FR3144000A1 - Process for treating keratin materials using at least one (co)polymer of polyvinyl alcohol (PVA) with acetoacetate functions and at least one crosslinking agent - Google Patents

Abstract

Process for treating keratin materials using at least one (co)polymer of polyvinyl alcohol (PVA) with acetoacetate functions and at least one crosslinking agent The present invention relates to a process for treating keratin materials, comprising the application to said keratin materials, in one or more successive steps, of at least i) one or more (co)polymers having at least one unit of formula (I ), as well as its optical, geometric and/or solvated isomers, such as hydrates, or a composition containing it or them: (I) formula (I) in which Ra, Rb, Rc, Rd, and q are as defined in the description, ii) at least water, iii) at least one crosslinking agent and iv) optionally a cosmetic active ingredient. Figure for abstract: None

Description

Process for treating keratin materials using at least one (co)polymer of polyvinyl alcohol (PVA) with acetoacetate functions and at least one crosslinking agent

The present invention relates more particularly to the cosmetic field, in particular to the treatment of keratin materials, in particular to the care and/or makeup of the skin and/or lips and/or eyelashes and/or eyebrows.

It thus aims to propose in particular new treatment processes, in particular cosmetic ones, comprising the application to keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, of at least one (co)polymer of polyvinyl alcohol (PVA) with acetoacetate functions, water, at least one crosslinking agent, and possibly at least one cosmetic active ingredient, which are particularly interesting with regard to their technical performances, in particular in terms of the resistance of the deposits that they make it possible to obtain, and the sensory sensations that they provide to the user.

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

Thus, in the field of skin and/or lip makeup, it is particularly expected that the deposit formed does not transfer when in contact with fingers or clothing.

It must also have good resistance to contact with water, especially rain or showering, or even perspiration, as well as sebum, or even contact with fatty substances in food, especially cooking oils when this deposit forms on the lips. In addition, this deposit must be comfortable or even shiny.

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

However, the compositions of the prior art have unsatisfactory durability over time.

Compositions, in particular film-forming cosmetic compositions, are known, comprising at least one fatty phase and at least one copolymer obtained by the polymerization of ethylenic monomers, some of which carry particular groups (see for example WO 2022/136104). Such compositions nevertheless require the presence of a fatty phase which can reduce the field to certain applications. In addition, these compositions do not necessarily meet the need for naturalness expressed by certain consumers.

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 skeleton and at least two groups capable of forming at least three hydrogen bonds. However, with this alternative composition, the performance in terms of durability or water resistance obtained remains insufficient.

Also known from WO 2014/099108 are compositions and methods for forming deposits on keratin substrates having good resistance over time, using compounds with acetoacetate functions and active agents functionalized to be covalently linked to the keratin materials.

Furthermore, WO 06/042169 describes tissue adhesives, in medical and veterinary applications, formed by the reaction of poly(hydroxylic) compounds derivatized with acetoacetate groups and/or polyamino compounds derivatized with acetoacetamide groups with an aminofunctional crosslinking compound.

In general, the processes and treatments described above do not allow access to deposits, on keratin materials, in particular on the skin and/or lips, which satisfy all of the aforementioned requirements, namely very good resistance to water and/or fatty substances, in particular for the lips, which are also comfortable to wear for users, which allow the shine of the deposits to be modulated or which do not lead to visually unsightly deposits.

There is also significant consumer demand for the use of compositions with reduced environmental impact.

In the field of cosmetic products, film-forming compounds that can be transported in water are also being sought to be used in cosmetic treatments requiring fewer oils, or even aqueous formulations.

In particular, polyvinyl alcohol (PVA) is an interesting polymer for cosmetic applications. It is a film-forming polymer that can be transported in water, leading to deposits with good resistance properties to fatty substances such as olive oil or sebum…

However, PVA films have a major defect with a high sensitivity to water limiting the interest of PVA for application on keratin materials, in particular the skin and/or lips.

There therefore remains a need for a treatment process, in particular cosmetic, intended for application to keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, which makes it possible to obtain a film-forming, non-sticky deposit, which transfers little, if at all, is comfortable, and is persistent, in particular with respect to water and fatty substances, in particular oils.

There is also a need for a treatment process, particularly cosmetic, to obtain deposits that are resistant to water and fatty substances, particularly sebum.

There also remains a need for a treatment process, particularly cosmetic, making it possible to obtain deposits whose shine can be modulated and/or which are not visibly unsightly, ideally invisible if they are not colored.

There also remains a need for a treatment process, particularly cosmetic, using aqueous or predominantly aqueous compositions and leading to water-resistant deposits.

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

These problems are solved by implementing a process, in particular a cosmetic process, for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, comprising the application to said keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, in one or more successive steps, of at least:

(i) one or more (co)polymers having at least one unit of formula (I), as well as its optical, geometric and/or solvated isomers, such as hydrates, or a composition containing it or them:

(I)

formula (I) in which:

- R ^a represents a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^a represents a hydrogen atom,

- R ^b and R ^c , identical or different, represent a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^b and R ^c represent a hydrogen atom,

- R ^d represents a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^d represents a methyl group,

- p is an integer greater than or equal to 2,

and optionally at least one motif of formula (II):

(II)

formula (II) in which:

- q represents an integer greater than or equal to 2, and

- R ^a represents a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^a represents a hydrogen atom;

and optionally at least one motif of formula (III):

(III)

formula (III) in which:

- t represents an integer greater than or equal to 2, and

- R represents a hydrocarbon chain, cyclic or acyclic, linear or branched, saturated or unsaturated, aromatic or not, comprising from 1 to 10 carbon atoms, preferably R represents a (C ₁ -C ₆ )alkyl group, in particular methyl;

- R ^a represents a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^a represents a hydrogen atom; and

(ii) water;

(iii) one or more crosslinking agent(s); and

iv) optionally one or more cosmetic active ingredients chosen from a) coloring materials other than rhodamine B, b) active ingredients for caring for keratin materials, c) UV filters, and d) their mixtures.

According to a preferred embodiment, the treatment method of the invention comprises the application of at least iv) a cosmetic active ingredient as defined above and below, to keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows.

According to a preferred embodiment, the method according to the invention comprises the application i) of at least one (co)polymer as defined above, its optical, geometric isomers, and/or its solvates, such as hydrates, or of a composition containing it(them), the application ii) of at least water, iii) of at least one crosslinking agent and the application iv) of at least one cosmetic active agent chosen from a) coloring materials other than rhodamine B, b) care active agents on keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, c) UV filters, and d) their mixtures; more preferably a) the cosmetic active agent(s) are chosen from coloring materials other than rhodamine B.

Water (ii) may be applied at the same time as (i), (iii) or (iv), when (iv) is present, or at the same time as (i) and (iii), and possibly (iv).

Water ii) can also be applied before i), iii) and possibly iv).

According to a preferred embodiment, water is at least applied at the same time as i), that is, i) and ii) are applied simultaneously, i) being further able to be applied in the presence of ii) water or not, and when iv) is present, iv) being further able to be applied in the presence of ii) water or without water.

The application to keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows of ingredients i), ii), iii) and optionally iv), leads to deposits on said keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, exhibiting very good resistance to water.

The inventors have thus observed, surprisingly, that the application to keratin materials, in particular to the skin and/or lips and/or eyelashes and/or eyebrows of ingredients i), ii), iii) and possibly iv), leads to deposits on said keratin materials, in particular the skin, exhibiting good resistance to external aggressions such as for example water, oils, in particular food oils, sweat and/or sebum and therefore having very good resistance over time.

Advantageously, the deposits obtained with the methods according to the invention are also very comfortable. They do not stick and do not transfer. The deposits obtained with the methods according to the invention can also be shiny. The visual appearance of the deposits is also very satisfactory.

Definitions

For the purposes of the present invention, throughout the description, including the claims, and unless otherwise indicated:

- By “ (co)polymer ” we mean a copolymer or a homopolymer.

- By " copolymer " is meant a polymer formed by the chaining of monomeric units of different chemical structures; for example, a polymer consisting of at least one unit of formula (I) and at least one unit of formula (II) and/or formula (III) is a copolymer within the meaning of the invention.

- By “ cosmetic active ingredient ” we mean an organic or organosilicon compound, or a mineral compound that can be incorporated into a cosmetic composition to provide an effect on keratin materials, whether this effect is immediate or provided by repeated applications. Examples of cosmetic active ingredients according to the invention include a) coloring materials chosen from pigments, direct, anionic, cationic, zwitterionic or neutral dyes, non-fluorescent or fluorescent but different from rhodamine B, or such as optical brighteners, or UVA and/or UVB filters and mixtures thereof, b) active ingredients for caring for keratin materials, particularly skin, such as anti-aging active ingredients or active ingredients intended to provide a benefit to the skin, such as active ingredients having an action on the barrier function, deodorant active ingredients, antiperspirant active ingredients, desquamating active ingredients, antioxidant active ingredients, moisturizing active ingredients, sebum-regulating active ingredients, active ingredients intended to combat the effects of pollution, antimicrobial or bactericidal active ingredients, perfumes, fluorescent non-colored compounds such as optical brighteners, vitamins; and colouring matters other than Rhodamine B such as direct dyes or pigments, preferably pigments, c) UVA and/or UVB filters and d) the mixture of a) + b), or the mixture of a) + c), or the mixture of b)+c), or the mixture of a) + b) + c).

Preferably, the cosmetic active ingredients are chosen from a) coloring materials chosen from pigments, direct dyes other than rhodamine B (more particularly rhodamines), more preferably the direct dyes are non-fluorescent, and their mixtures, b) active ingredients for caring for keratin materials, preferably the skin, c) UV filters, and d) their mixtures.

- For the purposes of the present invention, the term " fatty substance " means an organic compound insoluble in water at room temperature (25°C) and atmospheric pressure (760 mm Hg) (solubility less than 5%, and preferably 1%, even more preferably 0.1%); in addition, fatty substances are soluble in organic solvents under the same temperature and pressure conditions, such as for example in halogenated solvents such as chloroform, dichloromethane, lower alcohols such as ethanol or aromatic solvents such as benzene or toluene.

- By “ (hetero)aryl ” we mean aryl or heteroaryl groups.

- By “ (hetero)cycloalkyl ” we mean cycloalkyl or heterocycloalkyl groups.

• un radical (poly)(hydroxy)alkyle en C₁-C₆, de préférence en C₁-C₄;
• un atome d’halogène tel que chlore, fluor ou brome ;
• un groupement hydroxy ;
• un radical alcoxy en C₁-C₂; un radical (poly)-hydroxyalcoxy en C₂-C₄;
• un radical amino ;
• un radical amino substitué par un ou deux radicaux alkyle, identiques ou différents, en C₁-C₆, C₁-C₆, de préférence en C₁-C₄;
• un radical acylamino (-N(R)-C(O)-R’) 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-C₄; un radical carbamoyle ((R)₂N-C(O)-) dans lequel les radicaux R, identiques ou non, représentent un atome d’hydrogène, un radical alkyle en C₁-C₄;
• un radical alkylsulfonylamino (R’-S(O)₂-N(R)-) 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-S(O)₂-) 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 (CN) ;
• un groupement polyhalogéno(C₁-C₄)alkyle, préférentiellement le trifluorométhyle (CF₃).

- The “ aryl ” or “ heteroaryl ” radicals or the aryl or heteroaryl part of a radical may be substituted by at least one substituent carried by a carbon atom, chosen from:

• a C ₁ -C ₆ (poly)(hydroxy)alkyl radical, preferably C ₁ -C ₄ ;
• a halogen atom such as chlorine, fluorine or bromine;
• a hydroxy group;
• a C ₁ -C ₂ alkoxy radical; a C ₂ -C ₄ (poly)-hydroxyalkoxy radical;
• an amino radical;
• an amino radical substituted by one or two alkyl radicals, identical or different, in C ₁ -C ₆ , C ₁ -C ₆ , preferably in C ₁ -C ₄ ;
• an acylamino radical (-N(R)-C(O)-R') in which the radical R is a hydrogen atom,
• a C ₁ -C ₄ alkyl radical and the radical R' is a C ₁ -C ₄ alkyl radical; a carbamoyl radical ((R) ₂ NC(O)-) in which the radicals R, identical or not, represent a hydrogen atom, a C ₁ -C ₄ alkyl radical;
• an alkylsulfonylamino radical (R'-S(O) ₂ -N(R)-) 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 NS(O) ₂ -) in which the radicals R, identical or not, 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 (CN);
• a polyhalo(C ₁ -C ₄ )alkyl group, preferably trifluoromethyl (CF ₃ ).

• hydroxy,
• alcoxy en C₁-C₄, (poly)hydroxyalcoxy en C₂-C₄,
• alkylcarbonylamino ((R-C(O)-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, amino substitué par un ou deux groupements alkyle identiques ou différents en C₁-C₄;
• alkylcarbonyloxy ((R-C(O)-O-) dans lequel le radical R est un radical alkyle en C₁-C₄, amino substitué par un ou deux groupements alkyle identiques ou différents en C₁-C₄;
• alkcoxycarbonyle ((R-O-C(O)-) dans lequel le radical R est un radical alkyle en C₁-C₄, amino substitué par un ou deux groupements alkyles identiques ou différents en C₁-C₄ ;

- The cyclic or heterocyclic part of a non-aromatic radical may be substituted by at least one substituent carried by a carbon atom chosen from the groups:

• hydroxy,
• C ₁ -C ₄ alkoxy, (poly)hydroxyalkoxy C ₂ -C ₄ ,
• alkylcarbonylamino ((RC(O)-NR'-) in which the radical R' is a hydrogen atom, a C ₁ -C ₄ alkyl radical and the radical R is a C ₁ -C ₂ alkyl radical, amino substituted by one or two identical or different C ₁ -C ₄ alkyl groups;
• alkylcarbonyloxy ((RC(O)-O-) in which the radical R is a C ₁ -C ₄ alkyl radical, amino substituted by one or two identical or different C ₁ -C ₄ alkyl groups;
• alkoxycarbonyl ((R-O-C(O)-) in which the radical R is a C alkyl radical₁-C₄, amino substituted by one or two identical or different C alkyl groups₁-C₄ ;

- A cyclic, heterocyclic radical, or a non-aromatic part of an aryl or heteroaryl radical, can also be substituted by 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.

- An “ aryl ” radical represents a mono or polycyclic hydrocarbon group, condensed or not, comprising from 6 to 14 carbon atoms, and of which at least one cycle is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl.

- A “ heteroaryl ” radical represents a mono or polycyclic group, condensed or not, comprising from 5 to 14 links, from 1 to 6 heteroatoms chosen from the nitrogen, oxygen, sulfur and selenium atom, and of which at least one cycle is aromatic; preferably a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, , thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, , xanthylyl.

- A “ cyclic ” or “ cycloalkyl ” radical is a non-aromatic, mono- or polycyclic, condensed or not, cyclic hydrocarbon radical containing from 5 to 14 carbon atoms, which may contain from 1 to several unsaturations, preferably the cycloalkyl is a cyclohexyl group.

- A “ heterocyclic ” or “ heterocycloalkyl ” radical is a non-aromatic mono or polycyclic cyclic radical, condensed or not, containing from 3 to 9 members, comprising from 1 to 4 heteroatoms chosen from the nitrogen, oxygen, sulfur and selenium atom, preferably the heterocycloalkyl is chosen from epoxide, piperazinyl, piperidinyl, morpholinyl, or dithiolane.

- An “ alkyl ” radical is a saturated, linear or branched hydrocarbon radical, in particular C ₁ -C ₆ , preferably C ₁ -C ₄ .

- An “ alkoxy ” radical is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in C ₁ -C ₆ preferably in C ₁ -C ₄ .

- A radical "(poly)(hydroxy)alkyl» denotes a C alkyl radical₁-C₆, preferably in C₁-C₄ optionally substituted by one or more hydroxy radicals, preferably substituted by 1 to 4 hydroxy groups, more particularly between 1 and 3.

- A " sugar " radical is a monosaccharide or disaccharide radical. Examples of sugar radicals include: sucrose (or saccharose), glucose, galactose, ribose, fucose, maltose, fructose, mannose, arabinose, xylose or lactose.

- By " monosaccharide " is meant a monosaccharide sugar comprising at least 5 carbon atoms of formula C _x (H ₂ O) _x , with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is inclusively between 5 and 7, preferably x is equal to 6, they can be of D or L configuration, and of alpha or beta anomer, as well as their salts and their solvates, such as hydrates.

