radical R est un radical alcoxy en C₁-C₄, G est un atome d’oxygène, ou un groupement amino éventuellement substitué par un groupement alkyle en C₁-C₄lui-même, ledit radical alkyle pouvant former avec l’atome d’azote auquel ils sont rattachés, un hétérocycle comprenant de 5 à 7 chaînons, saturé ou insaturé éventuellement substitué comprenant éventuellement au moins un autre hétéroatome différent ou non de l’azote ;
• un radical cyclique, hétérocyclique, ou une partie non aromatique d’un radical aryle ou hétéroaryle, peut également renfermer un ou plusieurs groupements oxo ;
• une chaîne hydrocarbonée est insaturée lorsqu’elle comporte une ou plusieurs liaisons doubles et/ou une ou plusieurs liaisons triples de préférence une ou plusieurs double liaisons ;
• un «radical hétéroaryle» représente un groupement mono ou polycyclique, condensé ou non, comprenant de 5 à 22 chaînons, de 1 à 6 hétéroatomes choisis parmi l’atome d’azote, d’oxygène, de soufre et de sélénium, et dont au moins un cycle est aromatique ; préférentiellement un radical hétéroaryle est choisis parmi acridinyle, benzimidazolyle, benzobistriazolyle, benzopyrazolyle, benzopyridazinyle, benzoquinolyle, benzothiazolyle, benzotriazolyle, benzoxazolyle, pyridinyle, tetrazolyle, dihydrothiazolyle, imidazopyridinyle, imidazolyle, indolyle, isoquinolyle, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyle, oxazolyle, oxazolopyridyle, phénazinyle, phénooxazolyle, pyrazinyle, pyrazolyle, pyrilyle, pyrazoyltriazyle, pyridyle, pyridinoimidazolyle, pyrrolyle, quinolyle, tétrazolyle, thiadiazolyle, thiazolyle, thiazolopyridinyle, thiazoylimidazolyle, thiopyrylyle, triazolyle, xanthylyle.

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

• an " alkyl radical " is a saturated C ₁ -C ₈ hydrocarbon group, linear or branched, in particular C ₁ -C _6, preferably C ₁ -C ₄ such as methyl, ethyl, isopropyl, and t-butyl ;
• an “ alkoxy radical ” is an alkyl-oxy group with alkyl as defined above, preferably C ₁ -C ₄ alkoxy such as methoxy, ethoxy;
• the expression “ optionally substituted ” attributed to the alkyl radical implies that the said alkyl radical can be substituted by one or more radicals chosen from the radicals i) hydroxy, ii) C ₁ -C ₄ alkoxy, iii) acylamino, iv) amino optionally substituted by one or two identical or different C ₁ -C ₄ alkyl radicals, said alkyl radicals being able to form with the nitrogen atom which carries them a heterocycle comprising from 5 to 7 members, optionally comprising another heteroatom different or not from nitrogen;
• when the alkoxy group is optionally substituted, this implies that the alkyl group is optionally substituted as defined above.
• a “ cycloalkyl ” radical is a saturated cyclic hydrocarbon group comprising from 1 to 3 rings, preferably 1 or 2 rings, in particular 2 rings and comprising from 3 to 13 carbon atoms, preferably between 5 and 10 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, norbornyl or isobornyl, the cycloalkyl radical possibly being substituted by one or more (C ₁ -C ₄ )alkyl groups such as methyl, preferably the cycloalkyl radical is an isobornyl group;
• a “ cyclic ” radical is a cyclic hydrocarbon group, saturated or unsaturated, aromatic or non-aromatic, comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms such as cyclohexyl or phenyl;
• a “ cyclic hetero ” radical is a saturated or unsaturated, aromatic or non-aromatic cyclic hydrocarbon group, comprising from 1 to 3 rings, preferably 1 ring, and comprising from 3 to 10 carbon atoms, and from 1 to 5 chosen heteroatoms from O, S, and N such as morpholinyl, piperazinyl, piperidinyl, furyl, pyridinyl, indolyl;
• an “ aryl ” radical is an aromatic unsaturated hydrocarbon cyclic radical comprising from 6 to 12 carbon atoms, mono or bicyclic, fused or not, preferably the aryl group comprises 1 ring and 6 carbon atoms, such as phenyl;
• an “aryloxy” radical is an aryl-oxy radical, ie aryl-O- with aryl as defined above, preferably phenoxy;
• an “aryl(C ₁ -C ₄ )alkoxy” radical is an aryl-(C ₁ -C ₄ )alkyl-O— radical, preferably benzoxy;
• an “ alkylene group ” represents a C ₁ -C ₁₈ divalent chain; particularly C ₁ -C ₆ , more particularly C ₁ -C ₂ when the chain is linear; optionally substituted by one or more, identical or different, groups chosen from (C ₁ -C ₂ )alkoxy, (di)(C ₁ -C ₂ ) (alkyl)amino, R ^a -Z ^a -C(Z ^b ) -, and R ^a -Z ^a -S(O) _t - with Z ^a , Z ^b , which are identical or different, representing an oxygen or sulfur atom, or a group NR ^a ', R ^a , representing an alkali metal , a hydrogen atom, an alkyl group or else is absent if another part of the cationic molecule and R ^a 'representing a hydrogen atom or an alkyl group and t is 1 or 2; preferably the “ alkylene ” group is a divalent C ₁ -C ₈ saturated hydrocarbon group, linear or branched, in particular C ₁ -C _6, preferably C ₁ -C ₄ such as methylene, ethylene or propylene;
• a "divalent C ₁ -C ₃₀ hydrocarbon chain , saturated or unsaturated, optionally substituted ", represents a hydrocarbon chain, particularly an C ₁ -C ₈ , optionally comprising one or more π double bonds, conjugated or not, particularly the hydrocarbon chain is saturated; said chain is optionally substituted by one or more, identical or different, groups chosen from (C ₁ -C ₂ )alkoxy, (di)(C ₁ -C ₂ ) (alkyl)amino, R ^a -Z ^a -C( Z ^b )-, and R ^a -Z ^a -S(O) _t - with Z ^a , Z ^b , which are identical or different, representing an oxygen or sulfur atom, or a group NR ^a ', R ^a , representing an alkali metal, a hydrogen atom, an alkyl group or else is absent if another part of the cationic molecule and R ^a 'representing a hydrogen atom or an alkyl group and t is equal to 1 or 2;

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

the cyclic or heterocyclic part of a non-aromatic radical can be substituted by at least one substituent chosen from the groups:

• C ₁ -C ₄ aloxy,
• C ₁ -C ₄ alkyl,
• alkylcarbonylamino (RCO-NR'-) in which the R' radical is a hydrogen atom, a C ₁ -C ₄ alkyl radical and the R radical is a C ₁ -C ₂ alkyl radical;
• alkylcarbonyloxy (RCO-O-) in which the R radical is a C ₁ -C ₄ alkyl radical, an amino group optionally substituted by one or two identical or different C ₁ -C ₄ alkyl groups, the said alkyl radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from nitrogen;
• alkoxycarbonyl (RG-CO-) in which the radical R is a C ₁ -C ₄ alkoxy radical, G is an oxygen atom, or an amino group optionally substituted by a C ₁ -C ₄ alkyl group itself , said alkyl radical being able to form with the nitrogen atom to which they are attached, a heterocycle comprising from 5 to 7 members, saturated or unsaturated optionally substituted optionally comprising at least one other heteroatom different or not from nitrogen;
• a cyclic or heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, can also contain one or more oxo groups;
• a hydrocarbon chain is unsaturated when it contains one or more double bonds and/or one or more triple bonds, preferably one or more double bonds;
• a “ heteroaryl radical ” represents a mono or polycyclic group, condensed or not, comprising from 5 to 22 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, and of which at least one ring is aromatic; préférentiellement un radical hétéroaryle est choisis parmi acridinyle, benzimidazolyle, benzobistriazolyle, benzopyrazolyle, benzopyridazinyle, benzoquinolyle, benzothiazolyle, benzotriazolyle, benzoxazolyle, pyridinyle, tetrazolyle, dihydrothiazolyle, imidazopyridinyle, imidazolyle, indolyle, isoquinolyle, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyle, oxazolyle, oxazolopyridyle , phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl.

The oily dispersion (A)

The process of the invention uses at least one oily dispersion (A) of i) particles of at least one surface-stabilized polymer with ii) at least one stabilizing agent in a preferably anhydrous medium, additionally containing iii) at least one hydrocarbon oil.

In addition, the dispersions according to the invention consist of particles, generally spherical, of at least one surface-stabilized polymer, in a preferably non-aqueous medium.

Polymer particles i)

The particle(s) of the dispersion of the process of the invention consists of one or more ethylenic copolymer(s) of a) (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ - C ₄ ) alkyl and b) an ethylenically unsaturated anhydride compound.

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

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

According to a preferred embodiment of the invention, the polymer constituting the particles i) is an acrylate copolymer:
a) of formula H ₂ C=C(R)-C(O)-O-R' with R representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl, and R' representing a (C ₁ -C ₄ )alkyl, linear or branched, preferably linear in particular (C ₁ -C ₃ )alkyl, such as methyl or ethyl, preferably C ₁ -C ₄ alkyl (meth)acrylate, linear or branched, preferably linear, in particular (C ₁ -C ₃ )alkyl; And
b) an ethylenically unsaturated anhydride monomer

In particular, the polymer of the particles is a polymer of C ₁ -C ₄ alkyl (meth)acrylate, linear or branched, preferably linear in particular (C ₁ -C ₃ )alkyl and of anhydride monomer with ethylenic unsaturation.

The monomers a) are preferably chosen from methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth)acrylate n-butyl, tert-butyl (meth)acrylate.

Advantageously, a C ₁ -C ₄ alkyl acrylate monomer, linear or branched, preferably linear in particular (C ₁ -C ₃ ) is used. Preferably a) is chosen from methyl acrylate and ethyl acrylate.

The polymer of the particles also comprises an ethylenically unsaturated anhydride monomer b).

Preferably, the ethylenically unsaturated anhydride compound(s) b) of the invention are chosen from derivatives of maleic anhydride (Ia) and itaconic anhydride (Ib).
Formulas (Ia) and (Ib) in which Ra, Rb and Rc, which are identical or different, represent a hydrogen atom or a (C1-C4)alkyl group, preferably Ra, Rb and Rc represent a hydrogen atom .

More preferably, the ethylenically unsaturated anhydride monomer of the invention is of formula (Ia) and even more preferably is maleic anhydride.

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

According to a preferred embodiment of the invention, the copolymer(s) of particles i) of dispersion (A) comprise, from 80 to 99.99% by weight, of ingredient a) and from 0.01 to 20 % by weight of ingredient b), relative to the total weight of the copolymer(s). The preferred amount of a) is between 80 and 99.99% by weight relative to the total weight of the copolymer(s), in particular between 85 and 98%, more preferably between 87 and 94% by weight relative to the total weight of the copolymer(s).

The polymer of the particles can be chosen from: methyl acrylate/maleic anhydride copolymers; ethyl acrylate/maleic anhydride copolymers; and methyl acrylate/ethyl acrylate/maleic anhydride copolymers.

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

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

The polymer of the particles may be present in the dispersion (A) in a content ranging from 20 to 60% by weight, relative to the total weight of the dispersion (A), in particular between 21% to 58.5% by weight, relative to the total weight of the dispersion (A), preferably ranging from 30 to 50% by weight, relative to the total weight of the dispersion (A), more preferably ranging from 36% to 42% by weight relative to the weight total scatter (A).

Preferably, the particle or particles consist of copolymer a) and b) which constitute the core of said particle.

According to a particular embodiment of the invention, the particles i) consist of copolymers a) and b) with a weight ratio a)/b) comprised inclusively between 5.5 and 20, preferably between 6.5 and 16, even more preferably between 6.6 and 15.6.

The stabilizing agent(s) ii)

The dispersion (A) according to the invention also comprises one or more stabilizing agents ii). Preferably only one type of stabilizer ii) is used in the invention.

The stabilizing agent(s) of the invention is (are) constituted by ethylenic polymers chosen from c) polymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl monomers; and d) copolymers of (C ₁ -C ₆ )(alkyl)acrylate, (C ₃ -C ₁₂ )cycloalkyl and (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl.

According to a preferred embodiment of the invention, the stabilizing agent ii) consists of ethylenic polymers chosen from
c) polymers of monomers of formula H₂C=C(R)-C(O)-O-R’’ with R representing a hydrogen atom or group (C₁-VS₄)alkyl such as methyl, and R’’ representing a group (C₅-VS₁₀)cycloalkyl such as norbornyl, or isobornyl preferably isobornyl ; And
d) copolymers of H₂C=C(R)-C(O)-O-R’ and of H₂C=C(R)-C(O)-O-R'' with R, R' and R'' as previously defined.

In particular, the stabilizing agent ii) is an isobornyl (meth)acrylate polymer selected from isobornyl (meth)acrylate homopolymer and random copolymers of isobornyl (meth)acrylate and isobornyl (meth)acrylate. C ₁ -C ₄ alkyl preferably present in a weight ratio of isobornyl (meth)acrylate/C ₁ -C ₄ alkyl (meth)acrylate greater than 4;Advantageously, said weight ratio ranges from 4.5 at 19.

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

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

Advantageously, the set ii) stabilizing agent(s)+i) particle(s) of polymer(s) present in the dispersion (A) comprises from 10 to 50% by weight of copolymers d) and from 50 to 90% by weight of polymers c), relative to the total weight of the whole ii) stabilizing agent(s)+i) particle(s) of polymer(s).

Preferably, the set ii) stabilizing agent(s)+ii) particle(s) of polymer(s) present in the dispersion comprises from 15 to 30% by weight of copolymers d) and from 70 to 85% by weight of polymers c), relative to the total weight of the whole ii) stabilizing agent(s)+i) particle(s) of polymer(s).

The hydrocarbon oil(s) iii)

Dispersion (A) according to the invention comprises one or more identical or different hydrocarbon-based oils, preferably identical.

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

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 can contain groups, ester, ether, carboxylic acid, amide.

Hydrocarbon oil can be volatile or non-volatile

According to a preferred embodiment of the invention, the hydrocarbon oil(s) are volatile or are a mixture of different volatile oils more preferably chosen from isododecane .

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

By “ volatile oil ”, is meant an oil (or non-aqueous medium) capable of evaporating on contact with the skin in less than one hour, at room temperature and at atmospheric pressure. The volatile oil is a volatile cosmetic oil, liquid at ambient temperature, having in particular a non-zero vapor pressure, at ambient temperature and at atmospheric pressure, in particular, having a vapor pressure ranging from 0.13 Pa to 40,000 Pa (10 ^-3 to 300 mm Hg), and preferably ranging from 1.3 Pa to 13,000 Pa (0.01 to 100 mm Hg), and preferably ranging from 1.3 Pa to 1300 Pa (0.01 to 10mm Hg).

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

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

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

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

Dispersion (A) may comprise a silicone oil in addition to the hydrocarbon oil. If silicone oil is present in the dispersion (A), it is preferably present in an amount which does not exceed 10% by weight relative to the weight of the dispersion (A), more particularly in an amount less than 5% and more preferably 2%. The term “ silicone oil ” means an oil comprising at least one silicon atom, and in particular at least one Si—O group. The silicone oil can be volatile or non-volatile.

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

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

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

Preferably, the hydrocarbon oil(s) of the invention are isododecane.

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

According to a particular embodiment of the invention, the compositions used in process (B) and (C) also comprise at least one oil as defined previously, in particular a hydrocarbon oil.

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

Dispersion preparation method (A)

Without this being limiting, in general, the dispersion according to the invention can be prepared in the following way:

The polymerization is carried out in " dispersion ", that is to say by precipitation of the polymer during formation, with protection of the particles formed with one or more stabilizing agents, preferably a stabilizing agent.
- In a first step, the stabilizing polymer (or stabilizing agent ii)) is prepared by mixing the monomer or monomers constituting the stabilizing polymer c) or d), with vi) a radical initiator, in a solvent called synthetic solvent, and by polymerizing these monomers;
- In a second step, the monomers constituting the polymer of the particles i) are added to the stabilizing polymer formed in the previous step and the polymerization of these added monomers is carried out in the presence of the radical initiator.

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

The cosmetic agent(s), preferably pigment(s), is (are) added during the first stage. According to another variant, the cosmetic agent(s), preferably pigment(s), is (are) added during the second stage or after the second stage.

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

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

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

The cosmetic agent(s) v) preferably pigment(s) little(ven)t added during the first step. According to another variant, the dye(s) and/or pigment(s) is (are) added during the second stage or after the second stage.

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

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

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

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

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

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

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

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

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

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

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

The composition according to the invention preferably comprises a content of particle polymers i) + dispersant polymers ii) ranging from 1 to 50% by weight, relative to the total weight of composition (A), and preferably ranging from 2 to 30% in weight.

According to a preferred embodiment of the invention, the dispersion (A) according to the invention is an anhydrous composition.

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

According to another embodiment of the present patent application, the dispersion (A) is in an inverse emulsion, i.e. of the water-in-oil (W/O) or “water-in-oil (W/O)” type. In this case the composition comprises one or more surfactants, preferably nonionic. The inverse emulsions of (A) are preferably chosen in makeup and in particular in mascaras.

Composition (B)

Composition B of the process of the invention comprises one or more compound(s) hydroxylated and/or thiolated(s), organic(s) or inorganic(s), polymeric or not, preferably organic( s) or silicone(s):

The hydroxylated and/or thiolated compound(s) iv):

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

According to an advantageous variant, the one or more hydroxylated and/or thiolated compound(s) is (are) silicone(s), that is to say they contain one or more hydroxyl groups, or one or more thiol groups or one or more hydroxy groups and one or more thiol groups, they also comprise at least one siloxane chain.

By “ hydroxylated compound(s) ” is meant one or more compounds comprising one or more hydroxy —OH groups, preferably several hydroxy groups.

By “ thiolated compound(s) ” is meant one or more compounds comprising one or more thiol or mercapto —SH groups, preferably several thiol groups.

By “ hydroxylated and thiolated compound(s) ” is meant one or more compounds comprising one or more thiol groups and one or more hydroxy groups.

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

The non-polymeric hydroxylated and/or thiolated compound(s)

• p et q, identiques ou différents, représentent un nombre entier étant entendu que la somme p+q est supérieure ou égal à 2, de préférence la somme p+q est comprise inclusivement entre 2 et 10, de préférence entre 2 et 5 ;
• L désigne un groupe multivalent (au moins divalent), en particulier comprenant entre 1 et 500 atomes de carbone et/ou de silicium, plus particulièrement entre 2 et 40 atomes de carbone et/ou de silicium, encore plus particulièrement entre 3 et 30 atomes de carbone et/ou de silicium, de préférence entre 6 et 20 atomes de carbone, linéaire ou ramifié, saturé ou insaturé, ou (hétéro)cyclique, saturé ou insaturé ;

L étant éventuellement interrompu et/ou terminé par un ou plusieurs hétéroatomes ou groupes choisis parmi O, S, N, Si, C(X), et leurs associations telles que –O-, –O-C(X)-, -N(R)-C(X)-, -Si(R_c)(R_d)-O- avec R représentant un atome d’hydrogène ou un groupe (C₁-C₆)alkyle tel que méthyle ; et/ou
L étant éventuellement substitué par un ou plusieurs atomes d’halogène, ou un groupe choisi parmi R_a(R_b)N-, -(X’)_a-C(X)-(X’’)_b-R_a,
- X, X’ et X’’, identiques ou différents, représentent un atome d’oxygène, de soufre, ou un groupe N(R_b) ;
- a, et b valant 0 ou 1, de préférence la somme de a + b vaut 1,
- R_aet R_b, identiques ou différents, représentent un atome d’hydrogène, ou un groupe (C₁-C₆)alkyle, ou aryl(C₁-C₄)alkyle tel que benzyle, de préférence R_aet R_breprésentent un atome d’hydrogène ;
- R_cet R_d, identiques ou différents, représentent un groupe (C₁-C₆)alkyle, aryl(C₁-C₄)alkyle ou (C₁-C₆)alcoxy.According to one embodiment of the invention, the hydroxylated compound(s) and/or thiolated compound(s) is (are) organic(s), nonpolymeric(s) of formula (II), as well as their solvates such as hydrates:
(HO)pL(SH)q (II)
Formula (II) in which:

• p and q, which are 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 comprised 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 atoms carbon and/or silicon, 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-, –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
L being optionally substituted by one or more halogen atoms, or a group chosen from R _a (R _b )N-, -(X') _a -C(X)-(X'') _b -R _a ,
- X, X' and X'', which are identical or different, represent an oxygen or sulfur atom, or an N(R _b ) group;
- a, and b being 0 or 1, preferably the sum of a + b is 1,
- R _a and R _b , identical or different, represent a hydrogen atom, or a group (C ₁ -C ₆ )alkyl, or aryl (C ₁ -C ₄ )alkyl such as benzyl, preferably R _a and R _b represent a hydrogen atom;
- R _c and R _d , which are identical or different, represent a (C ₁ -C ₆ )alkyl, aryl (C ₁ -C ₄ )alkyl or (C ₁ -C ₆ )alkoxy group.

By “ nonpolymeric ” compound(s) is meant one or more compound(s) which is or are not directly obtained by a polymerization reaction of monomers.

According to one embodiment of the invention, the hydroxylated compound(s) and/or thiolated compound(s), is (are) hydroxylated(s), nonpolymeric, i.e. of formula (II) in which q is 0, and p 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.

According to a particular embodiment of the invention, the hydroxylated and/or thiolated compound(s) is (are) chosen from polyhydroxylated compounds. In particular, the polyhydroxylated compound(s) particularly comprise from 2 to 20 carbon atoms, in particular the polyhydroxylated compound(s) is (are) non-polymeric.

The polyhydroxylated and/or thiolated compounds of the invention, fat-soluble or not, preferably 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.

The hydroxylated and/or thiolated compound(s) used in the process according to the invention is (are) chosen in particular from hydroxyalkoxysiloxane or thioalkoxysiloxane compounds, it being understood that these compounds can further comprise one or more primary or secondary amine groups.

The polyhydroxy compound used in the process of 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 in the method of 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 polyhydroxylated compounds such as a mixture of organic and inorganic polyhydroxylated compound(s).

According to another particular embodiment, the hydroxylated and/or thiolated compound(s) are chosen from polyhydroxylated, polythiolated, and polymeric polyhydroxylated and polythiolated compounds.

• p désigne un nombre entier supérieur ou égal à 2, de préférence compris inclusivement entre 2 et 10, de préférence entre 2 et 5 ;
• L est tel que défini précédemment, de préférence L désigne un radical multivalent (au moins divalent) comprenant entre 8 et 30 atomes de carbone et/ou de silicium, de préférence entre 10 et 20 atomes de carbone et/ou de silicium, linéaire ou ramifié, saturé ou insaturé, ou (hétéro)cyclique, saturé ou insaturé, L pouvant en outre être interrompu par un ou plusieurs atomes d’oxygène, et/ou comprendre une ou plusieurs fonctions choisies parmi les fonctions amino, éther, thioéther, ester, thioester, cétone, thiocétone, amide et thioamide.

According to one embodiment of the invention, the polyhydroxy compound is a compound
non-polymeric organic compound of formula (IIa):
L(OH)p(IIa)
Formula (IIa) 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 polyol compound is preferably a diol compound.

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

Preferably, the fat-soluble polyol is a C ₈ -C ₁₈ diol, in particular linear. Advantageously, the C ₈ -C ₁₈ chain is a hydrocarbon chain, ie 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 (IIa), 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 another particular embodiment of the invention, the hydroxylated and/or thiolated compound(s) are chosen from polythiolated compounds also called “ polymercapto ”.

The polythiolated compounds of the invention can be water-soluble or fat-soluble, preferably fat-soluble.

According to another particular embodiment of the invention, the hydroxylated and/or thiolated compound(s) is (are) chosen from polythiolated compounds. In particular, the polythiolated compound or compounds particularly comprise from 2 to 20 carbon atoms.

According to a preferred embodiment, the hydroxylated compound(s) and/or thiolated compound(s), is (are) thiolated(s), nonpolymeric, i.e. of formula (II) 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, the polythiolated compound(s) are non-polymeric organic compounds of formula (IIb):
L(SH)q (IIb)
Formula (IIb) in which L is as defined for (IIa) 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 compound or compounds 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, ie 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 (IIb), 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 hydroxylated compound(s) and/or thiolated compound(s), is (are) hydroxylated(s) and thiolated(s), non-polymeric i.e. of formula ( II) in which q and p are integers greater than or equal to 1, preferably the sum p + q is an integer comprised inclusively between 2 and 10, preferably between 2 and 5, preferably q > p.

According to yet another particular embodiment of the invention, the hydroxylated and/or thiolated compound(s) is (are) chosen from (poly)hydroxylated compounds and (poly) thiols. In particular, the (poly)hydroxylated and (poly)thiolated compound(s) particularly comprise from 2 to 20 carbon atoms, in particular the (poly)hydroxylated and (poly)thiolated compound(s) is (are) not polymer(s).

• R’₁est une chaîne hydrocarbonée en C₁-C₁₂, linéaire ou ramifiée, saturée ou insaturée, cyclique ou acyclique, substituée par un ou plusieurs groupements choisis parmi les groupements :

- hydroxy ou thiol, de préférence thiol,
- aryle, aryloxy, arylthio, arylamino, le groupe aryle étant substitué par un ou plusieurs groupements hydroxy, thiol, hydroxy(C₁-C₆)alkyle ou thiol(C₁-C₆)alkyle, de préférence thiol(C₁-C₆)alkyle, et
R’₁est éventuellement interrompu dans sa chaine hydrocarbonée par un ou plusieurs hétéroatomes tels que O, S, N, un groupe carbonyle (CO), ou leur association telles que ester –C(O)-O-, ou amide –C(O)-N(H)-, R’₁étant lié à l’atome de silicium directement via un atome de carbone,

• R’₂et R’₃identiques ou différents, représentent un groupe alkyle, linéaire ou ramifié, comprenant de 1 à 6 atomes de carbone, de préférence de 1 à 4 atome de carbone tel que méthyle,
• z désigne un nombre entier allant de 1 à 3,
• et x désigne un nombre entier allant de 0 à 2, avec z+x =3.

According to another particular embodiment of the invention, the compound(s) the hydroxylated and/or thiolated compound(s) iv) is (are) chosen from hydroxylated alkoxysiloxanes and/or thiolated, such as those of formula (III):
R' ₁ -Si(OR' ₂ ) _z (R' ₃ ) _x (III)
Formula (III) 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 atoms 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.

• p vaut 0 ou 1 ;
• X représente un atome d’oxygène ou de soufre, de préférence soufre ;
• R¹représente un radical (C₁-C₆)alkyle ;
• R²et R³, identiques ou différents, de préférence identiques, sont choisis parmi :

- un groupe (C₁-C₆)alcoxy, en particulier en C₁-C₄;
- un groupe (C₁-C₆)alkyle ;

• R⁴représente un atome d’hydrogène, ou un groupe (C₁-C₆)alkyle tel que méthyle;
• L¹représente un radical hydrocarboné linéaire ou ramifié divalent, saturé, en C₁-C₂₀.

According to an even more particular embodiment of the invention, the alkoxysiloxane compounds (III) are chosen from those of the following formula (III'):
(R ¹ O)(R ² )(R ³ )Si-CH ₂ -[N(R ⁴ )-L ¹ ] _p -XH (III')
Formula (III') 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.

• q vaut 0 ou 1 ;
• X représente un atome d’oxygène ou de soufre, de préférence soufre ;
• R’¹désigne un radical (C₁-C₆)alkyle ;
• R’²et R’³, identiques ou différents, de préférence identiques, sont choisis parmi :

- un groupe (C₁-C₆)alcoxy, en particulier en C₁-C₄;
- un radical (C₁-C₆)alkyle ;

• R⁵représente un atome d’hydrogène ou un groupe alkyle en C₁-C₄éventuellement substitué par un groupe amino, thiol ou hydroxy ;
• R⁴représente un atome d’hydrogène ou un groupe alkyle en C₁-C₄en particulier méthyle ;
• L²représente un groupe divalent hydrocarboné, linéaire ou ramifié saturé en C₁-C₂₀, éventuellement interrompu par un hétéroatome tel que –NH-, éventuellement substitué par un ou plusieurs groupes hydroxy, thiol ou amino .

According to an even more particular embodiment of the invention, the alkoxysiloxane compounds (III) are chosen from those of the following formula (III'')
(R' ¹ O)(R' ² )(R' ³ )Si-CH(R ⁴ )-CH(R ⁵ )-(L ² ) _q -XH (III'')
Formula (III'') 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 (III) is chosen from:

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

According to another embodiment, the thiolated compound is a particle bearing two or more thiol groups (silica functionalized by radicals, for example 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 may denote the 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 two or more 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 bearing two or more 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 (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) carrying two or more than two thiol functions.

The polymeric hydroxylated and/or thiolated compound(s):

The polymer(s) of the invention may be homopolymers, copolymers, star, combe, brush and dendritic 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.

• p et q, identiques ou différents, représentent un nombre entier étant entendu que la somme p+q est supérieure ou égal à 3 ;
• POLY désigne un radical polymérique de préférence carboné ou siliconé ;

POLY étant éventuellement interrompu par un ou plusieurs hétéroatomes ou groupes choisis parmi O, S, N, Si, C(X), et leurs associations telles que –O-, –O-C(X)-, -N(R)-C(X)-, -Si(R_c)(R_d)-O- avec R représentant un atome d’hydrogène ou un groupe (C₁-C₆)alkyle tel que méthyle ; et/ou
POLY étant éventuellement substitué par un ou plusieurs atomes d’halogène, ou un groupe choisi parmi R_a(R_b)N-, -(X’)_a-C(X)-(X’’)_b-R_a,
- X, X’ et X’’, identiques ou différents, représentent un atome d’oxygène, de soufre, ou un groupe N(R_b) ;
- a, et b valant 0 ou 1, de préférence la somme de a + b vaut 1 ;
- R_aet R_b, identiques ou différents, représentent un atome d’hydrogène, ou un groupe (C₁-C₁₀)alkyle, ou aryl(C₁-C₄)alkyle tel que benzyle, de préférence R_aet R_breprésentent un atome d’hydrogène ; et
- R_cet R_d, identiques ou différents, représentent un groupe (C₁-C₁₀)alkyle, aryl(C₁-C₄)alkyle ou (C₁-C₁₀)alkoxy.The thiolated and/or hydroxylated polymer(s) of the invention is (are) preferably organic or silicone(s), more preferably of formula (V):
(HO)pPOLY(SH)q (V)
Formula (V) in which:

• p and q, which are 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-, -(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 of the invention, the hydroxylated and/or thiolated compound(s) are chosen from (poly)hydroxylated polymers also called “ polyol ”.

• p désigne un entier supérieur ou égal à 2, et
• POLY désigne un radical polymérique carboné ou siliconé, POLY pouvant en outre renfermer un ou plusieurs hétéroatomes tels que O, N, S, et/ou une ou plusieurs fonctions choisies parmi les fonctions amino, (thio)esters, (thio)cétones, (thio)amides, (thio)urées, (thio)carbamates, et/ou être substitué par un ou plusieurs groupements (C₁-C₁₀)alkyle, linéaires ou ramifiés, (C₁-C₁₀)alcoxy, linéaires ou ramifiés, étant entendu que lorsque POLY est substitué, les fonctions hydroxy peuvent être portées par le/les substituant(s).

According to another embodiment of the invention, the (poly)hydroxylated polymer(s) are chosen from those of formula (V′):
POLY(OH)p (V')
Formula (V') in which:

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

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

Preferably, the (poly)hydroxylated polymers (V′) 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 mass (Mn) of less than 7000, preferably between 1000 and 5000. Mention will be made in particular of the hydroxylated polybutadienes marketed by the company CRAY VALLEY under the trademarks POLY BD R45HTLO, POLY BD R45V, and POLY BD R-20 LM, which will preferably be used hydrogenated; as well as hydrogenated (poly)hydroxylated (1,2-polybutadienes), such as GI3000 with Mn=3100, GI2000 (Mn=2100) and GI1000 (Mn=1500) marketed by the company Nisso. more preferably the (poly)ols are diols.

More particularly, the compounds of formula (V′) are polyolefins (poly)ols of formula (VI):

• ALK⁴et ALK⁵, identiques ou différents, de préférence différents, représentent un groupe (C₁-C₆)alkylène, linéaire ou ramifié, éventuellement substitué par un ou plusieurs groupe hydroxy, thiol, ou amino, de préférence ALK⁴représente un groupe (C₁-C₆)alkylène linéaire tel quen-butylène, et ALK⁵représente un groupe (C₃-C₆)alkylène ramifié tel quei-butylène ;
• X représente un atome d’oxygène, de soufre ou un groupe N(Ra) avec Ra représentant un atome d’hydrogène ou un groupe (C₁-C₄)alkyle, de préférence X représente un groupe hydroxy ou thiol, plus préférentiellement hydroxy, et
• n et m, identiques ou différents, représentent un entier, avec n + m représentant un entier supérieur ou égal à 1.

Formula (VI) in which:

• ALK ⁴ and ALK ⁵ , identical or different, preferably different, represent a (C ₁ -C ₆ )alkylene group, linear or branched, optionally substituted by one or more hydroxy, thiol or amino groups, preferably ALK ⁴ represents a linear (C ₁ -C ₆ )alkylene group such as n -butylene, and ALK ⁵ represents a branched (C ₃ -C ₆ )alkylene group such as i -butylene;
• X represents an oxygen or sulfur atom or an N(Ra) group with Ra representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably X represents 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.

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

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

The polydialkyllsiloxane (di)ols are particularly chosen from those of formula (VII):

• R^a, et R^b, identiques ou différents, de préférence identiques, représentent un groupe (C₁-C₆)alkyle éventuellement substitué par un ou plusieurs groupes hydroxy, amino ou thiol, (C₁-C₆)alkoxy tel que méthoxy, aryle tel que phényle, aryloxy tel que phénoxy, aryl(C₁-C₄)alkyle tel que benzyle, ou aryl(C₁-C₄)alkoxy tel que benzoxy, de préférence (C₁-C₄)alkyle tel que méthyle,
• n représente un entier supérieur ou égal à 1 et plus particulièrement la valeur de n est telle que le poids moléculaire moyen en poids de la silicone est compris entre 500 et 55 000 ; particulièrement n est un entier compris inclusivement entre 1 et 100, de préférence compris entre 5 et 50, et préférentiellement compris entre 10 et 30, et
• L⁴et L⁵, identiques ou différents, représentent une liaison covalente, ou une chaîne hydrocarbonée comprenant de 1 à 100 atomes de carbone, saturée ou insaturée, linéaire ou ramifiée, éventuellement cyclique, éventuellement interrompue par un ou plusieurs hétéroatomes tels que oxygène, soufre ou azote en particulier oxygène, plus préférentiellement un groupe (C₁-C₆)alkylène, (C₁-C₆)alkylène-oxy, oxy-(C₁-C₆)alkylène, (C₁-C₆)alkylène-oxy(C₁-C₆)alkylène, (C₁-C₆)alkylène-oxy(C₁-C₆)alkylènoxy ou oxy(C₁-C₆)alkylène-oxy(C₁-C₆)alkylène ;
• X représente un atome d’oxygène, ou de soufre, de préférence oxygène.

Préférentiellement les polydiméthylsiloxane sont des polydiols sont choisis parmi ceux de formule (VII’) : Formula (VII) in which:

• R ^a , and R ^b , identical or different, preferably identical, represent a (C ₁ -C ₆ )alkyl group optionally substituted by one or more hydroxy, amino or thiol groups, (C ₁ -C ₆ )alkoxy such as methoxy , aryl such as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl,
• n represents an integer greater than or equal to 1 and more particularly the value of n is such that the weight-average molecular weight of the silicone is between 500 and 55,000; particularly n is an integer comprised inclusively between 1 and 100, preferably comprised between 5 and 50, and preferentially comprised between 10 and 30, and
• L ⁴ and L ⁵ , identical or different, represent a covalent bond, or a hydrocarbon chain comprising from 1 to 100 carbon atoms, saturated or unsaturated, linear or branched, optionally cyclic, optionally interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen, in particular oxygen, more preferably a (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene group -oxy(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylenoxy or oxy(C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene;
• X represents an oxygen or sulfur atom, preferably oxygen.