- By " disaccharide " is meant a di-osidic sugar which is a compound consisting of two oses linked together by O-osidic bonds, said compounds being composed of two monosaccharides (also called mono-osidics) as defined above, said monosaccharide units comprising at least 5 carbon atoms, preferably 6, particularly the mono-osidic units are linked together in 1,4 or 1,6 in α (alpha) or β (beta) anomer, each osidic unit being able to be of L or D configuration, as well as its salts and its solvates such as the hydrates of said monosaccharides; these are more particularly polymers formed from two oses (or monosaccharides) having the general formula: -[C _x (H ₂ O) _y )] ₂ - or -[(CH ₂ O) _x ] ₂ -, with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is inclusively between 5 and 7, preferably x is equal to 6, and y an integer which represents x – 1.

- By " polysaccharide " is meant a polysaccharide sugar which is a polymer consisting of several oses linked together by O-osidic bonds, said polymers being composed of monosaccharide units (also called mono-osidic) as defined above, said monosaccharide units comprising at least 5 carbon atoms, preferably 6, particularly the mono-osidic units are linked together in 1,4 or 1,6 in α (alpha) or β (beta) anomer, each osidic unit being able to be of L or D configuration, as well as its salts and its solvates such as the hydrates of said monosaccharides; these are more particularly polymers formed from a certain number of oses (or monosaccharides) having the general formula: -[C _x (H ₂ O) _y )] _w - or -[(CH ₂ O) _x ] _w -, with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is inclusively between 5 and 7, preferably x is equal to 6, and y an integer which represents x - 1, and w is an integer greater than or equal to 2, particularly inclusively between 3 and 3000, more particularly between 5 and 2500, preferentially between 10 and 2300, particularly inclusively between 15 and 1000, more particularly between 20 and 500, preferentially between 25 and 200.

- A "anionic counterion» is an anion or an anionic group associated with the cationic charge; more particularly the anionic counterion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates among which C₁-C₆alkylsulfonates: Alk-S(O)₂O^-such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S(O)₂O^-such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkylsulfates: Alk-O-S(O)O^-such as methyl sulfate and ethyl sulfate; x) aryl sulfates: Ar-O-S(O)O^-such as benzene sulfate and toluene sulfate; xi) alkoxy sulfates: Alk-O-S(O)₂O^-such as methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfates: Ar-O-S(O)₂O^-, (xiii) phosphate; (xiv) acetate; (xv) triflate; and (xvi) borates such as tetrafluoroborate.

- “ Solvates ” represent hydrates as well as the association with linear or branched _C1 - _C4 alcohols such as ethanol, isopropanol, n-propanol.

- " UV-A filter " means a chromophore derived from a compound that filters (or absorbs) UV-A ultraviolet rays at a wavelength between 320 and 400 nm. A distinction can be made between short UV-A filters (absorbing rays at a wavelength between 320 and 340 nm) and long UV-A filters (absorbing rays at a wavelength between 340 and 400 nm).

- By "UV-B filter " we mean a chromophore derived from a compound which filters (or absorbs) UV-B ultraviolet rays at a wavelength between 280 and 320 nm.

- By " chromophore " is meant a radical derived from a colorless or colored compound capable of absorbing UV and/or visible radiation at a wavelength λ _abs between 250 and 800 nm. Preferably, the chromophore is colored, i.e. it absorbs wavelengths in the visible, i.e. preferably between 400 and 800 nm. Preferably, the chromophores appear colored to the eye; particularly between 400 and 700 nm ( Ullmann 's Encyclopedia , 2005, Wiley-VcH, Verlag "Dyes, General Survey", § 2.1 Basic Principle of Color).

- By " anhydrous composition" is meant that said composition contains a quantity of less than 5% by weight of water, preferably less than 3% by weight of water, better still less than 1% by weight of water, relative to the total weight of the composition in question, even more preferably the composition considered is free of water.

- The terms “ coloring agent ” and “ coloring matter ” are equivalent.

- The expression “ comprising one ” must be understood as being synonymous with “ comprising at least one ”, unless otherwise specified.

- The expressions “ between … and … ”, “ includes from … to … ”, “ formed from … to … ”, and “ ranging from … to … ” must be understood inclusively, unless otherwise specified.

It is understood that the treatment methods according to the invention, as well as the compositions used, are non-therapeutic.

Detailed description Treatment process

The first subject of the invention is a treatment method in one or more steps using on keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, in particular the skin:

(i) at least one or more (co)polymers, as defined above and below, or a composition containing it or them;

(ii) at least water;

(iii) at least one crosslinking agent, in particular as defined below; and

iv) optionally at least one cosmetic active ingredient, in particular as defined below.

According to a particular embodiment of the invention, the treatment method according to the invention implements the simultaneous application of ingredients i), ii), iii), and optionally iv).

According to another particular embodiment of the invention, the treatment method according to the invention comprises at least 2 steps in which the ingredients i), ii), iii), and optionally iv), are applied in separate and successive steps to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, it being understood that the cosmetic active ingredient(s) iv) may be found together with the ingredient i) and (ii) and/or with the ingredient(s) iii) themselves optionally associated with ii) water.

According to a particular embodiment, the ingredient(s) i) and ii) are applied simultaneously to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, then the ingredient(s) iii) are applied to said keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, it being understood that the ingredient ii) can also be applied with iii) and/or with iv), when iv) is present, and that the ingredient(s) iv), when present, can be applied together with i) and ii) and/or iii), preferably with i) and ii).

According to another particular embodiment, the ingredient(s) iii) are applied to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, then the ingredients i) and ii) are applied together to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, it being understood that the ingredient ii) can also be applied with iii) and/or with iv), when iv) is present, and that the ingredient(s) iv) can be applied with iii) and/or with i) and ii), when iv) is present.

According to a particular embodiment of the invention, the method for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, is a cosmetic treatment method for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows.

According to one embodiment of the invention, the method for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, according to the invention using ingredients i), ii), iii) and optionally iv), is a skin care method.

According to one embodiment of the invention, the method for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, is a method for making up the skin, lips, eyelashes and/or eyebrows. According to this embodiment, the method comprises at least one cosmetic active agent chosen from coloring materials other than rhodamine B, preferably pigments.

According to one embodiment of the invention, the method according to the invention is a method for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows, comprising the application to said keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows of at least:

- a composition, called “C1”, comprising i) at least one (co)polymer, as defined above and below and ii) water, and optionally iv) at least one cosmetic active ingredient, in particular as defined above and below; preferably the composition “C1” does not comprise iii) a crosslinking agent;

- a composition, called “C2”, comprising i) at least one (co)polymer, as defined above, ii) water, iii) at least one crosslinking agent as defined below, and optionally iv) at least one cosmetic active ingredient, in particular as defined above and below; preferably the composition “C2” does not comprise iv) a cosmetic active ingredient;

- a composition, called “C3”, comprising i) at least one (co)polymer, as defined above and below, ii) water, iii) at least one crosslinking agent, in particular as defined above and below, and iv) at least one cosmetic active ingredient, in particular as defined above and below;

- a composition, called “C4”, comprising iii) at least one crosslinking agent, in particular as defined above and below, optionally ii) water, and optionally iv) at least one cosmetic active ingredient, in particular as defined above and below; preferably the composition “C4” does not comprise i) at least one (co)polymer, as defined above and below; and/or

- a composition, called “C5”, comprising iv) at least one cosmetic active ingredient, in particular as defined above and below, and optionally ii) water; preferably the composition “C5” does not comprise i) at least one (co)polymer, as defined above and below and does not comprise iii) at least one crosslinking agent;

it being understood that the process uses together or separately i) at least one (co)polymer as defined previously and below, ii) water, iii) at least one crosslinking agent, and optionally iv) at least one cosmetic active ingredient in particular as defined previously and below, and that the compositions “C1”, “C2”, “C3”, “C4” and “C5” may further comprise one or more fatty substances v), in particular as defined previously and below.

According to one aspect of the invention, the method for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows, uses a composition, called “C3”, comprising i) at least one (co)polymer, as defined above and below, ii) water, iii) at least one crosslinking agent, in particular as defined above and below, and iv) at least one cosmetic active agent, in particular as defined below, in particular chosen from a) coloring agents other than rhodamine B, such as pigments, direct dyes, and mixtures thereof, b) active agents for the care of keratin materials, preferably the skin, c) UV filters, and d) mixtures thereof, and in particular at least one coloring agent other than rhodamine B, more particularly at least one pigment.

According to another aspect, the method for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows according to the invention, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows, uses a composition called “C1” and a composition called “C4”, said composition “C1” comprising i) at least one (co)polymer, as defined above and below, ii) water, and optionally iv) at least one cosmetic active agent, in particular as defined above and below, and said composition “C4” comprising iii) at least one crosslinking agent, in particular as defined above and below, optionally ii) water, and optionally iv) at least one cosmetic active agent, it being understood that at least one of the two compositions “C1” or “C4” comprises iv) at least one cosmetic active agent, in particular as defined above and below, in particular composition “C1” or the composition “C4” comprises iv) at least one cosmetic active ingredient, more particularly the composition “C1” comprises iv) at least one cosmetic active ingredient, in particular as defined previously and below, and the composition “C4” does not comprise any cosmetic active ingredient.

According to another aspect, the method for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows according to the invention, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows, uses a composition called "C2" and a composition called "C4", said composition "C2" comprising i) at least one (co)polymer, as defined above and below, ii) water, iii) at least one crosslinking agent, and optionally iv) at least one cosmetic active agent, in particular as defined above and below, and said composition "C4" comprising iii) at least one crosslinking agent, in particular as defined above and below, optionally ii) water, and optionally iv) at least one cosmetic active agent, in particular as defined above and below; it being understood that at least one of the two compositions “C2” or “C4” comprises iv) at least one cosmetic active ingredient, in particular as defined above and below, in particular the composition “C2” or the composition “C4” comprises iv) at least one cosmetic active ingredient, more particularly the composition “C2” comprises iv) at least one cosmetic active ingredient, in particular as defined above and below, and the composition “C4” does not comprise any cosmetic active ingredient.

According to another aspect, the method for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows according to the invention, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows, uses a composition called “C1” and a composition called “C4” and a composition called “C5”, said composition “C1” comprising i) at least one (co)polymer, as defined above and below, ii) water and optionally iv) at least one cosmetic active agent, in particular as defined above and below, said composition “C4” comprising iii) at least one crosslinking agent, in particular as defined above and below, optionally ii) water, and optionally iv) at least one cosmetic active agent, in particular as defined above and below, and said composition “C5” comprising iv) at least one cosmetic active agent, in particular as defined above and below, and optionally ii) water. water; in particular compositions “C1” and “C4” do not include any cosmetic active ingredient.

According to another aspect, the method for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows according to the invention, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows, uses a composition called “C2”, a composition called “C4” and a composition called “C5”, said composition “C2” comprising i) at least one (co)polymer, as defined above and below, ii) water, and optionally iv) at least one cosmetic active agent, in particular as defined above and below, said composition “C4” comprising iii) at least one crosslinking agent, in particular as defined above and below, optionally ii) water, and optionally iv) at least one cosmetic active agent, in particular as defined above and below, and said composition “C5” comprising iv) at least one cosmetic active agent, in particular as defined above and below, and optionally ii) water; in particular compositions “C2” and “C4” do not include any cosmetic active ingredient.

According to another aspect, the method for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows according to the invention, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows, uses a composition called "C3" and a composition called "C5", said composition "C3" comprising i) at least one (co)polymer, as defined above and below, ii) water, iii) at least one crosslinking agent, in particular as defined above and below, and iv) at least one cosmetic active agent, in particular as defined above and below, and said composition "C5" comprising iv) at least one cosmetic active agent, in particular as defined above and below, and optionally ii) water.

According to a variant of the process of the invention, the ingredient(s) i), ii), and optionally iv) are applied together, namely simultaneously, to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows during a first step, then during a subsequent step, the ingredient(s) iii), and optionally iv), are applied to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, preferably said process implements iv) either during the first step or during the second step, preferably iv) is applied together with i), and ii) during the first step.

According to a particular embodiment, the method according to the invention comprises two successive steps of application to keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, of two different compositions, preferably at least one of the compositions comprising iv) at least one cosmetic active ingredient as defined.

According to a particular embodiment of the method, during the first step a composition “C1” or “C2”, preferably composition “C1”, is applied to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, then a composition “C4” is applied to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, preferably at least one of the compositions used comprises iv) at least one cosmetic active ingredient as defined.

According to yet another variant of the process of the invention, the ingredient(s) iii) and optionally iv) and/or ii) is (are) applied to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, then the ingredient(s) i), ii) and optionally iv) at least one cosmetic active agent, in particular as defined above, are applied to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows; preferably said process implements iv) either during the first step or during the second step, preferably iv) is applied together with i), and ii) during the second step. In particular, the composition “C4” is applied to keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, then the composition “C1” is applied, preferably the composition “C4” and/or the composition “C1”, preferably the composition “C1”, comprises iv) at least one cosmetic active agent as defined.

According to another variant of the method according to the invention, a composition “C1” containing i), ii) water and optionally iv), is applied, and sequentially a composition “C4” containing iii), and optionally iv), preferably the composition “C1” being applied before the composition “C4”, preferably at least one of the compositions “C1” and/or “C4” contains iv), preferably “C1” contains iv).

The compositions “C1”, “C2”, “C3”, “C4” and/or “C5” of the process according to the invention which comprise at least one fatty substance, in particular at least one oil, and water, may be in the form of a direct or inverse emulsion.

The “C3” compositions of the process according to the invention can therefore be applied directly as such to keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, or even be formed directly on the surface of the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows.

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

According to one embodiment of the method of the invention, the method is carried out in one step by applying to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, the composition “C3” as defined above.

Thus, according to one embodiment, the treatment method according to the invention comprises a single step of applying the composition “C3” to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows.

The term “1-step application method” means the direct application to the target keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, of a single composition in accordance with the invention, namely composition “C3”.

After applying the “C3” composition, a permanent, non-sticky deposit is advantageously obtained. The deposit obtained is also resistant to cooking oils, water, sebum, and friction.

According to another embodiment of the method of the invention, the method is carried out in two steps.

The term “2-step application method” means the successive application, on keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, of two different compositions, for example “C1” and “C4”, or “C2” and “C4”, or “C3” and “C5”. Preferably, “C1” then “C4”, “C2” then “C4”, or “C3” then “C5”, more preferably “C1” then “C4”, preferably at least one of the compositions “C1”, and/or “C2” and/or “C4” comprises iv) at least one cosmetic active ingredient.

According to another embodiment, the method of the invention is carried out in 3 steps.

The term “3-step application mode” means the sequential application of 3 distinct compositions “C1” to “C5”, preferably at least one of the compositions used containing iv) at least one cosmetic active ingredient as defined. According to this application mode, for example, according to one embodiment, the sequential application to keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, is carried out, α) of a composition “C1”, and β) of a composition “C4”, and γ) of a composition “C5”, preferably the composition “C1” is applied before the composition “C4” or “C5”.

According to another embodiment, the sequential application to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, is carried out: α) of a composition “C2”, and β) of a composition “C4”, and γ) of a composition “C5”, preferably the composition “C2” is applied before the composition “C4” or “C5”.

In the 2 or 3-step application modes, the composition applied first, for example “C1” or “C2”, is conventionally referred to as a “base coat”, and the composition(s) superimposed on it, generally referred to as a “top coat”, preferably at least one of the compositions used contains iv) at least one cosmetic active ingredient as defined.

After applying the different compositions “C1” to “C5”, a permanent and non-sticky deposit is advantageously obtained. The deposit obtained is also resistant to cooking oils and water.

According to a particular embodiment, the compositions are applied to dry keratin materials, in particular to the skin and/or lips and/or eyelashes and/or dry eyebrows.

According to a particular embodiment, the compositions are applied to damp or wet keratin materials, in particular to damp or wet skin and/or lips and/or eyelashes and/or eyebrows, that is to say to keratin materials, in particular skin and/or lips and/or eyelashes and/or eyebrows, containing water on the surface.

According to one aspect, the present invention relates to a process, in particular a cosmetic process, for keratin materials, in particular for the skin and/or lips and/or eyelashes and/or eyebrows, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows, comprising a step of applying to said keratin materials, in particular said skin or said lips or said eyelashes or said eyebrows, a composition “C3”, in particular containing at least one coloring material other than rhodamine B, in particular as defined above, and more particularly at least one pigment.

According to another of its aspects, the present invention relates to a cosmetic treatment process for the care and/or makeup of keratin materials, in particular the skin, lips, eyelashes and/or eyebrows, comprising the successive application of at least:

- a composition, called “C1”, comprising i) at least one (co)polymer, as defined above and below, ii) water, and optionally iv) at least one cosmetic active ingredient, in particular as defined above and below; then

- a composition, called “C4”, comprising iii) at least one crosslinking agent, in particular as defined previously and below, optionally ii) water, and optionally iv) at least one cosmetic active ingredient, in particular as defined previously and below;

at least one of the compositions “C1” and/or “C4” containing at least one coloring matter other than rhodamine B, in particular as defined previously and below, preferably at least one pigment, and more preferably the composition “C1” comprises at least one pigment.