Preferably, the polydimethylsiloxanes are polydiols are chosen from those of formula (VII'):

• L⁴et L⁵sont tels que définis précédemment, de préférence représentent un groupe divalent choisi parmi –R₂–, –O–R₂–, –R₂–O–, –R₂–O–R’₂–, de préférence –R₂–O–R’₂–, avec R₂et R’₂, identiques ou différents, représentant un groupe (C₂-C₆)alkylène, linéaire ou ramifié, tel que éthylène ou propylène, et
• n représente un entier compris inclusivement entre 1 et 100, de préférence entre 5 et 50, et préférentiellement entre 10 et 30.

Formula (VII') 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 –, of 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 (VII'') is preferably used:

(VII'')
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 polydroxylated compound or compounds designate the compounds of formula (IIIa) below:

(IIIa)
Formula (IIIa) in which:
-R₁, identical or different, independently represents a hydroxy group; an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, especially 1 to 2 carbon atoms such as a methyl; an alkoxy group having 1 to 2 carbon atoms; or a group –(CH₂)_s-Si(R₄)₃in which s stands for an integer ranging from 1 to 4 such as 2 and R₄independently designates an alkoxy radical having 1 to 2 carbon atoms;
- R'₂and R''₂independently represent an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, especially 1 to 2 carbon atoms such as methyl;
-Todenotes an integer ranging from 0 to 10,bdenotes an integer ranging from 0 to 500, with a+b≥4

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

According to a preferred embodiment, the silicone(s) of formula (IIIa) used in the context of the invention are chosen from the compounds of formula (IIIa) in which:
- R ₁ independently represents an alkyl group having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms and more particularly from 1 to 2 carbon atoms such as a methyl;
- R' ₂ 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 methods for preparing the thiolated polymers according to the invention are known to those skilled in the art, several methods are reported below in a non-limiting manner.

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

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

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

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

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

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

• q désigne un entier supérieur ou égal à 2, et
• POLY désigne un radical polymérique carboné et/ou siliconé, de préférence siliconé, POLY pouvant en outre renfermer un ou plusieurs hétéroatomes tels que O, N, S, et/ou une ou plusieurs fonctions choisies parmi les fonctions, (thio)esters, (thio)cétones, (thio)amides, (thio)urées, (thio)carbamates, et/ou être substitué par un ou plusieurs groupements (C₁-C₁₀)alkyle, linéaires ou ramifiés, (C₁-C₁₀)alcoxy, linéaires ou ramifiés, étant entendu que lorsque POLY est substitué, les fonctions thiols peuvent être portées par le/les substituant(s).

According to one embodiment of the invention, the polythiol compound is a polymeric compound of formula (VIII):
POLY(SH)q (VIII)
Formula (VIII) 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 (VIII), is generally between 500 and 400,000, preferably between 500 and 150,000.

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

• R^a, et R^b, identiques ou différents, de préférence identiques, représentent un groupe (C₁-C₄)alkyle tel que méthyle, (C₁-C₄)alkoxy tel que méthoxy, aryle tel que phényle, aryloxy tel que phénoxy, aryl(C₁-C₄)alkyle tel que benzyle, ou aryl(C₁-C₄)alkoxy tel que benzoxy, de préférence (C₁-C₄)alkyle tel que méthyle,
• n représente un entier supérieur ou égal à 1 et plus particulièrement la valeur de n est telle que le poids moléculaire moyen en poids de la silicone est compris entre 500 et 55 000 ; particulièrement n est un entier compris inclusivement entre 1 et 100, de préférence compris entre 5 et 50, et préférentiellement compris entre 10 et 30, et
• L⁴et L⁵, sont tels que définis précédemment, en particulier représentent une liaison covalente, un groupe (C₁-C₆)alkylène, (C₁-C₆)alkylène-oxy, oxy-(C₁-C₆)alkylène, (C₁-C₆)alkylène-oxy(C₁-C₆)alkylène, (C₁-C₆)alkylène-oxy(C₁-C₆)alkylènoxy ou oxy(C₁-C₆)alkylène-oxy(C₁-C₆)alkylène, de préférence un groupe (C₁-C₆)alkylène, (C₁-C₆)alkylène-oxy, oxy-(C₁-C₆)alkylène, ou (C₁-C₆)alkylène-oxy(C₁-C₆)alkylène.

Formula (VIII') in which:

• R ^a , and R ^b , which are identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl,
• 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; particularly n is an integer comprised inclusively between 1 and 100, preferably comprised between 5 and 50, and preferentially comprised between 10 and 30, and
• L ⁴ and L ⁵ , are as defined above, in particular represent a covalent bond, a (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ ) group 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 (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene group, or (C ₁ - C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene.

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

• L⁴et L⁵représentent une chaîne hydrocarbonée comprenant de 1 à 100 atomes de carbone, saturée ou insaturée, linéaire ou ramifiée, éventuellement cyclique, éventuellement interrompue par un ou plusieurs hétéroatomes tels que oxygène, soufre ou azote en particulier oxygène, de préférence L⁴et L⁵représentent représentent un groupe (C₁-C₆)alkylène, (C₁-C₆)alkylène-oxy, oxy-(C₁-C₆)alkylène, ou (C₁-C₆)alkylène-oxy(C₁-C₆)alkylène, plus préférentiellement un groupe divalent choisi parmi –R₂–, –O–R₂–, –R₂–O–, –R₂–O–R₂–, de préférence –R₂–O–R₂–, avec R₂représentant un groupe (C₂-C₆)alkylène linéaire ou ramifié, de préférence linéaire, tel que éthylène ou n-propylène ;
• n représente un entier compris inclusivement entre 1 et 100, de préférence entre 5 et 50, et préférentiellement entre 10 et 30.

Formula (VIII'') 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 (C ₂ -C ₆ )alkylene group, preferably linear, such as ethylene or n-propylene;
• n represents an integer comprised inclusively between 1 and 100, preferably between 5 and 50, and preferably between 10 and 30.

As thiolated poly(C1-C4)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 the 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 (VIII'''):

(VIII''')

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

• R^a, R^b, et R^d, identiques ou différents, de préférence identiques, représentent un groupe (C₁-C₆)alkyle éventuellement substitué par un groupe hydroxy, ou amino, de préférence (C₁-C₄)alkyle tel que méthyle, (C₁-C₄)alkoxy tel que méthoxy, aryle tel que phényle, aryloxy tel que phénoxy, aryl(C₁-C₄)alkyle tel que benzyle, ou aryl(C₁-C₄)alkoxy tel que benzoxy, de préférence (C₁-C₄)alkyle tel que méthyle,

R^dpeut également représenter un groupe (C₁-C₆)alkyle substitué par un groupe (C₁-C₄)alkylamino ou amino, ou thiol, préférence (C₁-C₄)alkyle tel que méthyle ;

• ALK représente une chaîne hydrocarbonée comprenant de 1 à 100 atomes de carbone, saturée ou insaturée, linéaire ou ramifiée, éventuellement cyclique, éventuellement interrompue par un ou plusieurs hétéroatomes tels que oxygène, soufre ou azote (en particulier O), un groupe (thio)carbonyle C(X) avec X représentant O, ou S, ou leurs associations telles que –O–, –O-C(O)– ou –C(O)-O–, de préférence ALK représente un groupe (C₁-C₆)alkylène, plus préférentiellement (C₁-C₄)alkylène tel que propylène ; n et m, identiques ou différents, représentant un entier supérieur à 2 et plus particulièrement les valeurs de m et n sont telles que le poids moléculaire moyen en poids de la silicone est compris entre 1000 et 55 000 ;

Préférentiellement les polydi(C₁-C₄)alkylsiloxanes de formule (IX) sont de formule (IX’) suivante : Formula (IX) in which:

• R ^a , R ^b , and R ^d , identical or different, preferably identical, represent a group (C ₁ -C ₆ )alkyl optionally substituted by a hydroxy group, or amino, preferably (C ₁ -C ₄ )alkyl such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl (C ₁ -C ₄ )alkyl such as benzyl, or aryl (C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl,

R ^d can also represent a (C ₁ -C ₆ )alkyl group substituted by a (C ₁ -C ₄ )alkylamino or amino group, or thiol, preferably (C ₁ -C ₄ )alkyl such as methyl;

• ALK represents a hydrocarbon chain comprising from 1 to 100 carbon atoms, saturated or unsaturated, linear or branched, optionally cyclic, optionally interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen (in particular O), a group (thio) carbonyl C(X) with X representing O, or S, or their combinations such as –O–, –OC(O)– or –C(O)-O–, preferably ALK represents a group (C ₁ -C ₆ )alkylene, more preferably (C ₁ -C ₄ )alkylene such as propylene; n and m, 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 1,000 and 55,000;

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

(IX')
formula (IX'), in which the values of n and m are such that the weight-average molecular weight of the silcone is between 1000 and 55,000. As examples of silicone (IX'), mention may be made of those sold by Genesee GP -367 and other Polymers. Polythiol silicones are in particular polydimethylsiloxane comprising two or more thiol groups such as, for example, the products SMS-022, SMS 042 and SMS 992 sold by the company Gelest In https://www.gpcsilicones.com/products/silicone- fluids/mercapto-functional, https://www.shinetsusilicone-global.com/products/type/oil/detail/search/deg07.shtml, and 1053_Reactive Silicones_Silanes/Silicones - Gelest

According to another variant, the thiol compound is a particle bearing two or more thiol groups (silica functionalized by radicals, for example of the alkyl type, substituted by thiol functions) or a particle covered with compound(s) bearing two or more than two thiol functions (coating) said particle possibly being a sphere, a fiber, a rod (rod), an amorphous structure.

According to a particular embodiment of the invention, the hydroxylated and/or thiolated compound(s) are 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 originating from said ramifications of the molecule, and terminal functions.

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

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

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

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

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

Dendrimers are also called dense star polymers, or " dense star polymer ", 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(s) according to the invention denote a non-polymeric organic compound and can be represented by the formula (I):
W(SH) _n (I)
Formula (I) 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 multivalent (at least divalent) C ₂ -C ₈₀ linear or branched radical or (hetero)cyclic, saturated, 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, ketones) and/or be substituted by one or more linear or branched C ₁ -C ₁₀ alkyl groups, linear or branched C ₁ -C ₁₀ alkoxy groups, it being understood that when the radical W is substituted, the thiol functions can be carried by the substituent(s).

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

The molar mass of the compounds of formula (I) is generally between 90 and 1500.

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

According to this embodiment, the compound with a thiol unit of the invention 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 (I) 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 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 (I) is such that n=2 or 3 and W denotes a divalent or trivalent saturated linear or branched C3-C20 hydrocarbon radical, preferably linear C ₂ -C ₁₂ or branched, said radical containing one or more non-adjacent heteroatom(s) chosen from O, S.

According to this embodiment, the compound with a thiol unit can be chosen, for example, from:
C ₂ -C ₁₂ bis mercaptoalkyl ethers and sulphides such as bis(2-mercaptoethyl)ether, bis(2-mercaptoethyl)sulphide, bis-(2-mercaptoethylthio-3-mercaptopropane)sulphide
alkanes (C ₁ -C ₅ ) bis (2-mercapto alkyl (C ₁ -C ₃ )thio) or mercaptoalkanes (C ₁ -C ₅ ) bis (2-mercapto alkyl (C ₁ -C ₃ )thio) as by example bis(2-mercaptoethylthio)methane, 1,2-bis(2-mercaptoethylthio)ethane, 1,3-bis(2-mercaptoethylthio)propane, 1,2-bis(2-mercaptoethylthio)propanethiol, 1,2-bis(2-mercaptoethyl)thio-3-mercaptopropane, 1,2,3-tris(2-mercapto ethylthio)propane

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

According to another embodiment, the compound with a thiol unit of formula (I) is such that n denotes an integer greater than or equal to 2 and W denotes a linear or branched multivalent (at least divalent) saturated hydrocarbon C3-C20 radical, of preferably linear or branched C2-C12, said radical containing at least one ester function.

According to this embodiment, the compound with a thiol unit can be chosen, for example, from:
esters of polyols (glycols, triols, tetraols, pentaols, hexaols) and of C1-C6 mercaptocarboxylic acid such as ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(thioglycolate), trimethylolpropane tris (thioglycolate), trimethylolpropane tris (beta-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (.beta.-mercaptopropionate), dipentaerylthritol hexakis (.beta.-mercaptoproprionate ), tris(2-mercaptoacetate) trimethylolpropane, tris(3-mercaptopropionate) trimethylolpropane, tris(3-mercaptopropionate) pentaerythritol, tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), tetrakis(3-mercaptobutanate), pentaerythritol hex -3-mercaptopropionate,

Preferably, according to this 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), dipentaerythritol hex-3-mercaptopropionate.

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

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

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

According to a sixth embodiment, the compound with a thiol unit of formula (I) 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 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 (I) is such that n=3 and W denotes a cyclic radical of substituted isocyanurate type.

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

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

According to an eighth embodiment, the compound with a thiol unit of formula (I) 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 C ₁ -C alkyl type 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 embodiment, the compound with a thiol unit can be chosen, for example, from
1,2-dimercaptobenzene, 1,3-dimercaptobenzene,
1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene,
1,3-bis(mercaptomethyl)benzene,
1,4-bis(mercaptomethyl)benzene,
1,2-bis(2-mercaptoethyl)benzene,
1,3-bis(2-mercaptoethyl)benzene,
1,4-bis(2-mercaptoethyl)benzene,
1,2-bis(2-mercaptoethyleneoxy)benzene,
1,3-bis(2-mercaptoethyleneoxy)benzene,
1,4-bis(2-mercaptoethyleneoxy)benzene,
1,2,3-trimercaptobenzene,
1,2,4-trimercaptobenzene,
1,3,5-trimercaptobenzene,
1,2,3-tris(mercaptomethyl)benzene,
1,2,4-tris(mercaptomethyl)benzene,
1,3,5-tris(mercaptomethyl)benzene,
1,2,3-tris(2-mercaptoethyl)benzene,
1,2,4-tris(2-mercaptoethyl)benzene,
1,3,5-tris(2-mercaptoethyl)benzene,
1,2,3-tris(2-mercaptoethyleneoxy)benzene,
1,2,4-tris(2-mercaptoethyleneoxy)benzene,
1,3,5-tris(2-mercaptoethyleneoxy)benzene,
1,2,3,4-tetramercaptobenzene,
1,2,3,5-tetramercaptobenzene,
1,2,4,5-tetramercaptobenzene,
1,2,3,4-tetrakis(mercaptomethyl)benzene,
1,2,3,5-tetrakis(mercaptomethyl)benzene,
1,2,4,5-tetrakis(mercaptomethyl)benzene,
1,2,3,4-tetrakis(2-mercaptoethyl)benzene,
1,2,3,5-tetrakis(2-mercaptoethyl)benzene,
1,2,4,5-tetrakis(2-mercaptoethyl)benzene,
1,2,3,4-tetrakis(2-mercaptoethyleneoxy)benzene,
1,2,3,5-tetrakis(2-mercaptoethyleneoxy)benzene,
1,2,4,5-tetrakis(2-mercaptoethyleneoxy)benzene,
2,2'-dimercaptobiphenyl,
4,4'-dimercaptobiphenyl,
4,4'-dimercaptobibenzyl,
2,5-toluenedithiol,
3,4-toluenedithiol,
1,4-naphthalenedithiol,
1,5-naphthalenedithiol,
2,6-naphthalenedithiol,
2,7-naphthalenedithiol,
2,4-dimethylbenzene-1,3-dithiol,
4,5-dimethylbenzene-1,3-dithiol,
9,10-anthracenedimethanethiol,
1,3-bis(2-mercaptoethylthio)benzene,
1,4-bis(2-mercaptoethylthio)benzene,
1,2-bis(2-mercaptoethylthiomethyl)benzene,
1,3-bis(2-mercaptoethylthiomethyl)benzene,
1,4-bis(2-mercaptoethylthiomethyl)benzene,
1,2,3-tris(2-mercaptoethylthio)benzene,
1,2,4-tris(2-mercaptoethylthio)benzene,
1,3,5-tris(2-mercaptoethylthio)benzene,
1,2,3,4-tetrakis(2-mercaptoethylthio)benzene,
1,2,3,5-tetrakis(2-mercaptoethylthio)benzene,
1,2,4,5-tetrakis(2-mercaptoethylthio)benzene,
3,4-thiophenedithiol,.

According to this embodiment, compound (I) 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, 1,2,4,5-tetrakis(2-mercaptoethyleneoxy)benzene, 1,2,3-tris(2-mercaptoethylthio)benzene, 1,2,4-tris(2-mercaptoethylthio)benzene, 1,3,5-tris(2-mercaptoethylthio)benzene, 1,2, 3,4-tetrakis(2-mercaptoethylthio)benzene, 1,2,3,5-tetrakis(2-mercaptoethylthio)benzene, 1,2,4,5-tetrakis(2-mercaptoethylthio)benzene,3,4 -thiophenedithiol.