According to another of its aspects, the present invention relates to a cosmetic treatment process for the care and/or makeup of keratin materials, in particular the skin, lips, eyelashes and/or eyebrows, comprising the sequential application of at least:

- a composition “C1” or “C2” as defined above; and

- a “C4” composition as defined above; and

- a “C5” composition as defined above;

it being understood that the compositions “C1” and/or “C2” and/or “C4” and/or “C5” contain at least one coloring matter other than rhodamine B, in particular as defined below, preferably at least one pigment. Preferably, the composition “C5” comprises at least one pigment.

(Co)polymers of ’ has polyvinyl alcohol (PVA) functionalized s by acetoacetate functions

As indicated above, the treatment method according to the invention comprises the application to keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, i) of at least one (co)polymer having at least one unit of formula (I), optionally at least one unit of formula (II) and optionally at least one unit of formula (III), or a composition containing it/them.

Thus, the treatment method according to the invention comprises the application to keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, of at least:

(i) one or more (co)polymers, as well as its optical, geometric and/or solvated isomers, such as hydrates, having at least one unit of formula (I), or a composition containing it/them:

(I)

formula (I) in which:

- R ^a represents a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^a represents a hydrogen atom,

- R ^b and R ^c , identical or different, represent a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^b and R ^c represent a hydrogen atom,

- R ^d represents a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^d represents a methyl group,

- p is an integer greater than or equal to 2,

and optionally at least one motif of formula (II):

(II)

formula (II) in which:

- q represents an integer greater than or equal to 2, and

- R ^a represents a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^a represents a hydrogen atom;

and optionally at least one motif of formula (III):

(III)

formula (III) in which:

- t represents an integer greater than or equal to 2, and

- R represents a hydrocarbon chain, cyclic or acyclic, linear or branched, saturated or unsaturated, aromatic or not, comprising from 1 to 10 carbon atoms, preferably R represents a (C ₁ -C ₆ )alkyl group, in particular methyl;

- R ^a represents a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^a represents a hydrogen atom;

(ii) water;

iii) one or more crosslinking agent(s), and

iv) optionally one or more cosmetic active ingredients chosen from a) coloring materials other than rhodamine B, b) active ingredients for caring for keratin materials, c) UV filters, and d) their mixtures.

Preferably, the (co)polymer(s) of the invention are copolymers.

According to a preferred embodiment, the (co)polymer(s) according to the invention comprise at least one unit of formula (I) and at least one unit of formula (II).

According to another particular embodiment, the (co)polymer(s) according to the invention comprise at least one unit of formula (I) and at least one unit of formula (III).

According to a preferred embodiment, the (co)polymer(s) according to the invention comprise at least one unit of formula (I), at least one unit of formula (II) and at least one unit of formula (III).

According to a preferred embodiment, the (co)polymer(s) according to the invention comprise from 0.01% to 42% by mole of units of formula (I), preferably from 0.1% to 40% by mole of units of formula (I), and more preferably from 1% to 30% by mole of units of formula (I), better still from 5% to 28% by mole of units of formula (I), even better still from 10% to 25% by mole of units of formula (I).

According to a preferred embodiment, the (co)polymer(s) according to the invention comprise from 48% to 99.99% by mole of units of formula (II), in particular from 60% to 99.99% by mole of units of formula (II), in particular from 70% to 99.99% by mole of units of formula (II), in particular from 69.9% to 99.9% by mole of units of formula (II), preferably from 69% to 99% by mole of units of formula (II), more preferably from 65% to 95% by mole of units of formula (II), and better still from 65% to 90% by mole of units of formula (II).

According to a preferred embodiment, the (co)polymer(s) according to the invention comprise from 0% to 30% by mole of units of formula (III), preferably from 0% to 28% by mole of units of formula (III), and more preferably from 0.1% to 26% by mole of units of formula (III).

According to a preferred embodiment, the (co)polymer(s) according to the invention comprise:

- from 1% to 25% by mole of units of formula (I),

- from 49% to 99% by mole of units of formula (II),

- from 0% to 26% by mole of units of formula (III).

According to a particularly preferred embodiment, the (co)polymer(s) according to the invention comprise:

- from 6% to 25% by mole of units of formula (I),

- from 50% to 89% by mole of units of formula (II),

- from 5% to 25% by mole of units of formula (III).

According to a preferred embodiment, the (co)polymer(s) according to the invention have a mass average molecular weight varying from 1000 g/mole to 1000000 g/mole, preferably from 5000 g/mole to 500000 g/mole, and more preferably from 10000 g/mole to 300000 g/mole.

According to a particular embodiment, the (co)polymer(s) as defined above are present in a composition, in particular in a composition “C1”, “C2”, or “C3”, in a content ranging from 0.001% to 50% by weight, preferably from 0.01% to 30% by weight, and more preferably from 0.1% to 25% by weight, relative to the total weight of said composition.

The (co)polymer(s) of formula (I) according to the invention can be prepared by functionalizing poly(vinyl alcohol) (PVA), to obtain poly(vinyl alcohol) with acetoacetate functions.

The functionalization of the poly(vinyl alcohol) can be carried out by a transesterification reaction with an acetoacetate ester derivative (IV) from a compound of formula -[CH ₂ -C(R ^a )(OH)] _p - or -[CH ₂ -C(R ^a )(OH)] _p -[CH ₂ -C(R ^a )(-OC(O)-R)-] _t to lead to the (co)polymer(s) according to the invention, as illustrated in the following diagrams:

diagrams in which:

- R, R ^a , R ^b , R ^c , R ^d , p, and t are as defined previously;

- R ^e represents a hydrocarbon chain, cyclic or acyclic, linear or branched, saturated or unsaturated, aromatic or not, comprising from 1 to 10 carbon atoms, preferably R ^e represents a (C ₁ -C ₆ )alkyl group, in particular methyl, ethyl, n-propyl, isopropyl or terbutyl, more preferably terbutyl;

- p' is a non-zero integer less than or equal to p, preferably strictly less than p, and corresponding to the number of repeating units carrying -OC(O)-C(R ^b )(R ^c )-C(O)-R ^d groups grafted in place of the hydroxy group, p being as defined above;

- p’’ is an integer greater than or equal to 0, it being understood that preferably the sum of p’ + p’’ = p.

Preferably, p’ is non-zero and less than or equal to p multiplied by 0.4, more preferably p’ is less than or equal to p multiplied by 0.3.

Preferably, p’’ is non-zero and preferably less than or equal to p multiplied by 0.6, more preferably p’’ is less than or equal to p multiplied by 0.7.

According to a particular embodiment, p’ is between (0.001 multiplied by p) and (0.3 multiplied by p).

More particularly, the compound of formula (IV) is selected from methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate and tert-butyl acetoacetate. Preferably, the compound of formula (IV) is tert-butyl acetoacetate.

In particular, the (co)polymer(s) according to the invention may be prepared from poly(vinyl alcohol) (PVA) compounds of formula (II), partially or completely hydrolyzed, in particular those marketed under the reference Kuraray Poval by the company Kuraray, in particular the POVAL range, or those marketed by the company Sigma-Aldrich (see for example https://www.sigmaaldrich.com/FR/fr/search/poly(vinyl-alcohol)?focus=products&page=1&perpage=30&sort=relevance&term=poly%28vinyl%20alcohol%29&type=product).

This may in particular be poly(vinyl alcohol) chosen from:

- poly(vinyl alcohol) with an average molecular weight M _w of 89000-98000, hydrolyzed at more than 99%;

- poly(vinyl alcohol) with an average molecular weight M _w of 30000-70000, hydrolyzed from 87% to 90%;

- poly(vinyl alcohol) with an average molecular weight M _w of 13000-23000, hydrolyzed from 87% to 89%;

- poly(vinyl alcohol) with an average molecular weight M _w of 9000-10000, hydrolyzed at 80%;

- poly(vinyl alcohol) with an average molecular weight M _w of 146000-186000, hydrolyzed at more than 99%;

- poly(vinyl alcohol) with an average molecular weight M _w of 85000-124000, hydrolyzed at more than 99%;

- poly(vinyl alcohol) with an average molecular weight M _w of 31000-50000, hydrolyzed from 98% to 99%;

- poly(vinyl alcohol) with an average molecular weight M _w of 31000-50000, hydrolyzed from 87% to 89%;

- poly(vinyl alcohol) with an average molecular weight M _w of 85000-124000, hydrolyzed from 87% to 89%;

- poly(vinyl alcohol) with an average molecular weight M _w of 146000-186000, hydrolyzed from 87% to 89%;

- poly(vinyl alcohol) with an average molecular weight M _w of 13000-23000, hydrolyzed at 98%;

- poly(vinyl alcohol) with an average molecular weight M _w of 130,000, hydrolyzed to more than 99%;

- fully hydrolyzed poly(vinyl alcohol);

- poly(vinyl alcohol) marketed by Sigma-Aldrich under the reference 4-88 Emprove ^® Essantial;

- poly(vinyl alcohol) marketed by Sigma-Aldrich Company under the reference 8-88 Emprove ^® Essantial (Cas number No. 9002-89-5, M _w equal to 67,000); or

- poly(vinyl alcohol) marketed by Sigma-Aldrich under the reference 40-88 Emprove ^® Essantial.

Preferably, the (co)polymer(s) according to the invention can be prepared from partially hydrolyzed poly(vinyl alcohol), more preferably 88% hydrolyzed.

In particular, this may be poly(vinyl alcohol) marketed by the Sigma-Aldrich Company under the reference 8-88 Emprove ^® Essantial.

Crosslinking agent

The treatment method according to the invention as described above comprises the application to keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, (i) of at least one or more (co)polymers as defined above, and (iii) of at least one crosslinking agent.

For the purposes of the invention, the term “crosslinking agent”, also known as “R”, denotes a compound capable of establishing with at least one acetoacetate function of the (co)polymer(s) used in the treatment method according to the invention at least one covalent bond, and thus of crosslinking this or these compound(s).

Preferably, the term “crosslinking agent”, also called “R”, denotes a compound capable of establishing at least one covalent bond with an acetoacetate function of the (co)polymer(s) used in the treatment method according to the invention and thus of crosslinking this or these compound(s).

For the purposes of the present invention, it is understood that the terms “crosslinking agent” and “crosslinker” are equivalent.

Compositions “C2”, “C3” and “C4” as defined above contain at least iii) a crosslinking agent.

The compositions of the invention may comprise a fatty phase, an aqueous phase or may be in the form of a direct or inverse emulsion. The composition “C4” may be an aqueous composition.

Composition “C1” is an aqueous composition and more preferably does not contain v) fatty substances.

According to a particular embodiment, the composition “C3” is an aqueous composition and does not contain v) fatty substances.

The crosslinking agent(s) iii) are preferably present in a mass content ranging from 0.2% to 60% by weight, in particular ranging from 0.5% to 40% by weight, and more particularly from 1% to 20% by weight, even more particularly from 1% to 10% relative to the total weight of the composition containing it(them).

In particular, the crosslinking agent(s) iii) and the (co)polymer(s) i) as defined above are preferably present in a mass content ranging from 1% to 35% by weight, relative to the total weight of the composition comprising them.

More specifically, the crosslinking agent(s) iii) suitable for the invention may be chosen from compounds with amine, thiol, acrylate and/or carbonyl functions such as a ketone or aldehyde function.

Thus, according to a particular embodiment, the crosslinking agent iii) is chosen from (poly)amine, (poly)thiolated, (poly)carbonyl, (poly)acrylate compounds, and their mixtures, preferably chosen from (poly)amine, (poly)thiolated and (poly)acrylate compounds and their mixtures, and more preferably chosen from (poly)amine, (poly)thiolated compounds and their mixtures, and more preferably chosen from (poly)amine compounds.

By (poly)amino, (poly)thiolated, (poly)carbonyl and (poly)acrylate compounds, we mean compounds comprising respectively at least one primary or secondary amine, thiol, carbonyl (such as a ketone or aldehyde) or acrylate function.

A) (Poly)amino compounds

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

The (poly)amine compound may in particular be chosen from polyamine compounds having several primary amine and/or secondary amine groups or from amino alkoxysilanes, and more particularly from amino alkoxysilane compounds, diamine compounds, triamine compounds, and mixtures thereof.

The (poly)amino compound may be a compound comprising from 2 to 20 carbon atoms, in particular a non-polymeric compound, they may be acyclic, or cyclic, linear or branched, saturated or unsaturated, conjugated or non-conjugated, aromatic or non-aromatic, optionally interrupted by one or more heteroatoms chosen from O, S, Si(R') ₂ , N(R'') preferably O, Si(R') ₂ , or their associations such as -Si(R') ₂ -O- or -O-Si(R') ₂ -, with R', identical or different, representing a (C ₁ -C ₄ )alkyl group such as methyl, and R'' representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably a hydrogen atom.

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

As (poly)amino compounds, mention may in particular be made of N-methyl-1,3-diaminopropane, N-propyl 1,3-diaminopropane, N-isopropyl 1,3-diaminopropane, N-cyclohexyl 1,3-diaminopropane, 2-(3-aminopropylamino) ethanol, 3-(2-aminoethyl)aminopropylamine, bis(3-aminopropyl)amine, methyl bis(3-aminopropyl)amine, N-(3-aminopropyl)-1,4-diaminobutane, N,N-dimethyldipropylenetriamine, 1,2-bis(3-aminopropylamino)ethane, N,N'-bis(3-aminopropyl)-1,3-propanediamine, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, lysine, cystamine, xylenediamine, tris(2-aminoethyl)amine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, diaminopropanol, 4,7,10-Trioxa-1,13-tridecanediamine, spermidine and C36-alkylenediamines (respectively Priamine ^TM 1071, 1073, 1074, 1075), preferably spermidine.

According to a particular embodiment of the invention, the (poly)amino compound(s) are monoamino, namely they contain a single primary and/or secondary amine group, preferably primary (NH ₂ ).

The (poly)amino compound(s) may be chosen from amino alkoxysilanes, in particular of formula R' ₁ Si(OR' ₂ ) _z (R' ₃ ) _x in which:

- R’₁is a C hydrocarbon chain₁-C₆, linear or branched, saturated or unsaturated, cyclic or acyclic substituted by a group chosen from primary amine groups NH₂or secondary -N(H)R with R representing a C alkyl₁-C₄, an aryl, a benzyl substituted by an amino group or by a C aminoalkyl group₁-C₄ ; R’₁which can be interrupted in its chain by a heteroatom (O, S, NH) or a carbonyl group C(O), R’₁being linked to the silicon atom directly via a carbon atom,

- R' ₂ and R' ₃ , identical or different, represent a linear or branched (C ₁ -C ₆ )alkyl group,

- z denotes an integer from 1 to 3, and

- x denotes an integer ranging from 0 to 2,

with z + x = 3.

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

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

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

In particular, the (poly)amine compound(s) are chosen from amino alkoxysilanes comprising only one primary and/or secondary amine group, preferably primary (NH ₂ ), such as 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-(m-aminophenoxy)propyltrimethoxy-silane, p-aminophenyltrimethoxysilane, and N-(2-aminoethylaminomethyl)-phenethyltrimethoxysilane.

Preferably, the (poly)amine compound(s) are chosen from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, and N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and more preferably 3-aminopropyl triethoxysilane (APTES), in particular that marketed by Sigma Aldrich.

The (poly)amino compound may also be chosen from amino polymers, in particular having a weight-average molecular weight ranging from 500 g.mol ^-1 to 1,000,000 g.mol ^-1 , preferably ranging from 500 g.mol ^-1 to 500,000 g.mol ^-1 , and preferentially ranging from 500 g.mol ^-1 to 100,000 g.mol ^-1 .

According to a particular embodiment of the invention, the (poly)amino compound(s) are monoamino and chosen from polydialkylsiloxanes, in particular of formula (IV):

H ₂ N-ALK-Si(R' ₂ )(R' ₃ )-O-[ Si(R' ₂ )(R' ₃ )-O] _n - Si(R' ₂ )(R' ₃ )-R ' ₄ (IV)

formula (IV) in which:

- ALK represents a (C ₁ -C ₄ )alkylene group, linear or branched, preferably linear, such as propylene,

- R' ₂ , and R' ₃ , identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group such as methyl, and

- R' ₄ represents a linear or branched (C ₁ -C ₆ )alkyl group, preferably C ₄ , such as n-butyl, ne represents an integer greater than or equal to 2, preferably the value of n is such that the weight average molecular weight of the polydimethylsiloxane ranges from 500 to 3000 g.mol ^-1 . As an example of polydimethylsiloxanes (IV), mention may be made of those sold under the names "MCR-A11" and "MCR-A12" by the company Gelest.

According to a particular embodiment of the invention, the (poly)amino compound(s) are diamino, namely they contain two primary and/or secondary amine groups, preferably primary (NH ₂ ).

• ALK[(O-ALK’)_m-NH₂]₂(V)

More particularly, they are chosen from the compounds of formulas (V) or (VI):

• ALK[(O-ALK') _m -NH ₂ ] ₂ (V)

• H₂N-ALK-Si(R’)₂-[O-Si(R’)₂]_m-O-Si(R)₂-ALK’-NH₂(VI)

Or

• H ₂ N-ALK-Si(R') ₂ -[O-Si(R') ₂ ] _m -O-Si(R) ₂ -ALK'-NH ₂ (VI)

formulas (V) and (VI) in which:

- ALK and ALK', identical or different, represent a (C ₁ -C ₆ )alkylene group, linear or branched, preferably linear, such as propylene,

- R', identical or different, represents a (C ₁ -C ₄ )alkyl group, such as methyl,

- m represents an integer greater than or equal to 0, preferably the value of m is such that the weight average molecular weight of the compound (V) or (VI) ranges from 500 g.mol ^-1 to 55000 g.mol ^-1 .

Examples of compounds of formula (VI) include those sold under the names “DMS-A11”, “DMS-A12”, “DMS-A15”, “DMS-A21”, “DMS-A31”, “DMS-A32” and “DMS-A35” by the company Gelest.

The (poly)amine compound(s) which are diamined are particularly polyether diamines, in particular of formula H ₂ N-ALK-O-[ALK'-O] _m -ALK''-NH ₂ with ALK, ALK' and ALK'', identical or different, representing a linear or branched (C ₁ -C ₆ )alkylene group, and m representing an integer greater than or equal to 0, such as 4,7,10-trioxa-1,13-tridecanediamine or the compounds known under the reference Jeffamine from the company Hunstman, and more particularly α, ω-diamine polyethylene glycol and/or polypropylene glycol (with an amine function at the end of the chain) such as those sold under the names Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-9000, ED-2003.

According to a particular embodiment of the invention, the (poly)amino compound(s) are triaminated, namely they contain three primary and/or secondary amine groups, preferably primary (NH ₂ ). More particularly, they are chosen from polyether triamines in particular of formula ALK'''[(O-ALK') _m -NH ₂ ] ₃ with ALK' as defined above and ALK''', representing a trivalent (C ₁ -C ₆ )alkylene group, linear or branched, and m representing an integer greater than or equal to 0.

As (poly)amino compounds which are triaminated, polyether triamines are particularly cited, and in particular α, ω-diamine polyethylene glycol and/or polypropylene glycol (with amine function at the end of the chain) such as those sold under the names Jeffamine T-403.

According to another particular embodiment of the invention, the (poly)amine compound(s) comprise more than three primary and/or secondary amine groups, preferably primary (NH ₂ ).

In this variant, the (poly)amine compound(s) are chosen from poly(meth)acrylates or poly(meth)acrylamides bearing side primary or secondary amine functions, such as poly(3-aminopropyl)methacrylamide and poly(2-aminoethyl)methacrylate.

Preferably, the polyamine compounds are chosen from chitosans (in particular poly(D-glucosamine)), and polydimethylsiloxanes comprising primary amine groups at the end of the chain and/or on side chains.

According to this variant, the (poly)amine compound(s) are in particular chosen from poly(alkylene (C ₂ -C ₅ )imines), and preferably polyethyleneimines and polypropyleneimines, in particular poly(ethyleneimine), in particular that sold under the reference 408700 by the company Aldrich Chemical or under the trade name Lupasol by BASF, in particular with a molecular weight of between 1,200 and 25,000; poly(allylamine), in particular that sold under the reference 479136 by the company Aldrich Chemical; polyvinylamines and their copolymers, in particular with vinylamides, in particular vinylamine/vinylformamide copolymers such as those marketed under the name Lupamin ^® 9030 by the company BASF; polyamino acids having NH ₂ groups such as polylysine, in particular that sold by the company JNC Corporation (formerly Chisso); amino dextran, in particular that sold by the company CarboMer Inc; amino polyvinyl alcohol, in particular that sold by the company CarboMer Inc, copolymers based on acrylamido(C ₁ -C ₆ )alkylamine, in particular based on acrylamidopropylamine; and poly(D-Glucosamine) for example sold under the reference Kionutrime CSG ^® by the company Kytozyme.

According to a particular embodiment, the polydimethylsiloxanes comprising primary amine groups at the end of the chain and/or on side chains are chosen from the compounds of the following formula (VII):

R _a -Si(R _b )(R _c )-O-[Si(R _b )(R _c )-O] _m -[Si(ALK ¹ -NH ₂ )(R _a )-O] _n -Si( R _b )(R _c )-R _a (VII)

formula (VII) in which:

- R _a , identical or different, represents a hydroxy or (C ₁ -C ₄ )alkyl group,

- R _b and R _c , identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group, such as methyl,

- ALK ¹ represents a linear or branched (C ₁ -C ₆ )alkylene group, optionally interrupted by an N(H) group,

- m and n are integers greater than or equal to 1, preferably m and n are such that the weight average molecular mass of the compound of formula (VII) ranges from 1000 g.mol ^-1 to 500000 g.mol ^-1 .

According to a preferred variant, the formula (VII) is such that R _a , R _b , and R _c represent a methyl group, ALK ¹ represents a propylene group, n and m are such that the values of n and m are such that the weight average molecular weight of the polydimethylsiloxane ranges from 1000 g.mol ^-1 to 55000 g.mol ^-1 .

Examples of polydimethylsiloxanes of formula (VI) include those sold under the names “AMS-132”, “AMS-152”, “AMS-162”, “AMS-163”, “AMS-191” and “AMS-1203” by the company Gelest.

According to another variant, the formula (VII) is such that R _a represents a hydroxyl or (C ₁ -C ₄ )alkyl group, such as methyl, ALK ¹ represents a (C ₅ -C ₆ )alkylene group substituted by an NH group, preferably ALK ¹ represents -(CH ₂ ) ₃ -N(H)-(CH ₂ ) ₂ -, and m and n are such that the weight average molecular mass of the compound of formula (VI) ranges from 5000 g.mol ^-1 to 500000 g.mol ^-1 .

As amino polymers, α, ω-diamine polytetrahydrofurans (or polytetramethylene glycol) and α, ω-diamine polybutadienes can also be mentioned.

According to a particular embodiment of the invention, the (poly)amine compounds are chosen from hyperbranched polymers comprising at least one amino group and dendrimers carrying at least one amino group, such as polyamidoamine PAMAM dendrimers with an ethylenediamine core and a terminal amine function.

According to a preferred embodiment, the composition comprises a crosslinking agent R chosen from (poly)amine compounds, in particular chosen from chitosans, aminoalkoxysilanes, polydimethylsiloxanes comprising primary amine groups at the end of the chain or on side chains, amodimethicones, polyglucosamines, spermidine, and mixtures thereof.

More preferably, the composition comprises a crosslinking agent R chosen from chitosans, aminoalkoxysilanes and polydialkylsiloxanes comprising primary amine groups at the end of the chain or on side chains such as amodimethicones, and even more preferably chosen from poly(D-Glucosamine), 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl)-3-aminopropyltriethoxysilane, spermidine, and polydimethylsiloxanes comprising amino terminal groups at the end of the chain, such as Bis-Cetearyl Amodimethicone.

B) (Poly)thiolated compounds

According to a preferred embodiment, the crosslinking agent R is chosen from (poly)thiolated compounds also called “( poly)mercapto ”.

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

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

In a particular embodiment, the (poly)thiolated compound is inorganic. Examples that may be mentioned are silicone polythiols.

The (poly)thiolated compound may in particular be chosen from non-polymeric (poly)thiolated compounds.

By “ non-polymeric ” compounds, for the purposes of the present invention, we mean compounds which are not directly obtained by a polymerization reaction of monomers.

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

L(SH) _q (VIII)

formula (VIII) in which:

- q, represents an integer greater than or equal to 2, preferably q is inclusively between 2 and 10, preferably between 2 and 5;

- L denotes a multivalent (at least divalent) group, in particular comprising between 1 and 500 carbon and/or silicon atoms, more particularly between 2 and 40 carbon and/or silicon atoms, even more particularly between 3 and 30 carbon and/or silicon atoms, preferably between 6 and 20 carbon atoms, linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated; L being optionally interrupted and/or terminated by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their combinations 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 groups chosen from: -N(R _a )R _b , and -(X') _a -C(X)-(X'') _b -R _a ; with X, X' and X'', identical or different, representing an oxygen atom, 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 (C ₁ -C ₆ )alkyl group, 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 , identical or different, represent a (C ₁ -C ₆ )alkyl, aryl(C ₁ -C ₄ )alkyl or (C ₁ -C ₆ )alkoxy group.

According to a particular embodiment of the invention, the (poly)thiolated compound(s) are chosen from polythiolated compounds, in particular polythiolated compounds comprising from 2 to 20 carbon atoms.

According to a preferred embodiment, the (poly)thiolated compound(s) are non-polymeric, in particular of formula (VIII) defined above, in which q is an integer greater than or equal to 2, preferably q is an integer between 2 and 10 inclusive, preferably between 2 and 5.

The (poly)thiolated compounds suitable for the invention are preferably dithiol compounds.

Preferably, L denotes a multivalent C ₈ -C ₁₈ radical, in particular linear. Preferably, the liposoluble polythiol is a C ₈ -C ₁₈ dithiol, in particular linear. Preferably, the C ₈ -C ₁₈ chain is a hydrocarbon chain, i.e. formed of carbon and hydrogen. In particular, the liposoluble polythiol is a linear C ₈ -C ₁₆ diol, in particular C ₁₀ -C ₁₄ . As (poly)thiolated compounds of formula (VII), mention may be made more particularly 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 and/or 1,14-tetradecanedithiol are used, preferably 1,12-dodecanedithiol.

According to another particular embodiment of the invention, the (poly)thiolated compound(s) is(are) chosen from thiolated alkoxysiloxanes, such as those of formula (VIII’) below:

R' ₁ -Si(OR' ₂ )z(R' ₃ ) _x (VIII')

formula (VIII’) 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 thiol groups; and aryl, aryloxy, arylthio, arylamino, the aryl group being substituted by one or more thiol groups, or thiol(C ₁ -C ₆ )alkyl, 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 C(O), or their association such as ester -C(O)-O-, or amide -C(O)-N(H)-, R' ₁ being linked to the silicon atom directly via a carbon atom,

- R' ₂ and R' ₃ , identical or different, represent an alkyl group, linear or branched, comprising from 1 to 6 carbon atom(s), preferably from 1 to 4 carbon atom(s), such as methyl,

- z denotes an integer from 1 to 3, and

- x denotes an integer ranging from 0 to 2,

with z + x =3.

Preferably, R' ₂ represents a linear or branched alkyl group, preferably linear comprising from 1 to 4 carbon atoms, such as ethyl.

Preferably, R' ₃ represents a linear or branched alkyl group, preferably linear, comprising from 1 to 4 carbon atoms, such as methyl or ethyl.

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

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

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

Preferably, z is equal to 3.

According to a more particular embodiment of the invention, the thiolated alkoxysiloxanes are chosen from those of the following formula (IX):

(R ¹ O)(R ² )(R ³ )Si-[CH(R ⁴ )] _t -[N(R' ⁴ )-L ¹ ] _p -SH (IX)

formula (IX) in which:

- p is 0 or 1;

- t is an integer between 1 and 4, preferably 2;

- 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 )alkyl group, in particular C ₁ -C ₄ , such as methyl, and a (C ₁ -C ₆ )alkoxy group, in particular (C ₁ -C ₄₎ alkoxy, such as methoxy;

- R ⁴ and R' ⁴ , identical or different, represent a hydrogen atom, or a (C ₁ -C ₆ )alkyl group, such as methyl;

- L ¹ represents a linear or branched divalent, saturated, C ₁ -C ₂₀ hydrocarbon radical.

According to a particular embodiment of the invention, the thiolated alkoxysiloxane compounds are chosen from those of the following formula (IX’):

(R' ¹ O)(R' ² )(R' ³ )Si-CH(R ⁴ )-CH(R ⁵ )-(L ² ) _q -SH (IX')

formula (IX’) 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 , and 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 group, linear or branched saturated in C ₁ -C ₂₀ , optionally interrupted by a heteroatom such as -N(H)-, and/or optionally substituted by one or more hydroxy, thiol or amino groups.

Preferably, the thiolated alkoxysilane(s) are selected from 4-(trimethoxysilyl)-1-butanol, 3-(trimethoxysilyl)-1-propanol, 3-(triethoxysilyl)-1-propanol, 11-(trimethoxysilyl)-1-undecanethiol, 4-(trimethoxysilyl)-2-butanethiol, 2-(triethoxysilyl)-ethanethiol, 3-(triethoxysilyl)-1-propanethiol, 2-(trimethoxysilyl)-ethanethiol, 3-(trimethoxysilyl)-1-propanethiol and 3-(dimethoxymethylsilyl)-1-propanethiol.

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

According to a preferred embodiment of the invention, the (poly)thiolated compound(s) are chosen from polymeric (poly)thiolated compounds.

Polymeric (poly)thiolated compounds can be homopolymers, copolymers, stars, combs, brushes and dendritic with thiol units. The polymers can be of natural origin such as polysaccharides, polypeptides, or synthetic such as acrylics, polyesters, polyglycols. The thiol units can be present as terminal or pendant groups.

Examples include polymers described in the following documents: Polymers containing groups of biological activity, CG Overberger et al, Polytechnic Institute of Brooklyn , http://pac.iupac.org/publications/pac/pdf/1962/pdf/0402x0521.pdf ; EP 1 247 515 A2 ; US 3,676,440 ; and EP 1 572 778.

The polymeric (poly)thiolated compounds of the invention are preferably organic and/or silicone, more preferably of formula (X):

POLY(SH) _q (X)

formula (X) in which:

- q is greater than or equal to 2, preferably greater than or equal to 3;

- POLY denotes a polymeric radical, preferably carbon or silicone; POLY being optionally interrupted by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their combinations such as -O-, -OC(X)-, -N(R)-C(X)-, -Si(R _c )(R _d )-O- with R representing a hydrogen atom or a (C ₁ -C ₆ )alkyl group such as methyl; and/or POLY being optionally substituted by one or more halogen atoms, or a group chosen from R _a (R _b )N- and -(X') _a -C(X)-(X'') _b -R _a ; X, X' and X'', identical or different, represent an oxygen atom, 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 (C ₁ -C ₁₀ )alkyl group, or aryl(C ₁ -C ₄ )alkyl group, such as benzyl, preferably R _a and R _b represent a hydrogen atom; and R _c and R _d , identical or different, represent a (C ₁ -C ₁₀ )alkyl, aryl(C ₁ -C ₄ )alkyl or (C ₁ -C ₁₀ )alkoxy group.

The methods of preparing the polymeric (poly)thiolated compounds used according to the invention are known to those skilled in the art, several methods are reported below in a non-limiting manner. The polymeric (poly)thiolated compounds used according to the invention can be obtained by polymerization, polycondensation of monomer units with thiol or protected thiol functions, optionally by co-polymerization or co-polycondensation of monomer units devoid of thiol or protected thiol functions.

According to one embodiment of the invention, the polymeric (poly)thiolated compounds used according to the invention are polymers soluble in cosmetic media, particularly in aqueous or hydroalcoholic media. They are more preferably obtained from amino polymers and their ammonium salts or polyhydroxylated polymers.

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

According to one embodiment of the invention, the polythiol compound is a polymeric compound of formula (X) in which q denotes an integer greater than or equal to 2, and POLY denotes a carbon and/or silicone polymeric radical, preferably silicone, POLY being able to further contain one or more heteroatoms chosen from O, N, S and/or one or more functions chosen from the (thio)ester, (thio)ketone, (thio)amide, (thio)urea, (thio)carbamate functions, and/or be substituted by one or more linear or branched (C ₁ -C ₁₀ )alkyl, linear or branched (C ₁ -C ₁₀ )alkoxy groups, it being understood that when POLY is substituted, the thiol functions can be carried by the substituent(s).

The molar weight average molecular weight of polythiol polymer compounds, such as those of formula (X), is generally between 500 and 400000 g.mol ^-1 , preferably between 500 and 150000 g.mol ^-1 .