According to a ninth embodiment, the compound with a thiol unit of formula (I) 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 compound(s) the hydroxylated and/or thiolated compound(s) iv) is (are) chosen from the derivatives of triglycerides of hydroxylated and/or thiolated thiolated fatty acids, such as those of formula (IV):

• R¹, R²et R³, identiques ou différents, représentent un atome d’hydrogène, un groupe hydroxy, ou thiol, de préférence thiol ;
• ALK¹, ALK², et ALK³, identiques ou différents, représentent un groupe (C₁-C₃₀)alkylène éventuellement substitué par un ou plusieurs groupes hydroxy ou thiol, de préférence thiol,
• X¹, X²et X³, identiques ou différents, de préférence identiques, représentent un groupe -C(Y)-Y’- ou -Y’-C(Y)- avec Y et Y’, identiques ou différents, de préférence identiques, représente un hétéroatome tel que O, S, et N de préférence O ;

Formula (IV) in which:

• R ¹ , R ² and R ³ , which are 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, of preferably identical, represents a heteroatom such as O, S, and N, preferably O;

• R¹, R²et R³, représentent un atome d’hydrogène,
• ALK¹représente un groupe (C₁₀-C₂₄)alkylène, particulièrement (C₁₄-C₂₀)alkylène, de préférence linaire ;
• ALK²représente un représente un groupe (C₁₀-C₂₄)alkylène, particulièrement (C₁₄-C₂₀)alkylène, de préférence linaire, substitué par un ou plusieurs groupes thiols,
• ALK³représente un représente un groupe (C₁₀-C₂₄)alkylène, particulièrement (C₁₄-C₂₀)alkylène, de préférence linaire, substitué par un ou plusieurs groupes thiols, de préférence deux groupes thiols, et/ou
• X¹, X²et X³identiques, représentent un groupe -C(O)-O- ou -O-C(O)- ;

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

• 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, preferably linear, substituted by one or more thiol groups, preferably two thiol groups, and/or
• X ¹ , X ² and X ³ which are identical, represent a -C(O)-O- or -OC(O)- group;

More preferably derivatives of triglycerides of hydroxylated and/or thiolated thiolated fatty acids, such as those of the following formula:

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

(IV)

• R¹, R²et R³, identiques ou différents, représentent un atome d’hydrogène, un groupe hydroxy, ou thiol, de préférence thiol ;
• ALK¹, ALK², et ALK³, identiques ou différents, représentent un groupe (C₁-C₃₀)alkylène éventuellement substitué par un ou plusieurs groupes hydroxy ou thiol, de préférence thiol,
• X¹, X²et X³, identiques ou différents, de préférence identiques, représentent un groupe -C(Y)-Y’- ou -Y’-C(Y)- avec Y et Y’, identiques ou différents, de préférence identiques, représente un hétéroatome tel que O, S, et N de préférence O ;

Formula (IV) in which:

• R ¹ , R ² and R ³ , which are 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, of preferably identical, represents a heteroatom such as O, S, and N, preferably O;

• R¹, R²et R³, représentent un atome d’hydrogène,
• ALK¹représente un groupe (C₁₀-C₂₄)alkylène, particulièrement (C₁₄-C₂₀)alkylène, de préférence linaire ;
• ALK²représente un représente un groupe (C₁₀-C₂₄)alkylène, particulièrement (C₁₄-C₂₀)alkylène, de préférence linaire, substitué par un ou plusieurs groupes thiols,
• ALK³représente un représente un groupe (C₁₀-C₂₄)alkylène, particulièrement (C₁₄-C₂₀)alkylène, de préférence linaire, substitué par un ou plusieurs groupes thiols, de préférence deux groupes thiols, et/ou
• X¹, X²et X³identiques, représentent un groupe -C(O)-O- ou -O-C(O)- ;

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

• 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, preferably linear, substituted by one or more thiol groups, preferably two thiol groups, and/or
• X ¹ , X ² and X ³ which are identical, represent a -C(O)-O- or -OC(O)- group;

More preferably derivatives of triglycerides of hydroxylated and/or thiolated thiolated fatty acids, such as those of the following formula:

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 polymercaptan® products from Chevron Phillips such as polymercaptan 358 (mercaptanised soybean oil) and polymercaptan 407 (mercapto hydroxy soybean oil)

Polymercaptan 358

According to a particular embodiment of the invention, the hydroxylated and/or thiolated compound(s) are 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, preferably ranging from 500 to 500,000, and preferentially ranging from 500 to 100,000.

According to this variant, the compounds of formula (I) 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 (I) 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 (I) denote trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3- mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutanate), dipentaerythritol hex-3-mercaptopropionate, tris((mercaptopropionyloxy)-ethyl)isocyanurate.

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

The molar mass of the compounds of formula (II') is generally between 500 and 400,000, preferably between 500 and 150,000.

POL can designate a multivalent radical of the homopolymer or copolymer type;
POL can refer to a star-, comb-, brush-, or dendritic-like polymeric radical. The POL radical can be of natural origin (such as polysaccharides, peptides) or synthetic (such as acrylic polymers, polyesters, polyglycols).
The thiol functions (-SH) can be terminal and/or pendent groups.

According to a first embodiment, the thiol compound of formula (II′) is such that POL denotes a hydrocarbon polymer 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 (II′) such as poly(vinylmercaptan), poly(4-mercaptostyrene), poly(vinylbenzylmercaptan), poly(4-mercaptostyrene)-co-poly(methylmethacrylate), as well as polymers containing amide functions in the polymer such as poly(hexamethylene adipamide thiolated).

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

The thiol compounds of formula (II) also designates the compounds of formula (II) 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 transformed into a thiolated polymer of formula (II) according to the diagram below:

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

The compound with a thiol unit of formula (II′) can also denote a hyperbranched or dendritic polymer modified by thiol functions as described in application FR 2761691.

• Y représente un atome d’oxygène, de soufre, ou un groupement NR’,
• X représente i) un atome d'oxygène ou ii) un groupement –N(R')- dans lequel R' est choisi parmi a) un atome d'hydrogène, b) un groupe alkyle en C₁-C₆, linéaire ou ramifié, saturé ou insaturé, c) un groupe mono- ou poly-hydroxyalkyle en C₁-C₆, linéaire ou ramifié, saturé ou insaturé, d) un groupe aminoalkyle en C₁-C₆ou un groupe polyalkylèneimine ; de préférence X représente -N(R’)- avec R’ représente un atome d’hydrogène ou un groupe (C₁-C₄)alkyle tel que méthyle ; et
• A représente un groupe (C₁-C₁₂)alkylène, linéaire, ramifié ou cyclique, saturé ou insaturé; ce groupe étant éventuellement interrompu par un ou plusieurs hétéroatomes tel que O, S, N et/ou éventuellement substitué par un ou plusieurs groupes choisis parmi amino (-NH₂), acylamino (-N(H)-C(O)-R) ou aminoacyle (RN(H)-C(O)-) dans lequel R représente un groupement alkyle en C₁-C₁₀linéaire, ramifié ou cyclique, saturé ou insaturé, carboxy (-C(O)OH), ester (-C(O)-OR) dans lequel R représente un groupement alkyle en C₁-C₁₀linéaire, ramifié ou cyclique, saturé ou insaturé.

By way of example of hyperbranched polymers and dendrimers comprising thiol functional groups of formula (X) below:
HS-AC(Y)-X-
Formula (X) in which:

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

Preferably, the 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 (X) as defined previously.

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):

• R¹, R², R³, R’¹, R’², R’³et R’⁴, R'''¹, R'''², identiques ou différents représentent : l’atome d’hydrogène; un radical alkyle en C₁-C₆, linéaire, ramifié ou cyclique, saturé ou insaturé; un radical amino (-NH₂); un radical acide carboxylique (-COOH); un radical alkylamino en C₁-C₁₀; un radical acylamino en C₁-C₁₀;
• R’’¹, R’’², R’’³et R’’⁴, identiques ou différents, représentent l’atome d'hydrogène ou un groupe alkyle en C₁-C₄, linéaire ou ramifié, saturé ou insaturé; les flèches indiquant les positions des substitutions; et
• k est un entier, préférentiellement 0 ou 1 ;
• représente le point d’attache avec le reste de la molécule sur le groupe phénylène en position 1-2, ou 1-3, ou 1-4; étant entendu que les radicaux R’’₁, R’’₂, et R’’₃et R’’₄se trouvent alors positionnés sur les atomes de carbone 3, 4, 5, 6, ou 2, 4, 5 ou 6 ou 2, 3, 5, 6 respectivement.

Formulas (a), (b), (c), and (d) in which

• R ¹ , R ² , R ³ , R' ¹ , R' ² , R' ³ and R' ⁴ , R''' ¹ , R''' ² , which are identical or different, represent: the hydrogen atom; a C ₁ -C ₆ alkyl 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 , which are identical or different, represent the hydrogen atom or a C ₁ -C ₄ alkyl group, linear or branched, saturated or unsaturated; the arrows indicating the positions of the substitutions; And
• k is an integer, preferably 0 or 1;
• represents the point of attachment with the rest of the molecule on the phenylene group in position 1-2, or 1-3, or 1-4; it being understood that the radicals R'' ₁ , R'' ₂ , and R'' ₃ and R'' ₄ are then positioned on the carbon atoms 3, 4, 5, 6, or 2, 4, 5 or 6 or 2, 3, 5, 6 respectively.

According to a preferred mode of the invention, the thiolated polymers are such as hyperbranched polymers and the dendrimers comprising functional groups of formula (X) such that A is chosen from:
-CH ₂ -CH(CO ₂ H)-NH- and Y represents an oxygen atom;
-(CH ₂ ) ₂ -(CH ₃ CONH)CH- and Y represents an oxygen atom;
-(CH ₂ ) ₃ - and Y represents an oxygen atom or an NH group.

In particular, A is the propylene group -CH ₂ -CH ₂ -CH ₂ -, and Y represents an oxygen atom, the compound according to the invention then corresponding to the following formula (XI):
HS- _CH2 - _CH2 - _CH2 -C(O)-X-(XI)

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

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

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

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

• p différent de p’ et p, p’ valent 0 ou 1 ;
• n vaut 3 ou 4 ;
• si p’ vaut 0, alors le NH voisin est engagé dans une polymérisation N-ε;
• si p vaut 0, alors le NH voisin est engagé dans une polymérisation N-α;
• si p ou p’ vaut 1, alors R ou R’ représente -B-SH, avec B représentant une chaîne hydrocarbonée en C₁-C₃₀, saturée ou non, linéaire ou ramifiée pouvant être interrompue par un ou plusieurs hétéroatomes ou groupes, seuls ou en combinaisons, tels que : -N(R¹)-, -O-, -S(O)_r-, -C(O)-, -C(S)-, -C(NR¹)-, avec r valant 0, 1 ou 2, ou/et par un ou plusieurs aryle, hétéroaryle, cycloalkyle ou hétérocycloalkyle à 5, 6 ou 7 chaînons et pouvant être substituée par un ou plusieurs atome halogène, ou groupements : hydroxy, amino, carboxy, (di)(C₁-C₈)alkylamino, (C₁-C₈)acylamino, (C₁-C₈)acyloxy, (C₁-C₈)alkyloxycarbonylamino, (C₁-C₈)alkylamino-carbonyloxy, (C₁-C₈)alkyl amino-carbonyle ;

sachant que R ou R’ peuvent, en partie seulement, également représenter un atome d’hydrogène,
et/ou –C(NH)- et ses sels
et/ou –C(NH)-N(H)-C(NH)-NH₂et ses sels

• R₁représente un atome d’hydrogène ou un groupment (C₁-C₈)alkyle, (C₁-C₈)acyle, (C₁-C₈)alkyloxycarbonyle, (C₁-C₈)alkyl amino-carbonyle, halogéno.
• B peut également représenter un groupement aryle, hétéroaryle, cycloalkyle, ou hétérocycloalkyle à 5, 6 ou 7 chaînons, éventuellement substitués ;
• m représente un entier compris inclusivement de 3 à 10000.

Formula (XII) in which:

• p different from p' and p, p' are 0 or 1;
• n is 3 or 4;
• if p' is 0, then the neighboring NH is involved in an N-ε polymerization;
• if p is 0, then the neighboring NH is involved in an N-α polymerization;
• if p or p' equals 1, then R or R' represents -B-SH, with B representing a C ₁ -C ₃₀ hydrocarbon chain, saturated or not, linear or branched which can be interrupted by one or more heteroatoms or groups, alone or in combinations, such as: -N(R ¹ )-, -O-, -S(O) _r -, -C(O)-, -C(S)-, -C(NR ¹ )-, with r equal to 0, 1 or 2, or/and by one or more aryl, heteroaryl, cycloalkyl or heterocycloalkyl with 5, 6 or 7 members and which may be substituted by one or more halogen atoms, or groups: hydroxy, amino, carboxy, (di)(C ₁ -C ₈ )alkylamino, (C ₁ -C ₈ )acylamino, (C ₁ -C ₈ )acyloxy, (C ₁ -C ₈ )alkyloxycarbonylamino, (C ₁ -C ₈ )alkylamino-carbonyloxy, (C ₁ -C ₈ )alkyl 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 inclusively from 3 to 10000.

Preferably, the thiol function grafting rate will be greater than or equal to 1%.
Advantageously, poly N-α- and N-ε- lysine and ornithine corresponding to formula (XII) exhibit: 5<m<1000.

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

By way of example of hyperbranched polymers, mention may very particularly be made of hyperbranched thiolated polyethyleneimines, such as those described in application EP103759, with a molecular molar mass of between 30×10 ⁴ and 50×10 ⁴ .

The concentration of thiolated polymers is between 0.001% and 40% of the composition, preferably between 0.1% and 15%, preferably between 0.4 and 10%, this percentage being expressed by weight for weight.

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

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

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

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

• R₁, R₂et R₃, identiques ou différents, de préférence identiques représentent un groupe hydroxy(C₁-C₆)alkyle ou thio(C₁-C₆)alkyle, de préférence thio(C₁-C₆)alkyle ;
• R₄représente un atome d’hydrogène, ou un groupe hhydroxy, thiol, amino, ou un groupe (C₁-C₆)alkyle, de préférence (C₁-C₄)alkyle tel que éthyle ;
• X₁et X₂, identiques ou différents, de préférence identiques, représente un atome d’oxygène, de soufre, ou amino, de préférence oxygène ;
• m, n et l, identiques ou différents, représentent un nombre entier supérieur ou égal à 1.

Formula (XIII) in which:

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

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

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

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

According to a preferred embodiment of the invention, the hydrocarbon-based oil or oils of composition (B) are chosen from hydrocarbon-based oils having from 8 to 14 carbon atoms, in particular the apolar oils, described above. Even more preferably, the hydrocarbon oil(s) of composition (B) are isododecane.

According to a particular embodiment of the invention, composition (B) is aqueous or aqueous-alcoholic. By hydroalcoholic is meant a mixture of water and C ₂ -C ₄ alkanol, linear or branched, preferably ethanol.

According to an advantageous embodiment of the invention, composition (B) is aqueous or aqueous-alcoholic and preferably also comprises one or more chitosans and/or one or more polyamino acids, preferably polylysines.

According to another advantageous embodiment of the invention, composition (B) is aqueous and comprises one or more alkoxysilane f) as defined above in emulsion in water, in particular of the oil-in-water (W/O) or "water in oil (W/O)”.

According to yet another advantageous embodiment of the invention, composition (B) is aqueous and comprises iv) one or more hydroxylated and/or thiolated compound(s) one or more hydroxylated compound(s) , polymer(s) or not, preferably organic(s) or silicone(s);

as defined previously in emulsion of the oil-in-water (O/W) or “oil-in-water (O/W)” type.

Advantageously, the hydroxylated and/or thiolated compound(s) used in the process according to the invention are implemented according to a molar ratio of the hydroxylated and/or thiolated group of the hydroxylated and/or thiolated compound iv)/of anhydride compound with ethylenic unsaturated anhydride b) as defined previously ranging from 0.01 to 10, preferably ranging from 0.1 to 5, preferentially ranging from 0.1 to 2, and more preferentially ranging from 0.1 to 1.

The at least two-step process of the invention makes it possible to obtain deposits of cosmetic agents and in particular of pigments having good resistance to external attacks that keratin materials can undergo, in particular good resistance to water and/or soap, shower gel, and edible oils.

In addition, the method of the invention makes it possible to trap non-volatile compounds, in particular oils, for example to improve the cosmeticity, or to provide shine to keratin materials, preferably the skin, in particular the skin of the face such as the lips. and this in a remanent way vis-à-vis external aggressions.

As non-volatile oils, mention may be made of: hydrocarbon-based oils of animal origin such as perhydrosqualene; vegetable hydrocarbon oils such as liquid triglycerides of fatty acids with 4 to 10 carbon atoms such as triglycerides of heptanoic or octanoic acids, or else sunflower, corn, soybean, grapeseed, sesame, apricot, macadamia, castor, avocado, caprylic/capric acid triglycerides, jojoba oil, shea butter; linear or branched hydrocarbons, of mineral or synthetic origin such as paraffin oils and their derivatives, petroleum jelly, polydecenes, hydrogenated polyisobutene such as parleam; synthetic esters and ethers, in particular of fatty acids such as, for example, Purcellin's oil, isopropyl myristate, ethyl-2-hexyl palmitate, octyl-2-dodecyl stearate, erucate octyl-2-dodecyl, isostearyl isostearate; hydroxylated esters such as isostearyl lactate, octylhydroxystearate, octyldodecyl hydroxystearate, diisostearylmalate, triisocetyl citrate, heptanoates, octanoates, decanoates of fatty alcohols; polyol esters such as propylene glycol dioctanoate, neopentylglycol diheptanoate, diethyleneglycol diisononanoate; and pentaerythritol esters; 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 volatile or 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; their mixtures.

These oils can 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 dispersion (A).

Dispersion (A) and compositions (B) and (C) according to the invention may also comprise one or more dyestuffs chosen from fat-soluble dyes, and pulverulent dyestuffs such as pigments, nacres, and well-known flakes. known to those skilled in the art. The dyestuffs may be present, in the composition, in a content ranging from 0% to 30% by weight, relative to the weight of the dispersion or composition which comprises them, preferably from 0% to 10% by weight.

The dispersion (A) and the compositions (B) and (C) 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 weight of the dispersion or composition which includes them.

the cosmetic active ingredient(s) iv)

The cosmetic active(s) of the invention is (are) chosen from a) coloring agents chosen from pigments, direct dyes and mixtures thereof, b) active ingredients for caring for keratin materials preferably skin and c) UV filters and d) mixtures thereof.

According to a preferred embodiment of the present patent application, the cosmetic active ingredient(s) of the invention is (are) chosen from coloring agents and preferably a) pigments.

According to a particular embodiment of the present patent application, the cosmetic active ingredient(s) of the invention is (are) chosen from b) active ingredients for the care of keratin materials, preferably active ingredients skin or hair.

According to yet another particular embodiment of the present patent application, the cosmetic active ingredient(s) of the invention is (are) chosen from c) UV filters.

According to a particular embodiment of the invention, the dispersion (A) and/or the composition (B) and/or the composition (C) of the invention comprise v) one or more cosmetic active ingredient(s).

According to a particular embodiment of the invention, the dispersion (A) comprises v) one or more cosmetic active agents, preferably one or more pigment(s).

According to another particular embodiment of the invention, composition (B) comprises v) one or more cosmetic active agents, preferably one or more pigment(s).

According to a preferred embodiment of the invention, composition (C) comprises v) one or more cosmetic active agents, preferably one or more pigment(s).

The hair dye(s) represent more particularly from 0.001 to 10% by weight of the total weight of the composition which comprises them, and preferably from 0.005 to 5% by weight.

According to a particular embodiment of the invention, the dispersion (A) comprises v) one or more cosmetic active ingredient(s), in particular one or more pigment(s).

According to another particular embodiment of the invention, composition (B) comprises v) one or more cosmetic active ingredient(s), in particular one or more pigment(s).

According to yet another preferred embodiment of the invention, composition (C) comprises v) one or more cosmetic active ingredient(s), in particular one or more pigment(s).

By “ pigment ”, is meant all the pigments providing color to keratin materials, of synthetic or natural origin. The solubility of the pigments in water at 25° C. and at atmospheric pressure (760 mmHg) is less than 0.05% by weight, and preferably less than 0.01%.

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

The pigments which can be used are in particular chosen from the organic and/or inorganic pigments known in the art, in particular those which are described in the encyclopedia of chemical technology by Kirk-Othmer and in the encyclopedia of industrial chemistry by Ullmann. Mention may in particular be made, as pigments, of organic and inorganic pigments such as those defined and described in Ullmann's Encyclopedia of Industrial Chemistry "Pigment organics", 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a20 371 and ibid, "Pigments, Inorganic, 1. General” 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim10.1002/14356007.a20_243.pub3

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

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

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

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

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

According to a particular embodiment of the invention, pigment pastes of organic pigments such as the products sold by the company HOECHST under the name:
- YELLOW COSMENYL IOG: Pigment YELLOW 3 (Cl 11710);
- COSMENYL G YELLOW: Pigment YELLOW 1 (Cl 11680);
- ORANGE COSMENYL GR: Pigment ORANGE 43 (Cl 71105);
- COSMENYL RED R: Pigment RED 4 (Cl 12085);
- CARMIN COSMENYL FB: Pigment RED 5 (Cl 12490);
- VIOLET COSMENYL RL: Pigment VIOLET 23 (Cl 51319);
- COSMENYL BLUE A2R: Pigment BLUE 15.1 (Cl 74160);
- GREEN COSMENYL GG: Pigment GREEN 7 (Cl 74260);
- COSMENYL BLACK R: Pigment BLACK 7 (Cl 77266).

The pigments in accordance with the invention may also be in the form of composite pigments as described in patent EP 1 184 426. These composite pigments may be composed in particular of particles comprising:
- an inorganic core,
- at least one binder ensuring the fixing of the organic pigments on the core, and
- at least one organic pigment at least partially covering the core.

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

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

The 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, mention may be made of cochineal carmine. 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).

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 or pigments can also be special effect pigments.

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

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

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

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

By way of illustration of the nacres that can be used in the context of the present invention, mention may be made in particular of the gold-colored nacres marketed in particular by the company ENGELHARD under the name Gold 222C (Cloisonne), Sparkle gold (Timica), Gold 4504 (Chromalite) and Monarch gold 233X (Cloisonne); mother-of-pearl bronzes sold in particular by the company MERCK under the name Bronze fine (17384) (Colorona) and Bronze (17353) (Colorona), by the company Eckart under the name Prestige Bronze and by the company ENGELHARD under the name Super bronze (Cloisonne ); the orange nacres sold in particular by the company ENGELHARD under the name Orange 363C (Cloisonne) and Orange MCR 101 (Cosmica) and by the company MERCK under the name Passion orange (Colorona) and Matte orange (17449) (Microna); the brown mother-of-pearl in particular marketed by the company ENGELHARD under the name Nu-antique copper 340XB (Cloisonne) and Brown CL4509 (Chromalite); mother-of-pearl with a copper sheen sold in particular by the company ENGELHARD under the name Copper 340A (Timica) and by the company Eckart under the name Prestige Copper; nacres with a red sheen in particular marketed by the company MERCK under the name Sienna fine (17386) (Colorona); nacres with a yellow sheen in particular marketed by the company ENGELHARD under the name Yellow (4502) (Chromalite); nacres of red tint with a gold sheen in particular marketed by the company ENGELHARD under the name Sunstone G012 (Gemtone); black mother-of-pearl with a gold sheen marketed in particular by the company ENGELHARD under the name Nu antique bronze 240 AB (Timica), blue mother-of-pearl in particular marketed by the company MERCK under the name Matte blue (17433) (Microna), Dark Blue (117324) (Colorona), white nacres with a silver sheen in particular marketed by the company MERCK under the name Xirona Silver and pinkish orange-golden nacres in particular marketed by the company MERCK under the name Indian Summer (Xirona) and mixtures thereof.

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

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

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

The size of the pigment used in the cosmetic 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 product thanks to a dispersing agent.

By “ dispersing agent ” is meant a compound which makes it possible to protect the dispersed particles against their agglomeration or flocculation. This dispersing agent can be a surfactant, an oligomer, a polymer or a mixture of several of them, 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 dispersing agents also have at least one functional group that is compatible or soluble in the continuous medium. Said agent can be charged, it can be anionic, cationic, zwitterionic or neutral.

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

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 cosmetic composition according to the invention can be surface-treated with an organic agent.

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

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

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

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

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

The surface treatment can thus be carried out, for example, by chemical reaction of a surfactant with the surface of the pigments and creation of a covalent bond between the surfactant and the pigments or the fillers. This method is described in particular in US patent 4,578,266.

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

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

• un traitement PEG-Silicone comme le traitement de surface AQ commercialisé par LCW ;
• un traitement Chitosane comme le traitement de surface CTS commercialisé par LCW ;
• un traitement Triéthoxycaprylylsilane comme le traitement de surface AS commercialisé par LCW ;
• un traitement Méthicone comme le traitement de surface SI commercialisé par LCW ;
• un traitement Diméthicone comme le traitement de surface Covasil 3.05 commercialisé par LCW ;
• un traitement Diméthicone / Triméthylsiloxysilicate comme le traitement de surface Covasil 4.05 commercialisé par LCW ;
• un traitement Lauroyl Lysine comme le traitement de surface LL commercialisé par LCW ;
• un traitement Lauroyl Lysine Diméthicone comme le traitement de surface LL / SI commercialisé par LCW ;
• un traitement Myristate de Magnésium comme le traitement de surface MM commercialisé par LCW ;
• un traitement Dimyristate d’Aluminium comme le traitement de surface MI commercialisé par Miyoshi ;
• un traitement Perfluoropolyméthylisopropyl éther comme le traitement de surface FHC commercialisé par LCW ;
• un traitement Isostéaryl Sébacate comme le traitement de surface HS commercialisé par Miyoshi ;
• un traitement Disodium Stéaroyl Glutamate comme le traitement de surface NAI commercialisé par Miyoshi ;
• un traitement Diméthicone / Disodium Stéaroyl Glutamate comme le traitement de surface SA / NAI commercialisé par Miyoshi ;
• un traitement Phosphate de Perfluoroalkyle comme le traitement de surface PF commercialisé par Daito ;
• un traitement Copolymère acrylate / Diméthicone et Phosphate de Perfluoalkyle comme le traitement de surface FSA commercialisé par Daito ;
• un traitement Polyméthylhydrogène siloxane / Phosphate de Perfluoroalkyle comme le traitement de surface FS01 commercialisé par Daito ;
• un traitement Lauryl Lysine / Aluminium Tristéarate comme le traitement de surface LL-StAI commercialisé par Daito ;
• un traitement Octyltriéthylsilane comme le traitement de surface OTS commercialisé par Daito ;
• un traitement Octyltriéthylsilane / Phosphate de Perfluoroalkyle comme le traitement de surface FOTS commercialisé par Daito ;
• un traitement Copolymère Acrylate / Diméthicone comme le traitement de surface ASC commercialisé par Daito ;
• un traitement Isopropyl Titanium Triisostéarate comme le traitement de surface ITT commercialisé par Daito ;
• un traitement Cellulose Microcrystalline et Carboxyméthyl Cellulose comme le traitement de surface AC commercialisé par Daito ;
• un traitement Cellulose comme le traitement de surface C2 commercialisé par Daito ;
• un traitement copolymère Acrylate comme le traitement de surface APD commercialisé par Daito ;
• un traitement Phosphate de Perfluoroalkyle / Isopropyl Titanium Triisostéarate comme le traitement de surface PF + ITT commercialisé par Daito
• La composition conforme à la présente invention peut de plus comprendre un ou plusieurs pigments non traités en surface.
• Selon un mode de réalisation particulier de l’invention, le ou les pigments sont des pigments minéraux.
• Selon un autre mode particulier de l’invention, le ou les pigments sont choisis parmi les nacres.

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

• a PEG-Silicone treatment such as the AQ surface treatment marketed by LCW;
• a Chitosan treatment such as the CTS surface treatment marketed by LCW;
• a triethoxycaprylylsilane treatment such as the AS surface treatment marketed by LCW;
• a Methicone treatment such as the SI surface treatment marketed by LCW;
• a Dimethicone treatment such as the Covasil 3.05 surface treatment marketed by LCW;
• a Dimethicone/Trimethylsiloxysilicate treatment such as the Covasil 4.05 surface treatment marketed by LCW;
• a Lauroyl Lysine treatment such as the LL surface treatment marketed by LCW;
• a Lauroyl Lysine Dimethicone treatment such as the LL/SI surface treatment marketed by LCW;
• a Magnesium Myristate treatment such as the MM surface treatment marketed by LCW;
• an Aluminum Dimyristate treatment such as the MI surface treatment marketed by Miyoshi;
• a perfluoropolymethylisopropyl ether treatment such as the FHC surface treatment marketed by LCW;
• an Isostearyl Sebacate treatment such as the HS surface treatment marketed by Miyoshi;
• a Disodium Stearoyl Glutamate treatment such as the NAI surface treatment marketed by Miyoshi;
• a Dimethicone/Disodium Stearoyl Glutamate treatment such as the SA/NAI surface treatment marketed by Miyoshi;
• a Perfluoroalkyl Phosphate treatment such as the PF surface treatment marketed by Daito;
• an acrylate copolymer/dimethicone and perfluoalkyl phosphate treatment such as the FSA surface treatment marketed by Daito;
• a polymethylhydrogen siloxane/perfluoroalkyl phosphate treatment such as the FS01 surface treatment marketed by Daito;
• a Lauryl Lysine/Aluminum Tristearate treatment such as the LL-StAI surface treatment marketed by Daito;
• an Octyltriethylsilane treatment such as the OTS surface treatment marketed by Daito;
• an Octyltriethylsilane/Perfluoroalkyl Phosphate treatment such as the FOTS surface treatment marketed by Daito;
• an Acrylate/Dimethicone Copolymer treatment such as the ASC surface treatment marketed by Daito;
• an Isopropyl Titanium Triisostearate treatment such as the ITT surface treatment marketed by Daito;
• a Microcrystalline Cellulose and Carboxymethyl Cellulose treatment such as the AC surface treatment marketed by Daito;
• a Cellulose treatment such as the C2 surface treatment marketed by Daito;
• an Acrylate copolymer treatment such as the APD surface treatment marketed by Daito;
• a Perfluoroalkyl Phosphate / Isopropyl Titanium Triisostearate treatment such as the PF + ITT surface treatment marketed by Daito
• The composition in accordance with the present invention may also comprise one or more surface-untreated pigments.
• According to a particular embodiment of the invention, the pigment or pigments are mineral pigments.
• According to another particular embodiment of the invention, the pigment or pigments are chosen from nacres.

According to one particular embodiment of the invention, the dispersing agent is present with organic pigments in the dispersion (A), and/or the composition (B), and/or (C) or inorganic in the form sub-micron sized particle.

By “ sub-micronic ” or in English “ sub-micronic ” is meant pigments whose particle size has been micronized by the micronization method and whose average particle size is less than one micronmeter (μm), in particular between 0.1 and 0.9 μm, and preferably between 0.2 and 0.6 μm

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

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

“ Compatible ” means, for example, that said dispersing agent is miscible in the oily phase of the composition or of the dispersion containing the pigment(s), it does not delay or reduce the hardening. The dispersing agent is preferably cationic.

• les amino-silicones i.e. silicones comprenant un ou plusieurs groupes amino telles que celles commercialisées sous les noms et références :BYK LPX 21879, par BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP-967 et GP-988-1, commercialisée par Genesee les polymères,
• les acrylates de silicone telles que Tego^®RC 902, Tego^®RC 922, Tego^®RC 1041, et Tego^®RC 1043, par commercialisée Evonik,
• les silicones polydiméthylsiloxanes (PDMS) à groupes carboxyliques tel que X- 22162 et X-22370 par Shin-Etsu, époxy de silicone tel que le GP-29, GP-32, GP-502, GP-504, GP-514, GP-607, GP-682, et GP-695, par Genesee Polymers, ou Tego^®RC 1401, Tego^®RC 1403, Tego^®RC 1412, par Evonik.

The dispersing agent(s) can therefore have a silicone backbone, such as silicone polyether and dispersants of the amino-silicone type. Among the suitable dispersing agents, mention may be made of:

• amino-silicones, ie silicones comprising one or more amino groups such as those marketed under the names and references: BYK LPX 21879, by BYK, GP-4, GP-6, GP-344, GP-851, GP-965, GP -967 and GP-988-1, marketed by Genesee polymers,
• silicone acrylates such as Tego ^® RC 902, Tego ^® RC 922, Tego ^® RC 1041, and Tego ^® RC 1043, marketed by Evonik,
• polydimethylsiloxane (PDMS) silicones with carboxylic groups such as X-22162 and X-22370 by Shin-Etsu, silicone epoxy such as GP-29, GP-32, GP-502, GP-504, GP-514, GP -607, GP-682, and GP-695, by Genesee Polymers, or Tego ^® RC 1401, Tego ^® RC 1403, Tego ^® RC 1412, by Evonik.

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

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

Preferably, the pigment(s) v) of the invention are chosen from carbon black, iron oxides, in particular black, and micas coated with iron oxide, triarylmethane pigments, in particular blue and violet, such as BLUE 1 LAKE, azo pigments, in particular red, such as D&C RED 7 alkali metal salt of lithol red such as the calcium salt of lithol red B.

The coloring agents can be chosen from direct dyes.

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, or as only colorants.

These direct dyes are, for example, chosen from neutral, acid or cationic nitrobenzene direct dyes, neutral, acid or cationic azo direct dyes, tetraazapentamethine dyes, quinone and in particular neutral, acid or cationic anthraquinone dyes, azine direct dyes , triarylmethane direct dyes, azomethine direct dyes and natural direct dyes.

Examples of suitable direct dyes include azo direct dyes; (poly)methine dyes such as cyanines, hemicyanines, and styryl dyes; carbonyls; azines; nitro (hetero)aryl; tri-(hetero)aryl methanes; porphyrins; phthalocyanines and natural direct dyes, alone or in mixtures.

Preferably, the direct dye(s) contain at least one quaternized cationic chromophore or at least one chromophore bearing a quaternized or quaternizable cationic group.

According to a particular embodiment of the invention, the direct dyes comprise at least one quaternized cationic chromophore.

By way of direct dye according to the invention, mention may be made of acridine dyes; acridones; anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azo, hydrazono or hydrazones, in particular arylhydrazones; azomethines; benzanthropes; benzimidazoles; benzimidazolones; benzindoles; benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines; bis isoindolines; carboxanilides; coumarins; cyanines such as azacarbocyanines, diazacarbocyanines, diazahemicyanines, hemicyanines, or tetraazacarbocyanines; diazines; diketopyrrolopyrroles; dioxazines; diphenylamines; diphenylmethanes; dithiazines; flavonoids such as flavanthrones and flavones; fluorindins; formazans; indamines; indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines; isoindolines; isoindolinones; isovianthrone; lactones; (poly)methines such as dimethines of the stilbene or styryl type; naphthalimides; naphthanilides; naphtholactams; naphthoquinones; nitro, in particular nitro(hetero)aromatics; oxadiazoles; oxazines; periones; perinones; perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanine; polyenes/carotenoids; porphyrins; pyranthrone; pyrazolanthrones; pyrazolones; pyrimidinoanthropes; pyronins; quinacridones; quinolines; quinophthalones; squares; tetrazoliums; thiazines, thioindigo; thiopyronines; triarylmethanes, or xanthenes.

For cationic azo dyes, particular mention may be made of those derived from the cationic dyes described in the Kirk Othmer Encyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & sons, updated on 04/19/2010.

Among the azo dyes that can be used according to the invention, mention may be made of the cationic azo dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954.

According to a preferred embodiment of the invention, the direct dye or dyes are chosen from cationic dyes called “basic dyes”.

Mention may be made, among the azo dyes described in the International Color Index 3rd edition, and in particular of the following compounds:
- Basic Red 22
- Basic Red 76
- Basic Yellow 57
- Basic Brown 16
- Basic Brown 17.
Among the cationic quinone dyes, those mentioned in the aforementioned International Color Index are suitable, and among these, the following dyes may be mentioned, among others:
- Basic Blue 22
- Basic Blue 99.
Among the azine dyes which are suitable, mention may be made of those listed in the International Color Index and for example the following dyes:
- Basic Blue 17
- Basic Red 2.
Among the cationic triarylmethane dyes which can be used according to the invention, mention may be made, in addition to those listed in the Color Index, of the following dyes:
- Basic Green 1
- Basic Purple 3
- Basic Purple 14
- Basic Blue 7
- Basic Blue 26.

Mention may also be made of cationic dyes in documents US 5888252, EP 1133975, WO 03/029359, EP 860636, WO 95/01772, WO 95/15144, EP 714954. Mention may also be made of those listed in the encyclopedia "The chemistry of synthetic dye" by K. VENKATARAMAN, 1952, Academic press vol 1 to 7, in the encyclopedia "Kirk Othmer" "Chemical technology", chapter "dyes and Dye intermediate", 1993, Wiley and sons, and in various chapters of ULLMANN's ENCYCLOPEDIA of Industrial chemistry 7th edition, Wiley and sons.

Preferably, the cationic direct dyes are chosen from those derived from azo and hydrazono type dyes.