According to a particular embodiment of the invention, the polythiolated compounds are chosen from polyorganosiloxanes comprising thiol groups on terminal chains, such as those of formula (XI):

HS-L ⁴ -Si(R ^a )(R ^b )-O-[Si(R ^a )(R ^b )-O] _n -Si(R ^a )(R ^b )-L ⁵ -SH (XI)

formula (XI) in which:

- R ^a and R ^b , identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group, such as methyl, (C ₁ -C ₄ )alkoxy, such as methoxy, aryl, such as phenyl, aryloxy, such as phenoxy, aryl(C ₁ -C ₄ )alkyl, such as benzyl, or aryl(C ₁ -C ₄ )alkoxy, such as benzoxy, preferably (C ₁ -C ₄ )alkyl, such as methyl,

- n represents an integer greater than or equal to 1, and more particularly the value of n is such that the weight-average molecular weight of the silicone is from 500 to 55000 g.mol ^-1 ; particularly n is an integer from 1 to 100, preferably from 5 to 50, and preferentially from 10 to 30, and

- L ⁴ and L ⁵ , identical or different, preferably identical, 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, in particular represent a covalent bond, a (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylenoxy or oxy(C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene group, preferably a (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkyleneoxy, oxy-( _C1 - _C6 )alkylene, or ( _C1 - _C6 )alkyleneoxy( _C1 - _C6 )alkylene.

Preferably, the (poly)thiolated compounds are polythiolated polyorganosiloxanes, more preferably polythiolated polydimethylsiloxanes, notably chosen from those of formula (XII):

HS-L ⁴ -Si(CH ₃ ) ₂ -O-[Si(CH ₃ ) ₂ -O] _n -Si(CH ₃ ) ₂ -L ⁵ -SH (XII)

formula (XII) in which:

- L ⁴ and L ⁵ , are as defined above in formula (XI), in particular L ⁴ and L ⁵ represent a (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkyleneoxy, oxy-(C ₁ -C ₆ )alkylene, or (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene group, more preferably a divalent group chosen from -R ₂ -, -OR ₂ -, -R ₂ -O-, -R ₂ -OR ₂ -, preferably -R ₂ -OR ₂ -, with R ₂ representing a linear or branched (C ₂ -C ₆ )alkylene group, preferably linear, such as ethylene or propylene, preferably n-propylene; and

- n is as defined in formula (XI).

As polythiolated compounds of formula (XII), mention may be made of mercaptosiloxanes or thiolated siloxanes, in which the thiol functions are located at the ends of the chain, marketed by the company SHIN-ETSU under the reference X-22-167B and mercaptosiloxane, in which the mercapto functions are pendant, marketed by the company SHIN-ETSU under the reference KF-2001, or by polydimethylsiloxane in which the thiol functions are located at the ends of the chain by thio-n-propyl groups, 80-120 marketed by Gelest under the name DMS – SM 21.

Preferably, the polythiolated compounds are polyorganosiloxanes comprising thiol groups on side chains such as those of formula (XIII):

R ^a -Si(R ^b )(R ^d )-O-[Si(R ^a )(R ^b )-O] _m -[Si(R ^b )(ALK ₁ -SH)-O] _n -Si(R ^b )(R ^d )-R ^a (XIII)

formula (XIII) in which:

- R ^a , and R ^b , are as defined in formula (XI) and R ^d is as defined for R ^a and R ^b , preferably R ^a , R ^b , and R ^d , identical, represent a (C ₁ -C ₆ )alkyl group, such as methyl;

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

- ALK ₁ represents a divalent 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, a (thio)carbonyl group C(X) with X representing O, or S, or their associations such as -O-, -OC(O)- or -C(O)-O-, preferably ALK ₁ represents a (C ₁ -C ₆ )alkylene group, more preferably (C ₁ -C ₄ )alkylene, such as propylene;

- n and m, identical or different, represent an integer greater than 2, and more particularly the values of m and n are such that the weight average molecular weight of said polyorganosiloxane is between 1000 and 55000 g.mol ^-1 .

Examples of polythiolated compounds of formula (XIII) include those sold by Genesee Polymers under the names GP-367, GP-71-SS, GP-800 and GP-710s, preferably GP-367, marketed by Genesee Polymers.

Polythiolated compounds are in particular polydimethylsiloxanes comprising at least two thiol groups, such as for example the products SMS-022, SMS-042 and SMS-992 sold by the company Gelest in https://www.gpcsilicones.com/products/silicone-fluids/mercapto-functional, https://www.shinetsusilicone-global.com/products/type/oil/detail/search/deg07.shtml, and 1053_Reactive Silicones_Silanes/Silicones – Gelest.

According to a particular embodiment of the invention, the (poly)thiolated compounds are chosen from hyperbranched polymers comprising at least one thiol group and dendrimers carrying at least one thiol group such as thiolated PAMAMs.

Preferably, the (poly)thiolated compounds used according to the invention are chosen from polydiallylsiloxanes, in particular polydimethylsiloxanes comprising at least two thiol groups such as those of formula (XIII).

C) (Poly)acrylate compounds

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

By " (poly)acrylate " is meant a compound which comprises at least one acrylate ester group H ₂ C=C(R ^e )-C(O)-Y- with R ^e representing a hydrogen atom or (C ₁ -C ₄ )alkyl group, such as methyl, preferably R ^e representing a hydrogen atom, and Y representing an oxygen atom or an amino group -N(H)-, preferably an oxygen atom.

More particularly, the (poly)acrylate(s) of the invention are of formula (XIV):

L[-YC(O)-C(R ^e )=CH ₂ ] _q (XIV)

formula (XIV) in which q and L are as defined in formula (VIII), Y and R ^e being as defined previously, preferably Y = O and R ^e = H.

According to a preferred embodiment, the compounds of formula (XIV) are such that L represents a di or trivalent, preferably trivalent, hydrocarbon chain comprising from 1 to 8 carbon atoms, q is 2 or 3, preferably 3, Y represents O, and R ^e represents a hydrogen atom.

According to a particular embodiment, the (poly)acrylate compounds are chosen from polyorganosiloxanes comprising at least one acrylate group on the side chain such as those of formula (XV):

R ^a -Si(R ^b )(R ^d )-O-[Si(R ^a )(R ^b )-O] _m -[Si(R ^b )(ALK ₁ -YC(O)-C(R ^e ) =CH ₂ )-O] _n -Si(R ^b )(R ^d )-R ^a (XV)

formula (XV) in which:

- R ^a , R ^b , and R ^d , are as defined in formula (XIII), preferably, R ^a , R ^b , and R ^d represent a (C ₁ -C ₆ )alkyl group, such as methyl,

- ALK ₁ is as defined for formula (XIII), preferably ALK ₁ represents a (C ₁ -C ₆ )alkylene group, more preferably (C ₁ -C ₄ )alkylene, such as propylene,

- n and m, identical or different, represent an integer greater than 2, and more particularly the values of m and n are such that the weight average molecular weight of said polyorganosiloxane is between 1000 and 55000 g.mol ^-1 ,

- Y is as defined above, preferably is an oxygen atom.

More particularly, the (poly)acrylate compound may be selected from 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, di(trimethylolpropane) tetraacrylate, glycerol 1,3-diglycerolate diacrylate, glycerol propoxylate (1PO/OH) triacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol ethoxylate diacrylate, hydroxypivalyl hydroxypivalate, neopentyl glycol diacrylate, neopentyl glycol propoxylate (1PO/OH) diacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, poly(propylene glycol) diacrylate, tricyclo[5.2.1.02,6]decanedimethanol diacrylate, trimethylolpropane ethoxylate (1EO/OH) methyl ether diacrylate, trimethylolpropane propoxylate triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tri(propylene glycol) diacrylate, trimethylolpropane triacrylate and tris[2-(acryloyloxy)ethyl] isocyanurate.

The (poly)acrylate compound may also be chosen from N,N’-methylene bis-acrylamide.

According to this embodiment, the (poly)acrylate compound is associated in its implementation with an amine catalyst as described for example in the articles Progress in coating 129, 21-25 (2019) and Progress in coating 135, 510-516 (2019). Preferably, the amine catalyst(s) are chosen from piperidine, DMAP (Dimethylaminopyridine), DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), DABCO (1,4-diazabicyclo[2.2.2]octane), DBN (1,5-Diazabicyclo[4.3.0]non-5-ene), more preferably chosen from DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), DABCO (1,4-diazabicyclo[2.2.2]octane), DBN (1,5-Diazabicyclo[4.3.0]non-5-ene), and in particular the catalyst is DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene).

More particularly, the (poly)acrylate compounds are chosen from those of formula (XIV), in particular trimethylolpropane triacrylate, and those of formula (XV), in particular the copolymers of dimethylsiloxane and acryloxypropyl)methylsiloxane.

D) (Poly)carbonyl compounds

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

In particular, the (poly)carbonyl compound is chosen from terephthalaldehyde, 5,5-dimethyl-1,3-cyclohexanedione, phenylglyoxal, isophthalaldehyde, 4-acetylbenzaldehyde, 4,4-diformyltriphenylamine,2-acetylbenzaldehyde, 3-(2-furoyl)quinoline-2-carboxaldehyde, 3-acetylbenzaldehyde, 9-(2-ethylhexyl)carbazole-3,6-dicarboxaldehyde, phthaldialdehyde, 1,3-cyclohexanedione, 4,4'-biphenyldicarboxaldehyde, benzene-1,3,5-tricarboxaldehyde, and nonionic or anionic oxidized polysaccharides such as oxidized inulins, in particular those of formula (II) as defined below. In particular, the (poly)carbonyl compounds comprise a _C5 - _C7 carbocycle, saturated or unsaturated, aromatic, preferably aromatic, such as phenyl, or non-aromatic and saturated such as cyclohexyl, more preferably unsaturated and aromatic, such as terephthalide.

According to a particular embodiment, the (poly)carbonyl compound(s) are chosen from nonionic or anionic oxidized polysaccharides comprising one or more aldehyde groups, and optionally one or more anionic groups.

These anionic groups are preferably carboxy or carboxylate groups.

The oxidized nonionic or anionic polysaccharides according to the invention can be represented by the following formula (II):

P–(CHO) _m (COOQ) _n (II)

formula (II) in which:

- P represents a polysaccharide chain, preferably consisting of monosaccharides comprising 5 carbon atoms or more than 5 carbon atoms, preferably 6 or more than 6 carbon atoms, and more particularly 6 carbon atoms;

- Q is chosen from a hydrogen atom, ions derived from an alkali or alkaline earth metal, such as sodium, potassium, ammonia, organic amines, such as monoethanolamine, diethanolamine, triethanolamine and 3-aminopropanediol-1,2 and basic amino acids, such as lysine, arginine, sarcosine, ornithine, citrulline;

- m + n is greater than or equal to 1;

- m is such that the degree of substitution of the polysaccharide by one or more aldehyde groups (DS(CHO)) is within the range from 0.001 to 2, preferably from 0.005 to 1.5;

- n is such that the degree of substitution of the polysaccharide by one or more carboxylic groups (DS(COOX)) is within the range from 0 to 2, preferably from 0.001 to 1.5.

By degree of substitution DS(CHO) or DS(COOX) of the polysaccharides according to the invention, is meant the ratio between the number of carbons oxidized into an aldehyde or carboxylic group for all the repeating units and the number of elementary monosaccharides (even opened by pre-oxidation) constituting the polysaccharide. The CHO and COOX groups can be obtained during the oxidation of certain carbon atoms, for example on carbon atoms 2, 3 or 6, of a saccharide unit with 6 carbon atoms.

Preferably, the oxidation can be carried out at carbon 2 and 3, more particularly from 0.01% to 75% by number, and preferably from 0.1% to 50% by number of the cycles which may have been opened.

The polysaccharide chain, represented by P, is preferably chosen from celluloses, starches, maltodextrins, guar gums, xanthan gums, pullulan gums, agar-agar gums, carrageenan gums, gellan gums, gum arabic, polyxylans and tragacanth gums and their derivatives.

By derivative is meant the compounds obtained by chemical modification of the compounds mentioned. These may be esters, amides, ethers of said compounds.

The oxidation can be carried out according to a method known in the art, for example according to the method described in FR 2 842 200, in the document FR 2 854 161 or in the article “Hydrophobic films from maize bran hemicelluloses” by E. Fredon et al, Carbohydrate Polymers 49, pages 1 to 12 (2002).

Another oxidation process is described in the article "Water soluble oxidized starches by peroxide reaction extrusion" Industril Crops and Products 7 , RE Wing, JL Willet 45-52 (1997).

According to this embodiment, the (poly)carbonyl compound is associated in its implementation with an amine catalyst, as described in the articles Progress in coating 129, 21-25 (2019) and Progress in coating 135, 510-516 (2019). Preferably, the amine catalyst(s) are chosen from piperidine, DMAP (Dimethylaminopyridine), DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), DABCO (1,4-diazabicyclo[2.2.2]octane), DBN (1,5-Diazabicyclo[4.3.0]non-5-ene), more preferably chosen from DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), DABCO (1,4-diazabicyclo[2.2.2]octane), DBN (1,5-Diazabicyclo[4.3.0]non-5-ene), and in particular the catalyst is DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene).

According to a preferred embodiment, the crosslinking agent is chosen from the compounds A) (poly)amino, B) (poly)thiolated, C) (poly)acrylates, and preferably from the compounds A) (poly)amino and B) (poly)thiolated, and more preferentially from the compounds A) (poly)amino.

In particular, said (poly)amino compounds A) are chosen from a) chitosans, such as poly(D-glucosamine), b) diamino polyethers, particularly α, ω-diamino polyethylene glycols (with an amine function at the chain end), c) triamino polyethers, such as Polyetheramine (or jeffamine), d) aminoalkoxysilanes, such as APTES, and e) polydialkylsiloxanes comprising primary amine groups at the chain end or on side chains, particularly polydimethylsiloxanes comprising primary amine groups, such as poly(dimethoxysiloxane) terminated with bis(3-aminopropyl) (PDMS-diNH ₂ ) and amodimethicones comprising amine groups on side chains such as bis-cetearyl amodimethicone, in particular that marketed by Momentive Performance Materials.

According to a preferred embodiment, said (poly)amine compounds A) are chosen from a) chitosans, such as poly(D-Glucosamine), c) polyether triamines, such as Polyetheramine (or jeffamine), and e) polydialkylsiloxanes comprising primary amine groups at the end of the chain or on side chains, particularly polydimethylsiloxanes comprising primary amine groups, such as poly(dimethoxysiloxane) terminated with bis(3-aminopropyl) (PDMS-diNH ₂ ) and amodimethicones comprising amine groups on side chains such as bis-cetearyl amodimethicone, in particular that marketed by Momentive Performance Materials.

In particular, said (poly)thiolated compounds B) are chosen from a) polydialkylsiloxanes with thiol functions, and b) alkoxysilanes with thiol functions, particularly are chosen from a) polydialkylsiloxanes with thiol functions, preferentially polydimethylsiloxanes comprising thiol groups on the side chain (such as mercaptopropyl), in particular those of formula (XIII).

In particular, said (poly)acrylate compounds C) are chosen from those of formula (XIV), in particular trimethylolpropane triacrylate, and those of formula (XV), in particular copolymers of dimethylsiloxane and acryloxypropyl)methylsiloxane, preferably trimethylolpropane triacrylate.