According to a particular embodiment, the direct dyes are cationic azo, described in EP 850636, FR 2788433, EP 920856, WO 9948465, FR 2757385, EP 850637, EP 918053, WO 9744004, FR 2570946, FR 2285851, DE 3,53836 2189006, fr 1560664, fr 1540423, fr 1567219, FR 1516943, FR 1221122, of 4220388, of 4137005, WO 0166646, US 5708151, WO 9501772, WO 515144, GB 1195386, US 35248413, GB 738585, DE 2527638, FR 2275462, GB 1974-27645, Acta Histochem. (1978), 61(1), 48-52; Tsitologiya (1968), 10(3), 403-5; Zh. Obshch. Khim. (1970), 40(1), 195-202; Ann. Chem. (Rome) (1975), 65(5-6), 305-14; Journal of the Chinese Chemical Society (Taipei) (1998), 45(1), 209-211; Rev. rum. Chem. (1988), 33(4), 377-83; Text. Res. J. (1984), 54(2), 105-7; Chem. Ind. (Milan) (1974), 56(9), 600-3; Khim. Tekhnol. (1979), 22(5), 548-53; Ger. Monatsh. Chem. (1975), 106(3), 643-8; Mr R. L. Bull. Res. Dev. (1992), 6(2), 21-7; Lihua Jianyan, Huaxue Fence (1993), 29(4), 233-4; Pigment dyes. (1992), 19(1), 69-79; Pigment dyes. (1989), 11(3), 163-72.

Preferably, the cationic direct dye or dyes include a quaternary ammonium group, more preferably the cationic charge is endocyclic.

These cationic radicals are for example a cationic radical:
- with exocyclic charge (di/tri)(C1-C8)alkylammonium, or
- with an endocyclic charge such as comprising a cationic heteroaryl group chosen from: acridinium, benzimidazolium, benzobistriazolium, benzopyrazolium, benzopyridazinium, benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium, bi-pyridinium, bis-tetrazolium, dihydrothiazolium, imidazopyridinium, imidazolium, indolium, isoquinolium, naphthoimidazolium, naphthooxazolium, naphthopyrazolium, oxadiazolium, oxazolium, oxazolopyridinium, oxonium, phénazinium, phénooxazolium, pyrazinium, pyrazolium, pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium, pyrylium , quinolium, tétrazolium, thiadiazolium, thiazolium, thiazolopyridinium, thiazoylimidazolium, thiopyrylium, triazolium ou xanthylium.

Mention may be made of the hydrazono cationic dyes of formula (III) and (IV), the azo compounds of formulas (V) and (VI) below:

[Chem 34]

formulas (III) to (VI) 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 i) (C ₁ -C ₈ )alkyl optionally substituted, ii) (C ₁ -C ₈ )alkoxy optionally substituted, iii) (di)(C ₁ -C ₈ )(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group, iv) aryl(C ₁ -C ₈ )alkylamino, v) 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;
▪ R _a and R _b , 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 R _a with a substituent of Het ⁺ and/or R _b with a substituent of Ar form together with the atoms which carry them a (hetero)cycloalkyl; particularly R _a and R _b , 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 sulfate.

In particular, mention may be made of direct dyes with cationic charge, endocyclic azo and hydrazono of formula (III) to (VI) as defined above. More particularly the cationic direct dyes of formula (III) to (VI) with endocyclic cationic charge described in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferably, the following direct dyes:

[Chem 35]

formulas (III-1) and (V-1) 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 (III-1) and (V-1) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives:

[Chem 36]

with Q ^- an anionic counterion as defined previously, particularly halide such as chloride or an alkyl sulphate such as methyl sulphate or mesytyl.

According to a particular embodiment of the invention, the direct dyes are fluorescent, that is to say they contain at least one fluorescent chromophore as defined above.

As fluorescent dyes, mention may be made of the radicals resulting from the dyes acridines, acridones, benzanthrones, benzimidazoles, benzimidazolones, benzindoles, benzoxazoles, benzopyrans, benzothiazoles, coumarins, difluoro{2-[(2H-pyrrol-2-ylidene-kN) methyl]-1H-pyrrolato-kN}bores (BODIPY®), diketopyrrolo-pyrroles, fluorindines, (poly)methines (including cyanines and styryls/hemicyanines), naphthalimides, naphthanilides, naphthylamine (such as dansyls), oxadiazoles, oxazines, periones , perinones, perylenes, polyenes/carotenoids, squaranes, stilbenes, xanthenes.

Mention may also be made of the fluorescent dyes described in the documents EP 1133975, WO 03/029359, EP 860636, WO 95/01772, WO 95/15144, EP 714954 and those listed in the encyclopedia "The chemistry of synthetic dye" by K VENKATARAMAN, 1952, Academic press vol 1 to 7, in the encyclopedia "Kirk Othmer" "Chemical technology", chapter "dyes and Dye intermediate", 1993, Wiley and sons, and in various chapters of the encyclopedia "ULLMANN's ENCYCLOPEDIA of Industrial chemistry" 7th edition, Wiley and sons, in The Handbook — A Guide to Fluorescent Probes and Labeling Technologies, 10th Ed Molecular Probes/Invitrogen – Oregon 2005 distributed via the Internet or in previous printed editions.

According to a preferred variant of the invention, the fluorescent dye or dyes are cationic and comprise at least one quaternary ammonium radical such as those of formula (VII) below:

formula (VII) in which:
▪ W ⁺ represents a cationic heterocyclic or heteroaryl group, particularly comprising a quaternary ammonium optionally substituted by one or more (C ₁ -C ₈ )alkyl groups optionally substituted in particular by one or more hydroxyl groups;
▪ Ar representing an aryl group such as phenyl or naphthyl, optionally substituted preferentially by i) one or more halogen atoms, such as chlorine, fluorine; ii) one or more (C ₁ -C ₈ )alkyl groups, preferably C ₁ -C ₄ such as methyl; iii) one or more hydroxyl groups; iv) one or more (C ₁ -C ₈ )alkoxy groups such as methoxy; v) one or more hydroxy(C ₁ -C ₈ )alkyl groups such as hydroxyethyl, vi) one or more amino or (di)(C ₁ -C ₈ )alkylamino groups, preferably with the C ₁ -C alkyl part ₄ optionally substituted by one or more hydroxyl such as (di)hydroxyethylamino, vii) by one or more acylamino groups; viii) one or more heterocycloalkyl groups such as piperazinyl, piperidinyl or 5 or 6 membered heteroaryl such as pyrrolidinyl, pyridinyl and imidazolinyl;
▪ m' represents an integer ranging from 1 to 4, particularly m is 1 or 2; more preferably 1;
▪ R _c , R _d , identical or different, represent a hydrogen atom or an optionally substituted (C ₁ -C ₈ )alkyl group, preferably C ₁ -C ₄ , or else R _c contiguous to W ⁺ and/or R _d contiguous to Ar form with the atoms which carry them a (hetero)cycloalkyl, particularly R _c is contiguous to W ⁺ and forms a (hetero)cycloalkyl such as cyclohexyl;
▪ Q ^- is an organic or inorganic anionic counterion as previously defined.

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.

According to a particular embodiment of the invention, the quantity of coloring agents, in particular of pigments varies from 0.5% up to 40%, and preferably from 1 to 20% relative to the weight of the composition and dispersion understanding them.

the plasticizer(s) vi)

According to a particular embodiment, the method uses one or more plasticizers. The said plasticizer(s) possibly being in the composition (A), and/or (B) and/or (C).

By " plasticizer " or " plasticizing agent " is meant an organic chemical compound, which is in the solid state or in the liquid state, at room temperature and at atmospheric pressure, and which is added to a composition comprising different types of polymerizable ingredients (monomers), to make the polymer softer, more flexible, and/or improve its mechanical strength. Plasticizers are known to those skilled in the art, mention may be made, for example, of “Plasticizers”, Encyclopedia of polymer Science and Technology , Helmut Reinecke, Rodrigo Navarro, Mónica Pérez, https://doi.org/10.1002/0471440264.pst245. pub215 September 2011.

The plasticizers within the meaning of the invention have a molecular weight of between 200 and 1000 g/mol, particularly between 300 and 700, preferably between 350 and 600. The agents are also organic compounds consisting of carbon atoms , hydrogen, and one or more heteroatoms chosen from oxygen, sulfur and silicon atoms, in particular chosen from oxygen and silicon atoms, preferably at least 3 heteroatoms even more preferably between 4 and 10 heteroatoms, and may have one or more aryl groups such as benzyl. In particular, they comprise one or more groups chosen from esters, phthalates, benzoates, sulphonates, citrates and siloxanes.

Preferably, the plasticizer(s) of the invention are chosen from those of the families of phthalates, esters, citrates, benzoates and siloxanes.

According to a particular embodiment of the invention, the plasticizer(s) are chosen from the compounds (XIV) and (XV) below:

(XIV)
Formula (XIV) in which:
- R ^h , and R ⁱ , which are identical or different, represent a group (C ₁ -C ₂₀ )alkyl, aryl such as phenyl, aryl (C ₁ -C ₄ )alkyl such as benzyl, preferably (C ₁ -C ₄ ) alkyl such as n -butyl;

- n is 1, 2 or 3, preferably 2; And

- L represents a group a) C ₁ -C ₁₀ alkyl, di, tri or tetravalent, preferably (C ₂ -C ₈ ) trivalent alkyl, said di, tri or tetravalent alkyl, possibly being substituted by one or more groups hydroxy, b) di, or trivalent cycloalkyl, or c) di, tri or tetravalent aryl, preferably di, or trivalent phenyl, preferably L represents a group a);

(XV)

Formula (XV) in which:
-R^I, identical or different, preferably identical, represents a group (C₁-VS₁₀)alkyl, aryl such as phenyl, aryl(C₁-VS₄)alkyl such as benzyl, preferably aryl such as phenyl,
-R^I identical or different, preferably identical represents a hydrogen atom, or a hydroxy group, (C₁-VS₆)alkyl, or (C₁-VS₆)alkoxy,
-L' represents a group selected from a) C-alkyl₂-VS₁₀, divalent, preferably (C₄-VS₈)divalent alkyl, which may be optionally substituted by one or more hydroxy groups, and/or interrupted by one or more oxygen atoms, and/or interrupted by one or more divalent groups -Si(R^I)(R^k)- with R^Iand R^kas previously defined, b) di, or trivalent cycloalkyl, c) di, tri or tetravalent aryl, and d) -Si(R^I)(R^k)-, preferably L' represents a group d) -Si(R^I)(R^k)-.

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

(XV')

Formula (XV) in which:
- R ^h , and R ⁱ , which are identical or different, represent a group (C ₁ -C ₆ )alkyl, aryl (C ₁ -C ₄ )alkyl such as benzyl, preferably (C ₁ -C ₄ )alkyl such as n - butyl;

- n is 1, or 2, preferably 2; And

- L represents a group a) C ₂ -C ₆ alkyl, di, tri or tetravalent, preferably (C ₂ -C ₈ )trivalent alkyl, said alkyl possibly being substituted by one or more hydroxy groups, preferably substituted by a hydroxy group.
According to a particular embodiment of the invention, the compounds of formula (XV) are chosen from the compounds of formula (XV'):

(XV')

Formula (XV') in which:
-R^I, identical or different, preferably identical, represents an aryl group such as phenyl, aryl(C₁-VS₄)alkyl such as benzyl, preferably aryl such as phenyl, and
-R^I identical or different, preferably identical, represents a group represents (C₁-VS₆)alkyl, preferably (C₁-VS₄)alkyl such as methyl.

In particular, the plasticizer(s) of the invention are chosen from: di n -hexyl phthalate (DnHP), diisoheptyl phthalate (DIHP), diheptyl phthalate (DnHP), di(2-ethylhexyl) phthalate (DEHP), diheptylnonyl phthalate (DnHNP ), di n -octyldecylphthalate (DNODP), diheptylnonylundecylphthalate (DnHNUP), diisononyl phthalate (DINP), dinonyl phthalate (DNP), di n -nonyl phthalate (DnNP) diisodecyl phthalate (DIDP), di n -nonyldecylundecyl phthalate (DnNDUP), dinonylundecyl phthalate (DnNUP), diundecyl phthalate (DUP), diisoundecyldodecylphthalate (UDP), ditridecyl phthalate (DTDP), di(2-ethylhexyl)teraphthalate (DOTP), butylbenzyl phthalate (BBP), diheptylnonyl adipate (DnHNA), di(2- ethylhexyl) adipate (DEHA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), triheptylnonyl trimellitate (TnHNTM), tri(2-ethylhexyl)trimellitate (TOTM), triisononyl trimellitate (TINTM), di(2-ethylhexyl) sebacate ( DOS), di(2-ethylhexyl) azelate (DOZ), tributyl citrate and trimethylpentaphenyltrisiloxane, preferably the plasticizer(s) of the invention are chosen from: tri(C ₁ -C ₆ )alkyl citrates such as tributyl citrate and trimethylpentaphenyltrisiloxane .

The plasticizer(s) vi) of the invention may be present in composition (A), and/or in composition (B), and/or in another composition (C). Preferably, the plasticizer(s) of the invention are present in composition (A) or (C), preferably (A).

According to a particular embodiment of the invention, the plasticizer(s) is present in an amount of between 5 and 50% by weight, relative to the total weight of the polymer(s) a) to d) of the particles.

According to a particular embodiment of the invention of the invention, the plasticizer(s) is present in an amount of between 0.5 and 30% by weight, in particular between 1 and 20%, preferably from 1.5 to 10 % by weight relative to the total weight of composition (A), and/or in composition (B), and/or in another composition (C), preferably relative to the total weight of composition (A).

The process of the invention:

The present invention relates to a method for treating keratin materials, preferably keratin fibers, in particular human fibers such as the hair, or human skin, in particular the lips, said method preferably consisting of at least two steps implementing in a first time the application to said materials of an oily dispersion A) comprising i) particles of copolymers of alkyl acrylates and acrylic anhydrides, ii) stabilizing agents, iii) one or more hydrocarbon oils; then in a second step the application to said materials of a composition (B) comprising iv) one or more hydroxylated and/or thiolated compounds, it being understood that the process of the invention implements v) one or more active ( s) cosmetic(s) chosen from a) pigments, b) active agents for caring for keratin materials, preferably the skin, and c) UV screening agents as well as d) mixtures thereof; the ingredients a) to d) possibly being in composition (A), and/or in composition (B), and/or in another composition (C).

According to a particular embodiment of the invention, the process is a process for the treatment of keratin materials, in particular keratin fibers, in particular human fibers such as the hair or skin, preferably human, and more preferentially of the face such as the lips, including:
1) the application to said materials of an oily dispersion (A), preferably anhydrous, comprising:
i) one or more particle(s) consisting of one or more ethylenic copolymer(s):
a) (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl, preferably (meth)acrylate (C ₁ -C ₄ )alkyl and
b) an ethylenically unsaturated anhydride compound, preferably maleic anhydride; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from:
c) polymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl monomers; And
d) copolymers of (C ₁ -C ₆ )(alkyl)acrylate, (C ₃ -C ₁₂ )cycloalkyl and (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl; And
iii) one or more hydrocarbon oil(s);
2) the application to said materials of a composition (B), preferably anhydrous, comprising:
iv) one or more hydroxylated and/or thiolated compound(s), polymer(s) or not, preferably organic(s) or silicone(s);
Being heard that :
- the process of the invention uses v) one or more cosmetic active ingredient(s) chosen from a) pigments, b) active ingredients for caring for keratin materials, preferably the skin and c) the UV filters as well as d) their mixtures the ingredients a) to d) which is in another composition (C); And
- composition (A) is applied to said materials, then composition (B) is applied to said materials and then composition (C) is applied to said materials.

• le procédé de l’invention met en œuvre v) un ou plusieurs actif(s) cosmétique(s) choisi(s) parmi les a) pigments, b) les actifs de soin des matières kératiniques de préférence de la peau et c) les filtres UV ainsi que d) leur mélanges les ingrédients a) à d) – de préférence a) - qui se trouve dans la composition (C) ; et
• la composition (C) est appliquée sur lesdites matières, puis la composition (A) est appliquée sur lesdites matières puis la composition (B) être appliquée sur lesdites matières.

According to another particular embodiment of the invention, the method is a method for treating keratin materials, in particular keratin fibres, in particular human fibers such as the hair, or the skin, preferably human, and more preferably of the face such as the lips, using the compositions (A), (B) and (C) in which:

• the process of the invention uses v) one or more cosmetic active ingredient(s) chosen from a) pigments, b) active ingredients for caring for keratin materials, preferably the skin, and c) UV filters as well as d) their mixtures the ingredients a) to d) - preferably a) - which is in the composition (C); And
• composition (C) is applied to said materials, then composition (A) is applied to said materials and then composition (B) is applied to said materials.

• le procédé de l’invention en œuvre v) un ou plusieurs actif(s) cosmétique(s) choisi(s) parmi les a) pigments, b) les actifs de soin des matières kératiniques de préférence de la peau et c) les filtres UV ainsi que d) leur mélanges les ingrédients a) à d) – de préférence a) - qui se trouve dans la composition (C) ; et
• la composition (C) est appliquée sur lesdites matières, puis la composition (A) et (B) sont appliquée simultanément sur lesdites matières ou alors un mélange de composition (A) + (B) est appliqué sur lesdites matière après l’application de la composition (C) sur lesdites matières.

According to yet another embodiment of the invention, the method is a method for treating keratin materials, in particular human keratin fibers, such as the hair, or the skin, preferably human, and more preferably of the face such as lips, using the compositions (A), (B) and (C) in which in which:

• the process of the invention uses v) one or more cosmetic active ingredient(s) chosen from a) pigments, b) active ingredients for caring for keratin materials, preferably the skin, and c) filters UV as well as d) their mixtures the ingredients a) to d) - preferably a) - which is in the composition (C); And
• composition (C) is applied to said materials, then composition (A) and (B) are applied simultaneously to said materials or else a mixture of composition (A) + (B) is applied to said materials after the application of composition (C) on said materials.

Process in at least 2 application steps:

According to an advantageous variant of the invention, the method of the invention is a method for treating keratin materials, in particular human keratin fibers, in particular hair, or skin, preferably human, and more preferably of the face such as the lips, including:
1) the application to said materials of an oily dispersion (A) comprising:
i) one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined previously; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously;
iii) one or more hydrocarbon-based oil(s) as defined above and v) one or more cosmetic agent(s), preferably pigment(s);
followed by
2) the application to said materials of a composition (B), comprising:
one or more hydroxylated and/or thiolated compound(s), polymer(s) or not, preferably organic(s) or silicone(s);

According to another advantageous variant of the invention, the method of the invention is a method for treating keratin materials, in particular human keratin fibers, in particular hair, or skin, preferably human, and more preferably the face such as the lips, including:
1) the application to said materials of an oily dispersion (A) comprising:
i) one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined previously; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s) as defined above;
followed by
2) the application to said materials of a composition (B) comprising:
iv) one or more hydroxylated and/or thiolated compound(s), polymer(s) or not, preferably organic(s) or silicone(s);
; And
v) one or more cosmetic agent(s), preferably pigment(s).