According to a preferred embodiment, the crosslinking agent(s) is (are) chosen from:

A) (poly)amino compounds chosen from:

ia) chitosans such as poly(D-Glucosamine),

ib) polydialkylsiloxanes comprising primary amine groups at the chain end or on side chains, in particular polydimethylsiloxanes comprising primary amine groups, more particularly poly(dimethoxysiloxane) terminated with bis(3-aminopropyl) (PDMS-diNH ₂ ) and amodimethicones comprising amine groups on side chains, more particularly bis-cetearyl amodimethicone;

B) (poly)thiolated compounds chosen from:

(iia) polydialkylsiloxanes with thiol functions, and

(iib) alkoxysilanes with thiol functions,

and in particular chosen from compounds iia) polydialkylsiloxanes with thiol functions, preferably from polydimethylsiloxanes comprising thiol groups on the side chain, in particular mercaptopropyl, and more particularly chosen from compounds of formula (XIII):

R ^a -Si(R ^b )(R ^d )-O-[Si(R ^a )(R ^b )-O] _m -[Si(R ^b )(ALK ₁ -SH)-O] _n -Si(R ^b )(R ^d )-R ^a (XIII)

formula (XIII) in which:

- R ^a and R ^b , identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group, in particular methyl, a (C ₁ -C ₄ )alkoxy group, in particular methoxy, an aryl group, in particular phenyl, an aryloxy group, in particular phenoxy, an aryl(C ₁ -C ₄ )alkyl group, in particular benzyl, or an aryl(C ₁ -C ₄ )alkoxy group, in particular benzoxy, and preferably a (C ₁ -C ₄ )alkyl group, more preferably methyl,

- R ^d represents a (C ₁ -C ₄ )alkyl group, in particular methyl, a (C ₁ -C ₄ )alkoxy group, in particular methoxy, an aryl group, in particular phenyl, an aryloxy group, in particular phenoxy, an aryl(C ₁ -C ₄ )alkyl group, in particular benzyl, an aryl(C ₁ -C ₄ )alkoxy group, in particular benzoxy, or a (C ₁ -C ₆ )alkyl group substituted by a (C ₁ -C ₄ )alkylamino, amino, or thiol group, and preferably a (C ₁ -C ₄ )alkyl group, more preferably methyl,

and preferably R ^a , R ^b , and R ^d , are identical and represent a (C ₁ -C ₆ )alkyl group, more preferably methyl,

- ALK ₁ represents a divalent 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, a (thio)carbonyl group C(X) with X representing O or S, or their associations, in particular -O-, -OC(O)- or -C(O)-O-, preferably ALK ₁ represents a (C ₁ -C ₆ )alkylene group, more preferably (C ₁ -C ₄ )alkylene, even more preferably propylene,

- n and m, identical or different, represent an integer greater than 2, and in particular the values of m and n are such that the weight average molecular weight of said polyorganosiloxane is between 1000 and 55000 g.mol^-1 ; And

C) (poly)acrylate compounds of formula (XIV):

L[-YC(O)-C(R ^e )=CH ₂ ] _q (XIV)

formula (XIV) in which:

- q represents an integer greater than or equal to 2, in particular n is inclusively between 2 and 10, and preferably between 2 and 5,

- L denotes an at least divalent multivalent group, in particular comprising between 1 and 500 carbon and/or silicon atoms, more particularly between 2 and 40 carbon and/or silicon atoms, even more particularly between 3 and 30 carbon and/or silicon atoms, preferably between 6 and 20 carbon atoms, linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated; L being optionally interrupted and/or terminated by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their combinations, in particular -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, in particular methyl; and/or L being optionally substituted by one or more groups chosen from: -N(R _a )R _b , and -(X') _a -C(X)-(X'') _b -R _a , with X, X' and X'', identical or different, representing an oxygen atom, sulfur atom, or an N(R _b ) group, a and b being 0 or 1, preferably the sum of a and b being 1, R _a and R _b , identical or different, representing a hydrogen atom, a (C ₁ -C ₆ )alkyl group, or an aryl(C ₁ -C ₄ )alkyl group, in particular benzyl, preferably R _a and R _b represent a hydrogen atom, and R _c and R _d , identical or different, represent a (C ₁ -C ₆ )alkyl, aryl(C ₁ -C ₄ )alkyl or (C ₁ -C ₆ )alkoxy group,

- R ^e represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, in particular methyl, preferably R ^e represents a hydrogen atom, and

- Y represents an oxygen atom or an amino group -N(H)-, preferably an oxygen atom,

preferably Y is an oxygen atom and R ^e is a hydrogen atom, preferably L represents a di or trivalent, preferably trivalent, hydrocarbon chain comprising from 1 to 8 carbon atoms, q is 2 or 3, preferably 3, and

more preferably the compounds of formula (XIV) are trimethylolpropane triacrylate.

Cosmetic Active Ingredients iv)

According to a particular embodiment, the method of the invention further comprises the application of iv) at least one cosmetic active ingredient, to keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows.

More particularly, in the treatment method according to the invention, at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5” used comprises one or more cosmetic active ingredients.

In particular, the cosmetic active ingredient(s) iv) is (are) chosen from:

(a) colouring matters (or colouring agents) other than Rhodamine B, in particular chosen from pigments, direct dyes, anionic, cationic, zwitterionic or neutral, non-fluorescent or fluorescent, but other than Rhodamine B, and mixtures thereof,

b) active ingredients for the care of keratin materials, preferably skin,

c) UV filters, and

d) their mixtures.

According to a particular embodiment, the at least one cosmetic agent is chosen from coloring materials other than Rhodamine B, preferably chosen from pigments, direct dyes, anionic, cationic, zwitterionic or neutral, non-fluorescent or fluorescent, but different from Rhodamine B, and their mixtures, more preferably pigments.

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

Coloring materials

According to a particular embodiment, the method of the invention uses one or more coloring materials other than Rhodamine B.

More particularly, in the process of the invention, at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5” used, comprises at least one coloring matter other than Rhodamine B, particulate or not, water-soluble or not, and preferably at a rate of at least 0.01% by weight, relative to the total weight of the composition considered.

For obvious reasons, this quantity is likely to vary significantly with regard to the intensity of the desired color effect and the color intensity provided by the coloring materials considered and its adjustment clearly falls within the skills of those skilled in the art.

Preferably, at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5” comprises at least one coloring material different from Rhodamine B chosen from pigments, anionic, cationic, zwitterionic, neutral, non-fluorescent or fluorescent direct dyes, different from Rhodamine B (more particularly different from fluorescent dyes), and their mixtures, more preferably pigments.

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

Pigments

For the purposes of the invention, the term " pigment " means any compound capable of imparting color to keratin materials. These compounds have a solubility in water at 25°C and at atmospheric pressure (760 mmHg) of less than 0.05% by weight, and preferably less than 0.01% by weight.

As pigments suitable for the invention, mention may in particular be made of organic and/or mineral pigments known in the art, in particular those described in Kirk-Othmer's encyclopedia of chemical technology and in Ullmann's encyclopedia of industrial chemistry.

These pigments can be synthetic or natural.

These pigments can be presented in the form of powder or pigment paste.

They can be coated or uncoated.

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

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

By " mineral pigment " is meant any pigment that meets the definition of the Ullmann encyclopedia in the chapter on inorganic pigment. Among the mineral pigments useful in the present invention, mention may be made of manganese violet, ultramarine blue, chromium hydrate, ferric blue and oxides or dioxides of titanium, zirconium or cerium, as well as oxides of zinc, iron or chromium.

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

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

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

By " organic pigment " is meant any pigment that meets the definition of the Ullmann Encyclopedia in the organic pigment chapter. Among the organic pigments useful in the present invention, mention may be made of nitroso, nitro, azo, xanthene, pyrene, quinoline, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone. In particular, the white or colored organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 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, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole, phenolic derivatives as described in patent FR 2 679 771.

For example, we can also cite organic pigment pigment pastes such as the products sold by the company HOECHST under the name: COSMENYL YELLOW IOG: Pigment YELLOW 3 (CI 11710); COSMENYL YELLOW G: Pigment YELLOW 1 (CI 11680); COSMENYL ORANGE GR: Pigment ORANGE 43 (CI 71105); COSMENYL RED R: Pigment RED 4 (CI 12085); COSMENYL CARMINE FB: Pigment RED 5 (CI 12490); COSMENYL VIOLET RL: Pigment VIOLET 23 (CI 51319); COSMENYL BLUE A2R: Pigment BLUE 15.1 (CI 74160); COSMENYL GREEN GG: Pigment GREEN 7 (CI 74260); COSMENYL BLACK R: Pigment BLACK 7 (CI 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 organic pigment can also be a lake.

By " lake " is meant dyes adsorbed on insoluble particles, the whole thus obtained remaining insoluble during use.

Inorganic substrates on which the dyes are adsorbed include, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium. Among the dyes adsorbed on organic substrates, carminic acid may be mentioned. Also included are the dyes known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 (CI 42 090), FDC Red 4, D & C Red 6, D & C Red 22, D & C Red 28, D & C Red 30, D & C Orange 4, D & C Yellow 8, D & C Green 5, D & C Red 17, D & C Green 6, D & C Yellow 11, D & C Violet 2, Sudan Red, Carotenes (b-carotene, lycopene), Xanthophylls (capsanthin, capsorubin, lutein), Palm Oil, Sudan Brown, Quinoline Yellow, Annatto, Curcumin, Betanin (Beetroot), Carmine, Copper Chlorophyllin, Methylene Blue, Anthocyanins (Enocyanin, Black Carrot, Hibiscus, Elderberry), Caramel, Riboflavin, Beetroot Juice, and Caramel.

Examples of lacquers include the product known under the following name: D & C Red 7 (CI 15 850:1).

The pigment can also be a special effects pigment.

" Special effect pigments " are pigments that generally create a colored appearance (characterized by a certain shade, a certain liveliness and a certain clarity) that is non-uniform and changes depending on the observation conditions (light, temperature, observation angles, etc.). They are thus opposed to colored pigments that provide a conventional uniform opaque, semi-transparent or transparent shade.

There are several types of special effect pigments, those with a low refractive index such as fluorescent or photochromic pigments, and those with a higher refractive index such as pearls, interference pigments or glitters.

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

Pigments can be dispersed in the composition using a dispersing agent.

This dispersing agent may be a surfactant, an oligomer, a polymer or a mixture of several of them, carrying one or more functionalities having a strong affinity for the surface of the particles to be dispersed. In particular, they can attach physically or chemically to the surface of the pigments. These dispersants also have at least one functional group compatible or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of _C8 to _C20 fatty acid and of polyol such as glycerol, diglycerin, such as poly(12-hydroxystearic acid) stearate with a molecular weight of approximately 750 g/mol such as that sold under the name Solsperse 21 000 by the company Avecia, polyglyceryl-2 dipolyhydroxystearate (CTFA name) sold under the reference Dehymyls PGPH by the company Henkel or polyhydroxystearic acid such as that sold under the reference Arlacel P100 by the company Uniqema and their mixtures are used. As another dispersant that can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17 000 sold by the company Avecia, polydimethylsiloxane/oxypropylene mixtures such as those sold by the company Dow Corning under the references DC2-5185, DC2-5225 C. The pigments used in the composition can be surface-treated with an organic agent. According to a particular embodiment, the dispersing agent(s) are of the amino-silicone type, different from the alkoxysilanes previously described and are cationic. Preferably, the pigment(s) is (are) chosen from mineral, mixed mineral-organic or organic pigments.

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

According to another embodiment of the invention, the pigment(s) according to the invention are mineral pigments.

Direct Dyes

According to a particular embodiment of the invention, the cosmetic active ingredient is a coloring material chosen from one or more direct dye(s) other than Rhodamine B.

By " direct dye " we mean natural and/or synthetic dyes, different from oxidation dyes. These are dyes that will diffuse superficially on the keratin material. They can be ionic or non-ionic, anionic, cationic, zwitterionic or non-ionic, preferably cationic or non-ionic.

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

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

Hét ⁺ -C(Ra)=NN(Rb)-Ar, Q ^- (A)

Het ⁺ -N(Ra)-N=C(Rb)-Ar, Q ^- (B)

Het ⁺ -N=N-Ar, Q ^- (C)

Ar ⁺ -N=N-Ar'', Q ^- (D)

formulas (A) to (D) in which:

- Het ⁺ represents a cationic heteroaryl radical, preferably with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally substituted preferably 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 (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, aryl(C ₁ -C ₈ )alkylamino, and N-(C ₁ -C ₈ )alkyl-N-aryl(C ₁ -C ₈ )alkylamino optionally substituted or 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 groups;

- Ra and Rb, identical or different, representing a hydrogen atom or a (C ₁ -C ₈ )alkyl group optionally substituted, preferably by a hydroxyl group;

or the substituent Ra with a substituent of Het ⁺ and/or Rb with a substituent of Ar form together with the atoms which carry them a (hetero)cycloalkyl; particularly Ra and Rb, representing a hydrogen atom or a (C ₁ -C ₄ )alkyl group optionally substituted by a hydroxyl group;

- Q ^- represents an organic or inorganic anionic counterion such as a halide or an alkyl sulfate.

In particular, mention may be made of direct dyes with endocyclic azo and hydrazono cationic charges of formula (A) to (D) as defined above.

More particularly, the endocyclic cationic charge cationic direct dyes described in patent applications WO 95/15144, WO 95/01772 and EP-714954.

Preferably, the direct dyes are chosen from the compounds of the following formulas (E) and (F):

formula (E) or (F) in which:

- R ¹ represents a (C ₁ -C ₄ )alkyl group such as methyl;

- R ² and R ³ , identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group such as methyl;

- 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 counterion as defined above, particularly a halide such as chloride or an alkyl sulfate such as methyl sulfate or mesyl.

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

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

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

The anionic direct dyes may be selected from acid nitrated direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes other than Rhodamine B, acid indoamine dyes, acid anthraquinone dyes, indigoids and acid natural dyes.

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, purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidin, orceins. Extracts or decoctions containing these natural dyes and in particular poultices or extracts based on henna may also be used.

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

The coloring materials, preferably the pigments, may be present in concentrations ranging from 0.01% to 30% by weight, preferably from 0.02% to 20% by weight, more particularly from 0.05% to 15% by weight, relative to the total weight of the composition which contains them.

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

Preferably, the cosmetic active ingredient(s), in particular the coloring matter(s), and more particularly the pigment(s) are introduced into at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5”.

Active care ingredients

According to a particular embodiment, the method of the invention uses one or more care active ingredients.

More particularly, in the method of the invention, according to one embodiment, at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5” used comprises one or more care active ingredients, and preferably at a rate of at least 0.01% by weight, relative to the total weight of the composition considered. In particular, the care active ingredient may be at least one hydrophilic active ingredient and/or one lipophilic active ingredient, and preferably a hydrophilic care active ingredient.

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

The cosmetic care active ingredient(s) may in particular be chosen from: a) vitamins and their derivatives, in particular their esters, in particular tocopherol (vitamin E) and its esters (such as tocopheryl acetate), ascorbic acid (vitamin C) and its derivatives; b) humectants, in particular urea, hydroxyureas, glycerol, polyglycerols, glycerol glucoside, diglycerol glucoside, polyglyceryl glucosides, and xylityl glucoside, and in particular glycerol; c) C-glycoside compounds; d) antioxidant compounds; (e) anti-ageing active agents, in particular hyaluronic acid compounds, and in particular sodium hyaluronate, retinol and its derivatives, salicylic acid compounds and in particular n-octanoyl-5-salycilic acid (capryloyl salicylic acid), caffeine, adenosine, c-beta-d-xylopyranoside-2-hydroxy-propane and sodium salt of 3-hydroxy-2-pentylcyclopentyl)acetic acid; (f) skin care agents selected from allantoin, panthenol and protein hydrolysates; (g) polyphenols, in particular escin, ruscus, diosmin, hesperidin, resveratrol, and (h) mixtures thereof.

In particular, in the method of the invention, according to one embodiment, at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5” used comprises a moisturizing agent (also called a humectant). Preferably, the care active ingredient is a moisturizing agent, and in particular is glycerin (glycerol).

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

UV filters

According to one embodiment of the method of the invention, at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5” used comprises, as a cosmetic active ingredient, at least one UV filter.

The UV filter(s) is a UV filter commonly used in cosmetics.

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

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

They can be lipophilic, hydrophilic or insoluble organic.

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

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

By " insoluble UV filter " is meant any cosmetic or dermatological filter which is neither defined as a lipophilic UV filter nor as a hydrophilic UV filter, and which is in the form of particles in an aqueous or liquid oily phase. The UV filters of the composition according to the invention can provide UVA and/or UVB photoprotection.

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

In particular, the UV filter(s) are chosen from bis-resorcinyl triazine derivatives, dibenzoylmethane derivatives, benzylidene camphor derivatives, and mixtures thereof. The organic UV filters may also be chosen from anthranilics; cinnamic derivatives; salicylic derivatives; benzophenone derivatives; phenyl benzotriazole derivatives; benzalmalonate derivatives, in particular those cited in patent US 5,624,663; phenyl benzimidazole derivatives; imidazolines; 4,4-diarylbutadienes derivatives; bis-benzoazolyl derivatives, as described in patents EP 6,693 23 and US 2,463,264; p-aminobenzoic acid (PABA) derivatives; methylene bis-(hydroxyphenyl benzotriazole) derivatives, as described in applications US 5,237,071, US 5,166,355, GB 2303549, DE 197 26 184 and EP 893 119; benzoxazole derivatives, as described in patent applications EP 0 832 642, EP 1 027 883, EP 1 300 137 and DE 10162844; filter polymers and filter silicones such as those described in particular in application WO 93/04665; dimers derived from α-alkylstyrene such as those described in patent application DE 19855649; 4,4-diarylbutadienes as described in applications EP 0 967 200, DE 19746654, DE 19755649, EP 1 008 586, EP 1 133 980 and EP 133 981; other merocyanine derivatives such as those described in applications WO 04006878, WO 05058269 and WO 06032741 and mixtures thereof.