According to yet another variant of the invention, the method of the invention is a method for treating keratin materials, in particular human keratin fibers such as hair, or skin, preferably human, and more preferably of the face such than the lips, including:
1) the application to said materials of an oily dispersion (A) comprising:
i) one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined previously; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s) as defined above;
followed by
2) the application to said materials of a composition (B), comprising:
iv) one or more hydroxylated and/or thiolated compound(s), polymer(s) or not, preferably organic(s) or silicone(s);
followed by
3) the application to said materials of a composition (C) comprising:
v) one or more cosmetic active ingredient(s), preferably pigment(s).

According to yet another advantageous variant of the invention, the method of the invention is a method for treating keratin materials, in particular keratin fibers, in particular human fibers such as hair, or skin, preferably human, and more preferably of the face such as the lips, comprising:
1) the application to said materials of an oily dispersion (A) comprising:
i) one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined previously; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s) as defined above;
followed by
2) the application to said materials of a composition (C) comprising v) one or more cosmetic active ingredient(s), preferably pigment(s); followed by
3) the application to said materials of a composition (B) comprising:
iv) one or more hydroxylated and/or thiolated compound(s), polymer(s) or not, preferably organic(s) or silicone(s) as defined above.

According to a particularly preferred variant of the invention, the process of the invention is a process for treating keratin materials, in particular keratin fibers, in particular human fibers such as the hair or the skin, preferably human, and more preferably of the face such as the lips, including:
1) the application to said materials of a composition (C) comprising v) one or more cosmetic active ingredient(s), preferably pigment(s); followed by
2) the application to said materials of an oily dispersion (A) comprising:
i) one or more particle(s) consisting of one or more ethylenic copolymer(s) a) and b) as defined previously; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from c) and d) as defined previously; And
iii) one or more hydrocarbon oil(s) as defined above;
followed by
3) the application to said materials of a composition (B) comprising:
iv) one or more hydroxylated and/or thiolated compound(s), polymer(s) or not, preferably organic(s) or silicone(s) as defined above such than previously defined.

According to another particular variant of the invention, the cosmetic agent(s) v) as defined above, in particular the pigments, are found in a composition (C). The latter can be applied simultaneously with composition (A), or with composition (B). Preferably, composition (C) is applied after step 1) i.e. after application of composition (A), more preferably compositions (A) and (B) do not comprise hair dye and it is applied after step 1) of the process of the invention a composition (C) comprising one or more hair dyes v) as defined above, followed by the application to the keratin materials of the composition (B).

The present patent application also relates to a process, in particular cosmetic, for coloring keratin materials, in particular human keratin fibers such as the hair, comprising the topical application to the keratin materials of the compositions, in particular cosmetics, (A) and (B ) and optionally (C), as described above, it being understood that said coloring process uses v) one or more cosmetic active ingredient(s) chosen from a) pigments,

The dispersion of the invention the dispersion (A), and the compositions (B) and (C) are cosmetic, ie they only comprise cosmetically acceptable ingredients.
According to a preferred embodiment of the invention, the dispersion (A), and the compositions (B) and (C) are anhydrous.

According to another advantageous embodiment, dispersion (A) and composition (B) are anhydrous, and composition (C) is aqueous.

According to a particular embodiment of the invention, composition (B) is aqueous or aqueous-alcoholic.

According to another particularly advantageous embodiment of the invention, composition (C) is aqueous or aqueous-alcoholic.

According to yet another advantageous embodiment, dispersion (A) is anhydrous and composition (B) and composition (C) are aqueous or aqueous-alcoholic, preferably aqueous.

Compositions (B) and (C) and dispersion (A) according to the invention may comprise a cosmetic additive chosen from water, perfumes, preservatives, additional fillers different from cosmetic active agents v), additional oils different from hydrocarbon oils iii) of composition (A), waxes, surfactants, moisturizers, vitamins, ceramides, antioxidants, anti-free radical agents, additional polymers different from polymers i) and ii) of composition (A ), thickeners, coloring matter other than cosmetic active agents v).

The compositions (B) and (C) and dispersion (A) according to the invention can also comprise other dyestuffs such as fat-soluble dyes, water-soluble dyes. This dyestuff may be present in a content ranging from 0.01% to 30% by weight, relative to the total weight of the composition containing them, preferably from 0.01% to 10% by weight.

Examples of fat-soluble dyes are Sudan Red, D&C Red 17, D&C Green 6, β-carotene, soybean oil, Sudan Brown, D&C Yellow 11, D&C Violet 2, D&C Orange 5, quinoline yellow, annatto. Water-soluble dyes are for example beet juice, methylene blue.

According to one embodiment, the dispersion (A) and the compositions (B) and (C) according to the invention are anhydrous compositions.

Preferably, the first step of the process of the invention is the application of the dispersion (A) in one or more volatile apolar solvents, in particular isododecane.

According to another variant, step 2) follows step 1) without intermediate rinsing or drying. Preferably after application of the dispersion (A) during step 1), one waits between 1 minute and 6 hours, in particular between 10 minutes and 5 hours, more particularly between 30 minutes and 4 hours, preferably around 3 hours , to apply composition (B).

If the first step is the step of applying composition (C) followed by the application of the oily dispersion (A) then the application of composition (A) between the application of composition (C) (step 1) and the step of applying the dispersion (A) (step 2) the keratin materials are preferably air-dried.

If the first step is the step of applying the oily dispersion (A) and the second step is that of applying the composition (C) and the third step is that of applying the composition (B) between the application of composition (C) as defined above (step 2) and the step of applying composition (B) (step 3) the keratin materials are preferably air-dried.

If the first step is the application of the oily dispersion (A) then the application of the composition (B) then the application of the composition (C) between the application of the composition (C) (step 3) and the step of applying composition (B) (step 2) the keratin materials are preferably air-dried.

According to a variant, the treatment method according to the invention comprises a heating step, for example using a hair dryer or a heat lamp. In particular, this heating step occurs after application of composition (B).

The dispersion (A), and compositions (B) or (C) described above can be used on dry or wet keratin materials, as well as on all types of keratin materials, light or dark, and when the keratin materials are keratin fibres, these can be natural or colored, permed, bleached or straightened.

According to a particular embodiment of the method of the invention, the fibers are washed before application of the dispersion (A).

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

After the application of the dispersion (A), of the compositions (B), and (C), the fibers can be left to dry or dried, for example at a temperature greater than or equal to 30°C. According to a particular embodiment, this temperature is greater than 40°C. According to a particular embodiment, this temperature is above 45°C and below 220°C.

When the process for treating keratin fibers uses iv) one or more hydroxy compound(s), polymer(s) or not, preferably organic(s) or silicone(s) as defined( s) previously, then after the application of the dispersion (A), of the compositions (B), and (C), the keratin fibers are subjected to a temperature greater than or equal to 30°C. According to a particular embodiment, this temperature is greater than 45° C. and less than 220° C., for example with a hair dryer, a heating lamp then possibly with a straightening iron, the temperature being between 110 and 220° C. , preferably between 140 and 200°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 of the process of the invention can be implemented with a drying device such as a helmet, a hair dryer, a straightening iron, 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.

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

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

According to a preferred embodiment of the invention, step 1) is carried out on dry keratin fibers.

According to another particular embodiment of the process of the invention, step 1) is carried out on damp or wet keratin fibres.

According to an advantageous variant of the process of the invention, between step 1) and step 2), there is no rinsing, and the keratin fibers are dried in air or with the aid of drying device such as a hair dryer. Preferably after application of the dispersion (A) during step 1), one waits between 1 minute and 6 hours, in particular between 10 minutes and 5 hours, more particularly between 30 minutes and 4 hours, preferably around 3 hours , to apply composition (B).

According to a particular variant of the process of the invention, between step 1) and step 2), one or more successive rinsings with water are carried out, possibly followed by drying in air or using a drying device. such as a hair dryer.

According to another variant, step 2) follows step 1) without intermediate rinsing or drying. Preferably after application of the dispersion (A) during step 1), one waits between 1 minute and 6 hours, in particular between 10 minutes and 5 hours, more particularly between 30 minutes and 4 hours, preferably around 3 hours , to apply composition (B).

If the first step is the step of applying composition (C) followed by the application of the oily dispersion (A) then the application of composition (A) between the application of composition (C) (step 1) and the step of applying the dispersion (A) (step 2) the keratin fibers are preferably dried in the air or using a drying device such as a hair dryer.

If the first step is the step of applying the oily dispersion (A) and the second step is that of applying the composition (C) and the third step is that of applying the composition (B) between the application of composition (C) as defined above (step 2) and the step of applying composition (B) (step 3) the keratin fibers are preferably dried in the air or with the aid of drying device such as a hair dryer.

If the first step is the application of the oily dispersion (A) then the application of the composition (B) then the application of the composition (C) between the application of the composition (C) (step 3) and the step of applying composition (B) (step 2) the keratin fibers are preferably dried in the air or using a drying device such as a hair dryer.

The kit

• dans un premier compartiment : la dispersion (A) telle que définie précédemment,
• dans un deuxième compartiment distinct : la composition (B) telle que définie précédemment, et
• éventuellement dans un troisième compartiment distinct des deux autres : la composition (C) telle que définie précédemment.

The invention also relates to a kit or device with several separate compartments comprising:

• in a first compartment: the dispersion (A) as defined above,
• in a second separate compartment: composition (B) as defined above, and
• optionally in a third compartment separate from the other two: composition (C) as defined previously.

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

A subject of the invention is also the oily dispersion (A) as defined above comprising v) the cosmetic agent(s) as defined above, it being understood that when v) represents one or several pigment(s) then the dispersion is anhydrous and comprises iv) one or more hydroxylated and/or thiolated compound(s), polymer(s) or not, preferably organic(s) or silicone(s) ) as defined above.

A subject of the invention is also the oily dispersion (A) which is in an inverse emulsion (W/O) as defined previously and comprises iv) one or more hydroxylated and/or thiolated compound(s) ), polymer(s) or not, preferably organic(s) or silicone(s) as defined above.

The invention is further illustrated in the following examples.

EXAMPLES

Example 1 Example 2 Example 3 THIOL 1 THIOL 2 THIOL 3 Emulsion made with a fluid silicone that includes thiol groups
(Supplier ref: KM-9769) - SHIN-ETSU (Mercaptopropyl)Methylsiloxane - Dimethylsiloxane Copolymers
(CAS Number: [102783-03-9])
Supplier ref: SMS-042, GELEST (Mercaptopropyl)Methylsiloxane - Dimethylsiloxane Copolymers
(CAS Number: [102783-03-9])
Supplier ref: SMS-992: GELEST

Process for treating keratin materials in 2 steps:

• base coat: deposit of a pigmented solution of copolymers with maleic anhydride functions in volatile apolar solvents such as isododecane.
• top coat: deposit with crosslinkers

The various combinations were evaluated for the “ make-up ” or coating in particular of keratin fibers (hair), ie coating of the keratin fibers with dyes/pigments. A comparison to the resistance to shampoos of the coatings was carried out

Oily dispersions:

• 70 % en poids de a) de (C₁-C₄)(alkyl)acrylate de (C₁-C₄)alkyle (tel que l’Acrylate d’Ethyle),
• 10 % en poids de b) composé anhydride à insaturation éthylénique (tel que l’Anhydride Maléique), et à
• 20 % en poids de c) polymères de monomères (C₁-C₆)(alkyl)acrylate de (C₃-C₁₂)cycloalkyle (tel que l’Acrylate d’Isobornyle).

The oily dispersions (A) are formed as a whole [particles i) + stabilizing agent ii)] at:

• 70% by weight of a) (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl (such as Ethyl Acrylate),
• 10% by weight of b) ethylenically unsaturated anhydride compound (such as maleic anhydride), and
• 20% by weight of c) polymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl monomers (such as Isobornyl Acrylate).

The preparation of these oily dispersions was carried out in a 1 liter controlled reactor. The synthesis is carried out in two steps:

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

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

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

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

Quantity of reagents:

Step 1 :

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

Isododecane added between the two steps:

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

2nd step :

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

Experimental protocol :

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

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

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

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

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

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

Scatter (A1)

Ingredients Quantity (g) Oily dispersion stabilizing agent i) + particulate core ii) 15 (ma) BLUE 1 LAKE pigment and TRIETHOXYCAPRYLYLSILANE (CI 42090 & TRIETHOXYCAPRYLYLSILANE) 6 Isododecane Qsp 100 my. = amount of active ingredient

Membership (B1)

Ingredients Quantity (g) Compound THIOL 1 5 WATER Qsp 100

• Application sur les fibres kératiniques (cheveux secs) de la dispersion (Ax) selon un rapport de bain 0,5 g de dispersion ou composition / g de cheveu ;
• La mèche est séchée au sèche-cheveux ; puis
• Application de la composition (Bx) selon un rapport de bain de 0,5 g de composition (Bx) / g de cheveu ; puis
• La mèche est séchée au sèche-cheveux.
• La mèche peut également être lissée à l’aide d’un fer à lisser à une température de 180 °C, en appliquant 10 passages de manière régulière tout au long de la mèche.

The different stages of the application protocol on keratin fibers (90% white natural hair also called 90% BN):

• Application to the keratinous fibers (dry hair) of the dispersion (Ax) according to a bath ratio of 0.5 g of dispersion or composition/g of hair;
• The lock is dried with a hair dryer; Then
• Application of composition (Bx) according to a bath ratio of 0.5 g of composition (Bx)/g of hair; Then
• The wick is dried with a hair dryer.
• The wick can also be straightened using a hair straightener at a temperature of 180°C, applying 10 passes evenly throughout the wick.

Shampoo resistance evaluations are thus carried out 24 hours after application.

Study of resistance to shampoos combined with brushing:

The different combinations were evaluated for “hair make-up” or coating of keratin fibres, i.e. coating of keratin fibers with dyes/pigments. A comparison to the resistance to shampoos associated with brushing (brushing) of the coatings was also carried out:

2-step process:
The following dispersions and compositions were prepared. The amounts are given in g per 100 g of dispersion or composition.

Scatter (A3)

Ingredients Quantity (g) Oily dispersion stabilizing agent i) + particulate core ii) 15 (m.a.) IRON OXIDES and ISOPROPYL TITANIUM TRIISOSTEARATE 6 Isododecane Qsp 100

Membership (B2)

Ingredients Quantity (g) Compound THIOL 2 8 Isododecane Qsp 100

• Application sur les fibres kératiniques (cheveux secs) de la dispersion (Ax) selon un rapport de bain 0,5 g de dispersion ou composition / g de cheveu ;
• La mèche est séchée au sèche-cheveux ; puis
• Application de la composition (Bx) selon un rapport de bain de 0,5 g de composition (Bx) / g de cheveu ; puis
• La mèche est séchée au sèche-cheveux.
• La mèche peut également être lissée à l’aide d’un fer à lisser à une température de 180°C, en appliquant 10 passages de manière régulière tout au long de la mèche.
• La mèche est ensuite lavée au shampoing , puis
• La mèche est séchée et brossée 10 fois

The different stages of the application protocol on keratin fibers (90% white natural hair also called 90% BN):

• Application to the keratinous fibers (dry hair) of the dispersion (Ax) according to a bath ratio of 0.5 g of dispersion or composition/g of hair;
• The lock is dried with a hair dryer; Then
• Application of composition (Bx) according to a bath ratio of 0.5 g of composition (Bx)/g of hair; Then
• The wick is dried with a hair dryer.
• The wick can also be smoothed using a straightening iron at a temperature of 180°C, applying 10 passes evenly throughout the wick.
• The wick is then washed with shampoo, then
• The wick is dried and brushed 10 times

The last 2 steps are repeated 4 more times.

Example 4: Application in 2 steps: application of the dispersion (A1) comprising the oily dispersion stabilizing agent i) + particulate core ii) + Pigment BLUE 1 (CI 42090 & TRIETHOXYCAPRYLYLSILANE) then application of the composition (B1) comprising the compound THIOLE 1.

The following dispersions and compositions were prepared. The amounts are given in g per 100 g of dispersion or composition.

Scatter (A1)

Ingredients Quantity (g) Oily dispersion stabilizing agent i) + particulate core ii) 15 (m.a.) BLUE 1 LAKE and TRIETHOXYCAPRYLYLSILANE (CI 42090 & TRIETHOXYCAPRYLYLSILANE) 6 Isododecane Qsp 100

Membership (B1)

Ingredients Quantity (g) Compound THIOL 1 5 WATER Qsp 100

The results of the assessments are summarized in the table below:

The colorimetric data of each of the locks are then measured with a Minolta CM-3610d spectrophotometer.

Color measurements:

I To b ΔE without shampoo 35.17 -22.89 -12.61 40.59 after a shampoo 33.07 -22.15 -11.72 40.82

The coloring obtained is very aesthetic, with good intensity, rise and chromaticity of color. It also appears that the hold of the hair make-up is correct after shampooing.

Example 5: Application in 2 steps: application of the dispersion (A2) comprising the oily dispersion stabilizing agent i) + particulate core ii) + Pigment IRON OXIDES (and) MICA (code 79179) then application of the composition (B1) comprising the compound THIOLE 1.

The following dispersions and compositions were prepared. The amounts are given in g per 100 g of dispersion or composition.

Scatter (A2)

Ingredients Quantity (g) Oily dispersion stabilizing agent i) + particulate core ii) 15 (m.a.) IRON OXIDES and MICA 6 Isododecane Qsp 100

Membership (B1)

Ingredients Quantity (g) Compound THIOL 1 5 WATER Qsp 100

The results of the assessments are summarized in the table below:

The colorimetric data of each of the locks are then measured with a Minolta CM-3610d spectrophotometer.

Color measurements:

Number of shampoos To b VS* 0 shampoo 15.51 19.7 25.07 10 shampoos 13.83 18.88 23.40

The coloration obtained is very aesthetic, with good color chromaticity. It also appears that the hold to shampoos of the hair makeup remains correct, in particular in terms of chromaticity, even after 10 successive shampoos.

Study of resistance to shampoos combined with brushing:

Example 6: Application in 2 steps: application of the dispersion (A3) comprising the oily dispersion stabilizing agent i) + particulate core ii) + Iron oxide pigment (IRON OXIDES (and) ISOPROPYL TITANIUM TRIISOSTEARATE) then application of the composition (B2 ) comprising the compound THIOL 2.