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

The UV filter(s) can be mineral UVs which are generally pigments. Pigments can be coated or uncoated.

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

According to a particular embodiment, compositions “C1” to “C5” are free of mineral UV filters.

According to a particular embodiment, the amount of the mineral UV filter(s), present in the compositions “C1”, “C2”, “C3”, “C4” or “C5”, can range from 0.01% to 20% by weight, relative to the total weight of the composition which contains them. It ranges for example from 1% to 15% by weight, relative to the total weight of the composition.

According to a particular embodiment, at least one of the compositions “C1” to “C5” further comprises one or more organic UV filters and one or more mineral UV filters.

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

Preferably, the process for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, and the compositions “C1”, “C2”, “C3”, “C4” or “C5” use or comprise one or more coloring materials other than Rhodamine B, preferably chosen from pigments, direct dyes, anionic, cationic, zwitterionic or neutral, non-fluorescent or fluorescent, but different from Rhodamine B, and mixtures thereof; more preferably the pigment(s) of the invention are chosen from carbon black, iron oxides, in particular yellow, red and 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, even more preferably red iron oxides, yellow iron oxides and azo pigments, in particular red, such as D&C RED 7.

Fatty phase – Fatty substance

According to a particular embodiment, the method of the invention further uses v) one or more fatty substances, in particular one or more oils, preferably volatile.

In particular, at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5”, in particular at least the composition “C4”, used in the process of the invention contains a fatty phase.

In particular, at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5”, in particular at least the composition “C4”, used in the process of the invention comprises one or more fatty substances, in particular one or more oils, preferably volatile.

By " oil " we mean a fatty substance that is liquid at room temperature (20°C) and atmospheric pressure (760 mm Hg).

" Hydrocarbon oil " means an oil formed essentially, or even consisting of, carbon and hydrogen atoms, and possibly oxygen and nitrogen atoms, and not containing silicon or fluorine atoms. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

According to one embodiment of the invention, the oil(s) v) is (are) chosen from volatile oils, in particular:

- hydrocarbon oils having from 8 to 16 carbon atoms, in particular branched C ₈ -C ₁₆ alkanes, in particular isoalkanes, more particularly isoalkanes (also called isoparaffins), preferably C ₁₃ -C ₁₆ Isoparaffin, isododecane, isodecane, isohexadecane, for example oils sold under the trade names Isopars or Permetyls, alone or in mixtures, preferably isododecane (also called 2,2,4,4,6-pentamethylheptane), linear alkanes, in particular C ₁₁ -C ₁₆ , alone or in mixtures, in particular hexane, decane, undecane, tridecane, isoparaffins in particular n-dodecane (C ₁₂ ) and n-tetradecane (C ₁₄ ), the undecane-tridecane mixture, mixtures of n-undecane (C ₁₁ ) and n-tridecane (C ₁₃ ), and mixtures thereof as well as mixtures of n -undecane (C ₁₁ ) and n -tridecane (C ₁₃ ), and volatile non-aromatic cyclic C ₅ -C ₁₂ alkanes;

- short-chain esters having 3 to 8 carbon atoms in total, in particular ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate;

- carbonate hydrocarbon oils of structure R' ₁ -OC(O)-O-R' ₂ in which R' ₁ and R' ₂ independently denote a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably a C ₄ -C ₈ alkyl group, advantageously, more preferentially chosen from dibutylcarbonate or dipentylcarbonate;

- ether oils of formula R ₁ -OR ₂ , in which R ₁ and R ₂ denote, independently of one another, a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably a C ₄ -C ₈ alkyl group;

- silicone oils, in particular comprising from 2 to 7 silicon atoms, and optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms, in particular dimethicones with a viscosity of 5 and 6 cSt, cyclopentadimethylsiloxane, dodecamethylpentasiloxane, cyclohexadimethylsiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof;

more preferably the volatile oil(s) v) are chosen from C ₈ -C ₁₆ alkanes, in particular branched, preferably isododecane.

In particular, at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5”, in particular at least the composition “C4”, used in the process according to the invention comprises one or more non-volatile oils, preferably chosen from:

- non-volatile fluorinated oils, in particular chosen from fluorinated polyethers, fluorosilicone oils, fluorinated silicones;

- non-volatile silicone oils, in particular chosen from the following non-volatile silicones with the following INCI names: dimethicone, dimethiconol, trimethyl pentaphenyl trisiloxane, tetramethyl tetraphenyl trisiloxane, diphenyl dimethicone, trimethylsiloxyphenyl dimethicone, phenyltrimethicone, diphenylsiloxy phenyl trimethicone, and their mixtures;

- non-volatile apolar hydrocarbon oils, in particular chosen from linear or branched compounds, of mineral or synthetic origin: i) paraffin oil, ii) squalane, isoeicosane, iii) mixtures of linear, saturated hydrocarbons, more particularly C ₁₅ -C ₂₈ , in particular mixtures whose INCI names are (C ₁₅ -C ₁₉ )alkane, (C ₁₈ -C ₂₁ )Alkane, (C ₂₁ -C ₂₈ )alkane, iv) polybutenes, hydrogenated or not; v) polyisobutenes, hydrogenated or not, preferably hydrogenated, vi) polydecenes, hydrogenated or not, vii) decene/butene copolymers, butene/isobutene copolymers and viii) mixtures thereof;

- polar non-volatile hydrocarbon oils which may be chosen from:

i) saturated, unsaturated, linear or branched C ₁₀ -C ₂₆ fatty alcohols, preferably monoalcohols; in particular, C ₁₀ -C ₂₆ alcohols are fatty alcohols, preferably branched when they comprise at least 16 carbon atoms; preferably, the fatty alcohol comprises from 10 to 24 carbon atoms, and more preferably from 12 to 22 carbon atoms, in particular lauryl alcohol, isostearyl alcohol, oleyl alcohol, 2-butyloctanol, 2-undecyl pentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol, octyldodecanol and mixtures thereof;

(ii) triglycerides consisting of fatty acid esters of glycerol, in particular the fatty acids of which may have chain lengths varying from C ₄ to C ₃₆ , and in particular from C ₁₈ to C ₃₆ , these oils being able to be linear or branched, saturated or unsaturated; as examples, mention may in particular be made of heptanoic or octanoic triglycerides, caprylic/capric acid triglycerides; vegetable oils such as wheat germ, sunflower, grape seed, sesame, corn, apricot kernel, castor, shea, avocado, olive, soybean, sweet almond, palm, rapeseed, cottonseed, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, squash, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, candlenut, passionflower, musk rose, peanut, coconut, argan, kaya; the liquid fraction of shea butter, and the liquid fraction of cocoa butter; as well as mixtures thereof;

(iii) linear aliphatic hydrocarbon esters of formula R-C(O)-OR’ in which R-C(O)-O- represents the carboxylic acid residue containing from 2 to 40 carbon atoms, and R’ represents a hydrocarbon chain containing from 1 to 40 carbon atoms, aliphatic hydrocarbon esters of alkylene glycol, in particular ethylene glycol or propylene glycol; the total number of carbon atoms being in particular at least 10; in particular chosen from isoamyl laurate, cetostearyl octanoate, isopropyl myristate, isopropyl palmitate, isopropyl stearate or isostearate, ethyl palmitate, 2-ethylhexyl palmitate, isostearyl isostearate, octyl stearate, isostearyl heptanoate, octanoates, decanoates or ricinoleates of alcohols or polyalcohols such as propylene glycol dioctanoate, cetyl octanoate, tridecyl octanoate, ethyl 2-hexyl palmitate, alkyl benzoate, polyethylene glycol diheptanoate, propylene glycol diethyl 2-hexanoate and their mixtures, hexyl laurate, neopentanoic acid esters such as isodecyl neopentanoate, isotridecyl neopentanoate, isostearyl neopentanoate, octyl-2-docecyl neopentanoate, isononanoic acid esters, in particular isononyl isononanoate, isotridecyl isononanoate, octyl isononanoate, oleyl erucate; lauroyl isopropyl sarcosinate, diisopropyl sebacate, isocetyl stearate, isodecyl neopentanoate, isostearyl behenate, myristyl myristate;

iv) hydroxylated esters, in particular polyglycerol-2 triisostearate;

(v) aromatic esters, in particular tridecyl trimellitate, _C12 - _C15 alcohol benzoate, 2-phenyl ethyl ester of benzoic acid, butyl octyl salicylate;

(vi) esters of linear fatty acids having a total carbon number ranging from 35 to 70, in particular pentaerythrityl tetrapelargonate;

(vii) esters of fatty alcohols or branched C ₂₄ -C ₂₈ fatty acids, in particular triisoarachidyl citrate, pentaerythrityl tetraisononanoate, glyceryl triisostearate, glyceryl tridecyl-2-tetradecanoate, pentaerythrityl tetraisostearate, polyglyceryl-2 tetraisostearate or pentaerythrityl tetradecyl-2 tetradecanoate;

(viii) polyesters obtained by condensation of unsaturated fatty acid dimer and/or trimer and diol, in particular INCI name dilinoleic acid / butanediol copolymer, dilinoleic acid / propanediol copolymer; polyesters obtained by condensation of fatty acid dimer and diol dimer, in particular dimer dilinoleyl dimer dilinoleate;

(ix) synthetic ethers having from 10 to 40 carbon atoms, in particular dicaprylyl ether;

(x) dialkyl carbonates, the two alkyl chains being able to be identical or different, in particular dicaprylyl carbonate;

(xi) vinylpyrrolidone copolymers, in particular vinylpyrrolidone/1-hexadecene copolymer; and

(xii) their mixtures;

- the non-volatile carbonate oils may be chosen from carbonates of formula R ₈ -OC(O)-OR ₉ , with R ₈ and R ₉ , identical or different, representing a C ₄ to C ₁₂ alkyl chain, and preferably from C ₆ to C ₁₀ , linear or branched; the carbonate oils may be dicaprylyl carbonate (or dioctyl carbonate), di(ethyl-2-hexyl) carbonate, dipropylheptyl carbonate, dibutyl carbonate; di-neopentyl carbonate; dipentyl carbonate; di-neoheptyl carbonate; di-heptyl carbonate; di-isononyl carbonate; or di-nonyl carbonate; and preferably dioctyl carbonate;

- oils called non-volatile ether oils of formula R ₁ -OR ₂ in which R ₁ and R ₂ independently denote a linear, branched or cyclic C ₆ -C ₂₄ alkyl group, preferably a C ₆ -C ₁₈ alkyl group, and preferably a C ₈ -C ₁₂ alkyl group. It may be preferable for R ₁ and R ₂ to be identical. As a linear alkyl group, mention may be made of a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undodyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a behenyl group, a docosyl group, a tricosyl group and a tetracosyl group. As the branched alkyl group, there may be mentioned a 1,1-dimethylpropyl group, a 3-methylhexyl group, a 5-methylhexyl group, an ethylhexyl group, a 2-ethylhexyl group, a 5-methyloctyl group, a 1-ethylhexyl group, a 1-butylpentyl group, a 2-butyloctyl group, an isotridecyl group, a 2-pentylnonyl group, a 2-hexyldecyl group, an isostearyl group, a 2-heptylundecyl group, a 2-octyldodecyl group, a 1,3-dimethylbutyl group, a 1-(1-methylethyl)-2-methylpropyl group, a 1,1,3,3-tetramethylbutyl group, a 3,5,5-trimethylhexyl group, a 1-(2-methylpropyl)-3-methylbutyl group, a 3,7-dimethyloctyl group, and a 2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctyl group. As a cyclic alkyl group, there may be mentioned a cyclohexyl group, a 3-methylcyclohexyl group and a 3,3,5-trimethylcyclohexyl group, dilauryl ether, diisostearyl ether, dioctyl ether, nonylphenyl ether, dodecyl dimethylbutyl ether, cetyl dimethylbutyl ether, cetyl isobutyl ether and mixtures thereof;

Preferably, the non-volatile oil(s) is (are) chosen from polyisobutenes, hydrogenated or not, preferably hydrogenated, in particular the non-volatile compounds of the ^Parléam® range; mixtures of C ₁₅ -C ₁₉ Alkane, and from linear aliphatic hydrocarbon esters of formula RC(O)-OR' in which RC(O)-O represents a carboxylic acid residue comprising from 2 to 40 carbon atoms, and R' represents a hydrocarbon chain containing from 1 to 40 carbon atoms, as defined above, in particular isononyl isononanoate.

More preferably, the process of the invention uses one or more hydrocarbon oils having from 8 to 16 carbon atoms, and in particular branched C ₈ -C ₁₆ alkanes, in particular iso-alkanes, preferably C ₁₃ -C ₁₆ Isoparaffin, isododecane, isodecane, isohexadecane, alone or in mixtures, and more preferably isododecane.

In particular, the amount of oil(s) in at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5”, in particular at least the composition “C4”, used in the process according to the invention ranges from 1% to 99% by weight, relative to the total weight of the composition, more particularly from 2% to 98% by weight, preferentially from 3% to 97%, better still from 5% to 95% by weight, relative to the total weight of the composition.

According to a particular embodiment, the cosmetic active ingredients iv) are chosen from a) coloring materials chosen from pigments, direct dyes other than rhodamine B, more particularly other than rhodamines, more preferably the direct dyes are non-fluorescent, and mixtures thereof, b) active ingredients for caring for keratin materials, preferably the skin, and d) mixtures thereof. According to this embodiment, the composition(s) “C1” to “C5” do not contain filters as defined above.

According to another particular embodiment, the cosmetic active ingredients iv) are chosen from a) coloring materials chosen from pigments, direct dyes other than rhodamine B, more particularly other than rhodamines, more preferably the direct dyes are non-fluorescent, and their mixtures, c) UV filters and d) their mixtures. According to this embodiment, the composition(s) “C1” to “C5” do not contain care active ingredients as defined above.

According to a preferred embodiment, the cosmetic active agent(s) iv) are chosen from coloring agents other than Rhodamine B, as defined above, in particular chosen from anionic, cationic, zwitterionic or neutral direct dyes, non-fluorescent or fluorescent, but different from Rhodamine B, or pigments, more preferably from pigments. According to this embodiment, the composition(s) “C1” to “C5” do not contain filters or care active agents as defined above.

Compositions

According to the invention, the method for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows according to the invention, uses water. Thus, the compositions “C1”, “C2” and “C3” used in the method of the invention comprise water, and the compositions “C4” and “C5” optionally comprise water.

Thus, in particular, the composition “C1” is aqueous or hydroalcoholic. Preferably, the composition “C1” is aqueous.

In particular, the composition “C2” is aqueous or hydroalcoholic. Preferably, the composition “C2” is aqueous.

In particular, the composition “C3” is aqueous or hydroalcoholic. Preferably, the composition “C3” is aqueous.

In particular, the composition “C4” is aqueous or hydroalcoholic. Preferably, the composition “C4” is aqueous.

In particular, the “C5” composition is aqueous or hydroalcoholic.

According to a particular embodiment, the compositions “C1”, “C2”, “C3” and “C4” are aqueous.

According to a particular embodiment, the compositions “C1”, “C2” and “C3” are hydroalcoholic. In particular, they comprise a water/polar solvent mixture, preferably water/polar protic solvent, such as ethanol/water, in particular in a solvent/water volume ratio of between 1/99 to 99/1, more particularly between 10/90 to 90/10, even more particularly between 20/80 and 80/20, preferably 40/60 to 60/40, such as 50/50.

According to a particular embodiment, the compositions “C1”, “C2”, “C3”, “C4” or “C5” can be in the form of a water-in-oil emulsion or an oil-in-water emulsion.

According to a particular embodiment, the compositions “C4” or “C5” may be in anhydrous form, water-in-oil emulsion or oil-in-water emulsion.

According to a particular embodiment, the composition “C4” is anhydrous. In particular, the composition “C4” is anhydrous, and comprises at least one oil, in particular volatile, preferably isododecane.

The compositions “C1” to “C5” used in the process of the invention may also comprise one or more solvents, other than water.

According to a particular embodiment of the invention, the (co)polymer(s) i) as defined above are used in a medium containing at least one solvent, preferably at least one polar and/or protic solvent, other than water.

According to this embodiment, the composition “C1” and/or “C2” and/or “C3” and/or “C4” and/or “C5” used in the process of the invention, comprises one or more solvents, preferably one or more polar and/or protic solvents, other than water.

According to this embodiment, preferably, the composition “C1” and/or “C2” and/or “C3” and/or “C4” and/or “C5” used in the process of the invention comprises at least one polar and/or protic solvent chosen from monoalcohols having from 2 to 6 carbon atoms, in particular chosen from ethanol, propanol, n-butanol, isopropanol, isobutanol, tert-butanol, pentanol, hexanol, preferably n-butanol or ethanol, and even more preferably ethanol.