The following dispersions and compositions were prepared. The amounts are given in g per 100 g of dispersion or composition.

Scatter (A3)

Ingredients Quantity (g) Oily dispersion stabilizing agent i) + particulate core ii) 15 (m.a.) IRON OXIDES and ISOPROPYL TITANIUM TRIISOSTEARATE 6 Isododecane Qsp 100

Membership (B2)

Ingredients Quantity (g) Compound THIOL 2 8 Isododecane Qsp 100

The results of the assessments are summarized in the table below:

The colorimetric data of each of the locks are then measured with a Minolta CM-3610d spectrophotometer.

Color measurements:

I To b ΔE 40.04 18.80 16.88 29.72

The coloring obtained is very aesthetic, intense, with good color chromaticity.

Example 7: Application in 2 steps: application of the dispersion (A3) comprising Oily dispersion stabilizing agent i) + particulate core ii) + Iron oxide pigment (coded 80596 _ IRON OXIDES and ISOPROPYL TITANIUM TRIISOSTEARATE) then application of the composition (B3 ) comprising the compound THIOL 3.

The following dispersions and compositions were prepared. The amounts are given in g per 100 g of dispersion or composition.

Scatter (A3)

Ingredients Quantity (g) Oily dispersion stabilizing agent i) + particulate core ii) 15 (m.a.) IRON OXIDES and ISOPROPYL TITANIUM TRIISOSTEARATE 6 Isododecane Qsp 100

Membership (B3)

Ingredients Quantity (g) Compound THIOL 3 8 Isododecane Qsp 100

The results of the assessments are summarized in the table below:

The colorimetric data of each of the locks are then measured with a Minolta CM-3610d spectrophotometer.

Color measurements:

I To b ΔE 40.04 18.80 16.88 29.72 The coloration obtained is very aesthetic, intense, with good color chromaticity.
.

Claims (24)

Process for treating keratin materials, preferably α) keratin fibres, in particular human fibers such as the hair, or β) human skin, in particular the lips, comprising:
1) the application to said materials of an oily dispersion (A), preferably anhydrous, comprising:
i) one or more particle(s) consisting of one or more ethylenic copolymer(s):
a) (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl, preferably (meth)acrylate (C ₁ -C ₄ )alkyl and
b) an ethylenically unsaturated anhydride compound, preferably maleic anhydride; And
ii) one or more stabilizing agents consisting of ethylenic polymers chosen from:
c) polymers of (C ₁ -C ₆ )(alkyl)acrylate (C ₃ -C ₁₂ )cycloalkyl monomers; And
d) copolymers of (C ₁ -C ₆ )(alkyl)acrylate, (C ₃ -C ₁₂ )cycloalkyl and (C ₁ -C ₄ )(alkyl)acrylate (C ₁ -C ₄ )alkyl; And
iii) one or more hydrocarbon oil(s);
2) the application to said materials of a composition (B) distinct from (A), preferably anhydrous, comprising:
iv) one or more hydroxylated and/or thiolated compound(s) one or more hydroxylated compound(s), polymer(s) or not, preferably organic(s) or silicone(s) ;
Being heard that :
- the process uses v) one or more cosmetic active ingredient(s) chosen from a) coloring agents chosen from pigments, direct dyes and mixtures thereof, b) active ingredients for caring for keratin materials preferably of the skin and c) the UV filters as well as d) their mixtures the ingredients a) to d) which can be found in the composition (A), and/or in the composition (B), and/or in another composition (C); And
- the compositions (A), (B) and (C) can be applied together or separately. Process according to the preceding claim, in which the oily dispersion (A) comprises one or more particles consisting of one or more ethylenic copolymers of a) of (C ₁ -C ₄ )(alkyl)acrylate of (C ₁ -C ₄ )alkyl which has the formula H ₂ C=C(R)-C(O)-O-R' with R representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl, and R' representing a (C ₁ -C ₄ )alkyl, linear or branched, preferably linear in particular (C ₁ -C ₃ )alkyl such as methyl or ethyl, preferably C ₁ -C ₄ alkyl (meth)acrylate, linear or branched , preferably linear in particular in (C ₁ -C ₃ )alkyl _, particularly the polymer of the particles is a polymer of (meth)acrylate of C ₁ -C ₄ alkyl, linear or branched, preferably linear in particular in ( C ₁ -C ₃ )alkyl;
particularly a) is chosen from C ₁ -C ₄ alkyl (meth)acrylate such as methyl acrylate (meth)acrylate, ethyl (meth)acrylate, n- propyl, isopropyl (meth)acrylate, n-butyl (meth)acrylate, or tert-butyl (meth)acrylate; preferably chosen from methyl acrylate and ethyl acrylate. Process according to any one of the preceding claims, in which the oily dispersion (A) comprises one or more particles consisting of one or more ethylenic copolymers of b) ethylenically unsaturated anhydride compound b) chosen from derivatives of maleic anhydride (Ia) and itaconic anhydride (Ib):

Formulas (Ia) and (Ib) in which R _a , R _b and R _c , identical or different, representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably R _a , R _b , and R _c represent a hydrogen atom;
preferentially, ingredient b) is of formula (Ia) and more preferentially is maleic anhydride. Process according to any one of the preceding claims, in which the polymer or polymers of the particles i) of the dispersion (A) comprise, or consist essentially of, from 80 to 99.99% by weight relative to the total weight of the polymer or polymers, particular between 85 and 98%, more preferably between 87 and 94% by weight relative to the total weight of the polymer(s), of ingredient a) and from 0.01 to 20% by weight of ingredient b), for relative to the total weight of the polymer. Process according to any one of the preceding claims, in which the copolymer(s) of the particles the particles i) consist of polymers a) and b) with a weight ratio a)/b) comprised inclusively between 5.5 and 20, preferably between 6 .5 and 16, even more preferably between 6.6 and 15.6. Process according to any one of the preceding claims, in which the polymer of the particles i) is present in the dispersion (A) in an amount ranging from 20 to 60% by weight, relative to the total weight of the dispersion (A), in particular between 21% to 58.5% by weight, relative to the total weight of the dispersion (A), preferably ranging from 30 to 50% by weight, relative to the total weight of the dispersion (A), more preferably ranging from 36 % to 42% by weight relative to the total weight of the dispersion (A).
. Process according to any one of the preceding claims, in which the stabilizing agent(s) ii) of the dispersion (A) is (are) constituted by ethylenic polymers chosen from:
c) polymers of monomers of formula H₂C=C(R)-C(O)-O-R’’ with R representing a hydrogen atom or group (C₁-VS₄)alkyl such as methyl, and R’’ representing a group (C₅-VS₁₀)cycloalkyl such as norbornyl, or isobornyl preferably isobornyl ; And
d) copolymers of H₂C=C(R)-C(O)-O-R’ and of H₂C=C(R)-C(O)-O-R'' with R, R' and R'' as previously defined;
particularly the stabilizing agent ii) is a polymer of isobornyl (meth)acrylate chosen from isobornyl (meth)acrylate homopolymer and random copolymers of isobornyl (meth)acrylate and of (meth)acrylate d C-alkyl₁-VS₄preferably present in a weight ratio of isobornyl (meth)acrylate / C-alkyl (meth)acrylate₁-VS₄greater than 4; advantageously, said weight ratio ranges from 4.5 to 19 Process according to any one of the preceding claims, in which the combination of i) particle(s) + ii) stabilizing agent(s) present in the dispersion (A) comprises from 10 to 50% by weight of copolymers d) better from 15 to 30% by weight of copolymer d) and from 50 to 90% by weight of polymer c) better from 70 to 85% by weight of polymer c), relative to the total weight of the whole i ) stabilizing agent(s) + ii) polymer particle(s). Process according to any one of the preceding claims, in which the hydrocarbon oil(s) iii) of the dispersion (A) is (are) apolar, i.e. formed solely of carbon and hydrogen atoms, in particularly volatile; more particularly chosen from hydrocarbon oils having from 8 to 14 carbon atoms; preferentially isododecane and octyldodecanol, more preferentially isododecane; or else a mixture of non-volatile and volatile oil, preferably the mixture comprises isododecane as the volatile oil and a phenyl silicone oil such as a pentaphenyl silicone oil. Process according to any one of the preceding claims, in which the dispersion (A) is in an inverse emulsion, i.e. of the water-in-oil (W/O) type and comprises one or more surfactants, preferably nonionic. Process according to any one of the preceding claims, in which iv) the hydroxylated and/or thiolated compound(s) of composition (B) is (are) non-polymeric; preferably of formula (II), as well as their solvates such as hydrates:
(HO)pL(SH)q (II)
Formula (II) in which:

• p and q, which are 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 comprised 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 atoms, more particularly between 2 and 40 carbon atoms, even more particularly between 3 and 30 carbon atoms, preferably between 6 and 20 carbon atoms carbon, 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. Process according to any one of the preceding claims, in which iv) the hydroxylated and/or thiolated compound(s) is (are) nonpolymeric (s) chosen from the compounds of formulas (IIa) and (IIb) as well as their solvates such as hydrates:
L(OH)p (IIa) L(SH)q (IIb)
Formulas (IIa) and (IIb) in which:

• p and q denote an integer greater than or equal to 2, preferably comprised inclusively between 2 and 10, preferably between 2 and 5; And
• L is as defined in the preceding claim, preferably L denotes a multivalent (at least divalent) radical comprising between 8 and 30 carbon 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, preferably L denotes a C ₈ -C ₁₈ multivalent radical, in particular linear, more preferably, the polyol or polythiol is liposoluble, and/or is a C ₈ -C ₁₈ diol or dithiol, in particular linear in C ₈ -C ₁₆ , in particular in C ₁₀ -C ₁₄ .

Process according to any one of the preceding claims, in which iv) the hydroxylated and/or thiolated compound(s) is (are) chosen from 1,8-octanediol, 1,10- decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol1,8-octanedithiol, 1,10-decanedithiol, 1,12-dodecanedithiol, 1 ,14-tetradecanedithiol, 1,16-hexadecanedithiol, and 1,18-octadecanedithiol; preferably 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,12-dodecanediol, 1,10-decanedithiol, 1,12-dodecanedithiol, 1,14-tetradecanedithiol , more preferably 1,12-dodecanedithiol. Process according to any one of Claims 1 to 11, in which iv) the hydroxylated and/or thiolated compound(s) is (are) chosen from hydroxylated and/or thiolated alkoxysiloxanes, in particular those of formula (III):
R'₁-If(OR’₂)_z(R'₃)_x(III)
Formula (III) 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(C₁-VS₆)alkyl or thiol(C₁-VS₆)alkyl, preferably thiol(C₁-VS₆)alkyl, and
R'₁is 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'₁being bonded to the silicon atom directly via a carbon atom,
preferably R'₁is a C hydrocarbon chain₁-VS₆, linear or branched, saturated or unsaturated, substituted by one or more hydroxy or thiol groups, preferably thiol; more preferably, R'₁is a C hydrocarbon chain₂-VS₄, saturated linear substituted with hydroxy or thiol, preferably thiol

• R′ ₂ and R′ ₃ , which are identical or different, represent an alkyl group, linear or branched, comprising from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as methyl or ethyl;
• z denotes an integer ranging from 1 to 3, preferably z is equal to 3; And
• and x denotes an integer ranging from 0 to 2, with z+x=3.

Process according to any one of Claims 1 to 11 and 14, in which iv) the hydroxylated and/or thiolated compound(s) is (are) chosen from those of the following formula (III') :
(R¹GOLD²)(R³)Si-CH₂-[N(R⁴)-I¹]_p-X-H (III’)
Formula (III') 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 group (C₁-VS₆)alkoxy, especially C₁-VS₄;
- a group (C₁-VS₆)alkyl;

• 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;

preferably, the alkoxysilane of formula (III) is chosen from: 4-(trimethoxysilyl)-1-butanol; 3-(trimethoxysilyl)-1-propanol; 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 preferentially the alkoxysilane(s) of formula (III) are chosen from 2-(triethoxysilyl)-ethanethiol; and 3-(triethoxysilyl)-1-propanethiol. Process according to any one of Claims 1 to 10, in which iv) the hydroxylated and/or thiolated compound(s) is (are) polymeric; preferably of formula (V) as well as their solvates such as hydrates:
(HO)pPOLY(SH)q (V)
Formula (V) 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 and/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-, –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
POLY 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-VS₁₀)alkyl, or aryl(C₁-VS₄)alkyl such as benzyl, preferably R_Toand R_brepresent a hydrogen atom; And
-R_vsand R_d, identical or different, represent a group (C₁-VS₁₀)alkyl, aryl(C₁-VS₄)alkyl or (C₁-VS₁₀)alkoxy. Process according to any one of Claims 1 to 10 and 16, in which iv) the hydroxylated and/or thiolated compound(s) is (are) polymeric(s) chosen from the compounds of formulas (V') and (VIII) as well as their solvates such as hydrates:
POLY(OH)p (V’) POLY(SH)q (VIII)
Formula (V') and (VIII) in which:

• p and q, denote an integer greater than or equal to 2, and
• POLY denotes a carbonaceous or silicone polymeric radical, POLY possibly also containing one or more heteroatoms such as O, N, S, and/or one or more functions chosen from amino functions, (thio)esters, (thio)ketones, ( thio)amides, (thio)ureas, (thio)carbamates, and/or be substituted by one or more (C ₁ -C ₁₀ )alkyl groups, linear or branched, (C ₁ -C ₁₀ )alkoxy groups, linear or branched, it being understood that when POLY is substituted, the hydroxy functions can be carried by the substituent(s);

preferably those chosen from formulas (VII), and (VIII') as well as their solvates such as hydrates:

Formulas (VII) and (VIII') in which:

• R ^a , and R ^b , identical or different, preferably identical, represent a (C ₁ -C ₆ )alkyl group optionally substituted by one or more hydroxy, amino or thiol groups, (C ₁ -C ₆ )alkoxy such as methoxy , aryl such as phenyl, aryloxy such as phenoxy, aryl(C ₁ -C ₄ )alkyl such as benzyl, or aryl(C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl,
• n represents an integer greater than or equal to 1 and more particularly the value of n is such that the weight-average molecular weight of the silicone is between 500 and 55,000; particularly n is an integer comprised inclusively between 1 and 100, preferably comprised between 5 and 50, and preferentially comprised between 10 and 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, preferably a (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene group -oxy(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylenoxy or oxy(C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene, more preferably preferably a (C ₁ -C ₆ )alkylene group;
• X represents an oxygen or sulfur atom, preferably oxygenn,

Preferably, the polydimethylsiloxane thiols are chosen from those of formula (VIII'') as well as their solvates such as hydrates:

Formula (VIII’’) 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 (C ₂ -C ₆ )alkylene group, preferably linear, such as ethylene or n-propylene;
• n represents an integer comprised inclusively between 1 and 100, preferably between 5 and 50, and preferably between 10 and 30.

Process according to any one of Claims 1 to 10, 16 and 17, in which iv) the hydroxylated and/or thiolated compound(s) is (are) polymeric(s) chosen from the compounds of formula (IX) as well as their solvates such as hydrates:

Formula (IX) in which:

• R ^a , R ^b , and R ^d , identical or different, preferably identical, represent a group (C ₁ -C ₆ )alkyl optionally substituted by a hydroxy group, or amino, preferably (C ₁ -C ₄ )alkyl such as methyl, (C ₁ -C ₄ )alkoxy such as methoxy, aryl such as phenyl, aryloxy such as phenoxy, aryl (C ₁ -C ₄ )alkyl such as benzyl, or aryl (C ₁ -C ₄ )alkoxy such as benzoxy, preferably (C ₁ -C ₄ )alkyl such as methyl,

R^dcan also represent a group (C₁-VS₆)alkyl substituted by a group (C₁-VS₄)alkylamino or amino, or thiol, preferably (C₁-VS₄) 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 1,000 and 55,000;

preferably polydi(C₁-VS₄)alkylsiloxanes of formula (IX) are of the following formula (IX') as well as their solvates such as hydrates:
(IX')
formula (IX'), in which the values of n and m are such that the weight-average molecular weight of the silicone is between 1,000 and 55,000. Process according to any one of the preceding claims, in which the composition (B) comprises one or more hydrocarbon oil(s) iii) as defined in Claim 1 or 9; advantageously the hydrocarbon oils contained in the dispersion (A) and the composition (B) are identical; more preferably, the hydrocarbon oil or oils of composition (B) are isododecane. Process according to any one of Claims 1 to 19, in which the composition (B) is anhydrous. Process according to any one of the preceding claims, in which v) the cosmetic agent(s) is (are) chosen from coloring agents, and preferably pigments, more particularly chosen from:

• organic pigments nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone; the white or colored organic pigments are chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references pigment BLUE 1 LAKE Cl 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references Cl 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005 codified in the Color Index under the references Cl 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 15510, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120 , 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, Pigments obtained by oxidaning , or phenolics;
• Mineral pigments or inorganic pigments chosen from mineral pigments useful in the present invention, iron or chromium oxides, manganese violet, ultramarine blue, chromium hydrate, ferric blue and titanium oxide;

more preferably, the pigments v) are chosen from carbon black, iron oxides, in particular black, and micas coated with iron oxide, triarylmethane pigments, in particular blue and purple, such as BLUE 1 LAKE, azo pigments, in particular red, such as such as D&C RED 7 alkali metal salt of lithol red such as calcium salt of lithol red B. Process according to any one of the preceding claims, in which v) the cosmetic agent(s) as defined in claim 1, or 21 is (are) in the dispersion (A) such as defined in any one of claims 1 to 10. Process according to any one of the preceding claims, in which between stage 1) and stage 2), there is no rinsing, and the keratin materials are dried in air, preferably after application of the dispersion (A) during step 1) one waits between 1 minute and 6 hours, in particular between 10 minutes and 5 hours, more particularly between 30 minutes and 4 hours, preferably around 3 hours, to apply the composition ( B);
optionally after the application of the dispersion (A), of the compositions (B) and (C), the keratin fibers are subjected to a temperature greater than or equal to 30°C. Kit or device with several separate compartments comprising:

• in a first compartment: the dispersion (A) as defined in any one of claims 1 to 10,
• in a second separate compartment: composition (B) as defined in any one of claims 1, 11 to 20, and
• optionally in a third compartment separate from the other two: composition (C) comprising one or more cosmetic agents as defined in claim 1.