According to one embodiment, the composition “C1” and/or “C2” and/or “C3” and/or “C4” and/or “C5” used in the process of the invention comprises one or more solvents other than water in a content of less than 70% by weight, more preferably less than 50% by weight, even more preferably less than 40% by weight, relative to the total weight of water.

As organic solvent, mention may also be made of polyols miscible with water at room temperature (25°C), in particular chosen from polyols having in particular from 2 to 10 carbon atoms, preferably having from 2 to 6 carbon atoms, such as glycerin, propylene glycol, 1,3-propanediol, butylene glycol, pentylene glycol, hexylene glycol, dipropylene glycol, diethylene glycol, diglycerin; polyol ethers such as 2-butoxyethanol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol, and mixtures thereof.

According to a particular embodiment, the composition considered further comprises one or more polyols, notably chosen from polyols notably having from 2 to 10 carbon atoms, preferably having from 2 to 6 carbon atoms, preferably glycerin.

The compositions “C1”, “C2”, “C3”, “C4” or “C5” used in the process of the invention may further comprise one or more adjuvants commonly used in cosmetics, in particular chosen from thickeners, film-forming agents, gelling agents, trace elements, softeners, sequestering agents, perfumes, alkalizing or acidifying agents, dispersing agents, preservatives, fillers, surfactants, polymers other than i), or mixtures thereof.

Another subject of the invention is a composition “C3” comprising i) at least one (co)polymer as defined above, ii) water; iii) at least one crosslinking agent, in particular as defined above, and iv) at least one cosmetic active ingredient other than Rhodamine B, preferably at least one coloring matter other than Rhodamine B, and more preferably at least one pigment, as defined above.

Another object of the invention is the cosmetic use of the composition “C3” as defined above, for the treatment of keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows.

A composition “C1”, “C2”, “C3”, “C4” or “C5” is generally suitable for application to keratin materials, in particular application to the skin and/or lips, and therefore generally comprises a physiologically acceptable medium, i.e. compatible with keratin materials, in particular application to the skin and/or lips.

Said compositions “C1” to “C5” are cosmetic compositions, compounds i), iii), optionally iv) and optionally v) being in a cosmetically acceptable medium, that is to say which has a pleasant color, odor and feel and does not generate unacceptable discomfort, that is to say tingling, tightness, likely to discourage the user from applying this composition.

A composition “C1”, “C2”, “C3”, “C4” or “C5” may be in the form of a makeup product, in particular colored, for the skin, in particular a foundation, possibly having care properties, a blush, a blusher or eye shadow, a concealer, an eyeliner; a lip makeup product such as a lipstick, possibly having care properties, a lip gloss, lip pencils; a makeup product for the appendages such as the nails, the eyelashes in particular in the form of a mascara bread, the eyebrows and the hair, a temporary tattoo product for the skin of the body.

A composition “C1”, “C2”, “C3”, “C4” or “C5” may be in the form of a skin care product, in particular non-coloured, such as a care cream or a care fluid.

• soit d’un produit coloré pour les lèvres ; ou
• soit d’un produit de soin de la peau, éventuellement coloré, en particulier une crème ou un fluide présentant des propriétés hydratantes et/ou de comblement et/ou à effet tenseur.

According to a particular embodiment, a composition “C1”, “C2”, “C3”, “C4” or “C5” is in the form:

• either a colored lip product; or
• either a skin care product, possibly colored, in particular a cream or fluid with moisturizing and/or filling and/or tightening properties.

Kit

According to yet another of its aspects, the present invention also aims at a kit or device, in particular cosmetic, with several compartments comprising:

- at least one compartment containing at least i) at least one (co)polymer as defined above, ii) water, and optionally iv) at least one cosmetic active ingredient, in particular as defined above, in particular comprising the composition “C1” as defined above;

- at least one compartment distinct from that which contains i) and containing iii) at least one crosslinking agent, in particular as defined above, optionally ii) water, and optionally iv) at least one cosmetic active ingredient, in particular as defined above, in particular comprising the composition “C4” as defined above; and

- optionally, at least one compartment distinct from those which contain i) and iii), and containing iv) at least one cosmetic active ingredient, in particular as defined above, identical or different from that/those possibly contained in the compartments comprising i) and iii), preferably at least one of the compartments contains iv) at least one cosmetic active ingredient different from Rhodamine B.

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

Methods and Measures Skin application a) 1-step protocol

The polyvinyl alcohol compounds with acetoacetate functions, the crosslinking agents, and optionally the cosmetic active ingredients are mixed together using a Speed Mixer (2 minutes – 3500 r.p.m.) before application. The system remains fluid long enough to allow application to the substrate.

The compositions are applied to a Bioskin type vitro support from Maprecos (Bioskin plate #10) (support simulating an elastomer skin) using a film puller (wet thickness 100 µm). The deposit is left to dry for 24 hours.

After 24 hours of drying, deposit evaluations are carried out according to the protocols described below.

b) 2-step protocol

A first composition, called “base coat”, is applied to a Bioskin type vitro support from Maprecos (Bioskin plate #10) (support simulating an elastomer skin) using a film puller (wet thickness 100 µm). The deposit is left to dry for 24 hours.

After this first step, a second composition, called “top coat”, is applied in the same way.

The deposit is left to dry for 24 hours.

Deposit assessments are carried out according to the protocols described below.

Water resistance

0.5 mL of water is applied to the formulation film. After 5 minutes, the water is removed using 15 passes with a cotton pad. We thus look at the deterioration of the film following contact with the drop of aggressors.

In the case of a two-step protocol, for each association, the evaluations are conducted for the “base coat” composition alone after drying, and on the “base coat” + “top coat” composition system after drying. The objective is to observe the cosmetic properties improved by such associations.

Resistance is assessed according to the following scale:

+++: Cosmetic property rated as very high performance, no aggression of the deposit which is as originally;

++: Cosmetic property rated as average, a little transfer but the deposit is as original;

+: Cosmetic property rated as poorly performing, the deposit is slightly altered and a little transfer is noted;

0: Cosmetic property rated as non-performing, the deposit is completely degraded and there is a lot of transfer onto the cotton.

Resistance to scotch tape

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

Example 1 : Preparation d ’ a polyvinyl alcohol with acetoacetate functions

The synthesis is represented by the following preparation scheme:

113.6 g of PVA Mowiol 8-88 (marketed by Sigma Aldrich) and 400 g of DMSO are introduced into a 1 L reactor.

71.81 g (0.2 eq.) of tert-butylacetoacetate (marketed by Sigma-Aldrich) are added after solubilization of the medium.

The medium is heated to 120°C for 7 h, until a viscous yellow solution is obtained when hot.

Several precipitations in 5 liters of acetone are carried out to remove the DMSO.

The precipitate is resolubilized in water heated for 72 hours to a dry extract of 7%. The solution is then concentrated to 25% using a rotary evaporator.

Example 2: Preparation of compositions A and B

Composition A according to the invention comprising the polyvinyl alcohol compound with acetoacetate functions of example 1 and a crosslinker, and comparative composition B, comprising the polyvinyl alcohol compound with acetoacetate functions of example 1 but devoid of crosslinker, are prepared from the contents indicated in the table below. The contents are expressed as a percentage by weight, relative to the total weight of the composition.

Compositions A and B are prepared by simply mixing the ingredients detailed in Table 1 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3,500 rpm and at room temperature.

Example 3 : 1-step skin application of compositions A and B

Compositions A and B are applied according to the one-step skin application protocol described above.

The deposits are then evaluated according to the water resistance and scotch resistance protocols.

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

It appears that the application of composition A according to the process of the invention makes it possible to obtain significantly improved water persistence compared to the application of composition B.

It also appears that the application of formula A according to the invention makes it possible to obtain an improved cohesive and adherent deposit compared to the application of composition B (comparative).

Example 4: Preparation of compositions C and D

Compositions C and D are prepared from the contents indicated in the table below. The contents are expressed as a percentage by weight, relative to the total weight of the composition considered.

The “Base Coat” and “Top Coat” compositions are prepared by simply mixing the ingredients detailed in Table 3 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3,500 rpm and at room temperature.

Example 5 : Application skin in 2 stage s compositions C and D

Compositions C and D are applied according to the 2-step skin application protocol described above.

The deposits are then evaluated according to the water resistance and scotch resistance protocols.

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

It appears that the application of formula D ( base coat and top coat ) according to the process of the invention makes it possible to obtain significantly improved water resistance compared to the application of comparative composition C ( base coat only ).

It also appears that the application of formula D according to the invention makes it possible to obtain a cohesive and adherent deposit significantly improved compared to the application of composition C (comparative).

We therefore obtain, thanks to the application of formula D ( base coat and top coat ) according to the process of the invention, water-resistant deposits.

Example 6: Preparation of compositions E and F

Compositions E and F are prepared from the contents indicated in the table below. The contents are expressed as a percentage by weight, relative to the total weight of the composition considered.

The “Base Coat” and “Top Coat” compositions are prepared by simply mixing the ingredients detailed in Table 5 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3,500 rpm and at room temperature.

Example 7 : Application skin in 2 stage s compositions E and F

Compositions E and F are applied according to the 2-step skin application protocol as described previously.

The deposits are then evaluated according to the water resistance and scotch resistance protocols.

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

It appears that the application of formula F ( base coat and top coat ) according to the process of the invention makes it possible to obtain significantly improved water resistance compared to the application of composition E ( base coat only ),

It also appears that the application of formula F according to the invention makes it possible to obtain a cohesive and adherent deposit significantly improved compared to the application of composition E (comparative).

Example 8: Preparation of compositions G and H

Compositions G and H are prepared from the contents indicated in the table below. The contents are expressed as a percentage by weight, relative to the total weight of the composition considered.

The “Base Coat” and “Top Coat” compositions are prepared by simply mixing the ingredients detailed in Table 7 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3,500 rpm and at room temperature.

Example 9 : Application skin in 2 stage s compositions G and H

Compositions G and H are applied according to the 2-step skin application protocol described above.

The deposits are then evaluated according to the water resistance and scotch resistance protocols.

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

It appears that the application of formula H ( base coat and top coat ) according to the process of the invention makes it possible to obtain significantly improved water resistance compared to the application of composition G ( base coat only ),

It also appears that the application of formula H according to the invention makes it possible to obtain a cohesive and adherent deposit significantly improved compared to the application of composition G (comparative).

Claims (18)

Process, in particular cosmetic, for treating keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, comprising the application to said keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows, in one or more successive steps, of at least:
(i) one or more (co)polymers having at least one unit of formula (I), as well as its optical, geometric and/or solvated isomers, such as hydrates, or a composition containing it or them:
(I)
formula (I) in which:
- R ^a represents a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^a represents a hydrogen atom,
- R ^b and R ^c , identical or different, represent a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^b and R ^c represent a hydrogen atom,
- R ^d represents a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^d represents a methyl group,
- p is an integer greater than or equal to 2,
and optionally at least one motif of formula (II):
(II)
formula (II) in which:
- q represents an integer greater than or equal to 2, and
- R ^a represents a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^a represents a hydrogen atom;
and optionally at least one motif of formula (III):
(III)
formula (III) in which:
- t represents an integer greater than or equal to 2, and
- R represents a hydrocarbon chain, cyclic or acyclic, linear or branched, saturated or unsaturated, aromatic or not, comprising from 1 to 10 carbon atoms, preferably R represents a (C ₁ -C ₆ )alkyl group, in particular methyl;
- R ^a represents a hydrogen atom or a linear or branched (C ₁ -C ₄ )alkyl group, preferably R ^a represents a hydrogen atom; and
(ii) water;
(iii) one or more crosslinking agent(s); and
iv) optionally one or more cosmetic active ingredients chosen from a) coloring materials other than rhodamine B, b) active ingredients for caring for keratin materials, c) UV filters, and d) their mixtures. Treatment method according to the preceding claim, in which the (co)polymer(s) comprise at least one unit of formula (I) and at least one unit of formula (II), or at least one unit of formula (I) and at least one unit of formula (III). Treatment method according to any one of the preceding claims, in which the (co)polymer(s) comprise at least one unit of formula (I), at least one unit of formula (II) and at least one unit of formula (III). A treatment method according to any preceding claim, wherein the (co)polymers comprise:
- from 1% to 25% by mole of units of formula (I),
- from 49% to 99% by mole of units of formula (II),
- from 0% to 26% by mole of units of formula (III). Treatment method according to any one of the preceding claims, in which the (co)polymer(s) are present in a composition in a content ranging from 0.001% to 50% by weight, preferably from 0.01% to 30% by weight, and more preferably from 0.1% to 25% by weight, relative to the total weight of said composition. Treatment method according to any one of the preceding claims, in which the crosslinking agent(s) iii) is (are) chosen from (poly)amine, (poly)thiolated, (poly)carbonyl, (poly)acrylate compounds, and their mixtures, preferably chosen from (poly)amine, (poly)thiolated and (poly)acrylate compounds and their mixtures, and more preferably chosen from (poly)amine, (poly)thiolated compounds and their mixtures, and more preferably chosen from (poly)amine compounds. Treatment method according to any one of the preceding claims, in which the crosslinking agent(s) iii) is (are) chosen from:
A) (poly)amino compounds chosen from:
ia) chitosans such as poly(D-Glucosamine),
ib) polydialkylsiloxanes comprising primary amine groups at the chain end or on side chains, in particular polydimethylsiloxanes comprising primary amine groups, more particularly poly(dimethoxysiloxane) terminated with bis(3-aminopropyl) (PDMS-diNH₂) and amodimethicones comprising amine groups on side chains, more particularly bis-cetearyl amodimethicone;
B) (poly)thiolated compounds chosen from:
(iia) polydialkylsiloxanes with thiol functions, and
(iib) alkoxysilanes with thiol functions,
and in particular chosen from compounds iia) polydialkylsiloxanes with thiol functions, preferably from polydimethylsiloxanes comprising thiol groups on the side chain, in particular mercaptopropyl, and more particularly chosen from compounds of formula (XIII):
R^has-If(R^b)(R^d)-O-[Si(R^has)(R^b)-O]_m-[If(R^b)(ALK₁-SH)-O]_n-If(R^b)(R^d)-R^has(XIII)
formula (XIII) in which:
- R^hasand R^b, identical or different, preferably identical, represent a group (C₁-C₄)alkyl, in particular methyl, a group (C₁-C₄)alkoxy, in particular methoxy, an aryl group, in particular phenyl, an aryloxy group, in particular phenoxy, an aryl group(C₁-C₄)alkyl, in particular benzyl, or an aryl group(C₁-C₄)alkoxy, in particular benzoxy, and preferably a group (C₁-C₄)alkyl, more preferably methyl,
- R^drepresents a group (C₁-C₄)alkyl, in particular methyl, a group (C₁-C₄)alkoxy, in particular methoxy, an aryl group, in particular phenyl, an aryloxy group, in particular phenoxy, an aryl group(C₁-C₄)alkyl, in particular benzyl, an aryl group(C₁-C₄)alkoxy, especially benzoxy, or a group (C₁-C₆)alkyl substituted by a group (C₁-C₄)alkylamino, amino, or thiol, and preferably a group (C₁-C₄)alkyl, more preferably methyl,
and preferably R^has, R^b, and R^d, are identical and represent a group (C₁-C₆)alkyl, more preferably methyl,
- ALK₁represents a divalent 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, a (thio)carbonyl group C(X) with X representing O or S, or their combinations, in particular -O-, -O-C(O)- or -C(O)-O-, preferably ALK₁represents a group (C₁-C₆)alkylene, more preferably (C₁-C₄)alkylene, even more preferably propylene,
- n and m, identical or different, represent an integer greater than 2, and in particular the values of m and n are such that the weight average molecular weight of said polyorganosiloxane is between 1000 and 55000 g.mol^-1 ; And
C) (poly)acrylate compounds of formula (XIV):
L[-Y-C(O)-C(R^e)=CH₂]_q(XIV)
formula (XIV) in which:
- q represents an integer greater than or equal to 2, in particular n is inclusively between 2 and 10, and preferably between 2 and 5,
- L denotes an at least divalent multivalent group, in particular comprising between 1 and 500 carbon and/or silicon atoms, more particularly between 2 and 40 carbon and/or silicon atoms, even more particularly between 3 and 30 carbon and/or silicon atoms, preferably between 6 and 20 carbon atoms, linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated; L being optionally interrupted and/or terminated by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their combinations, in particular -O-, -O-C(X)-, -N(R)-C(X)-, -Si(R_c)(R_d)-O- with R representing a hydrogen atom or a group (C₁-C₆)alkyl, in particular methyl; and/or L being optionally substituted by one or more groups chosen from: -N(R_has)R_b, and -(X’)_has-C(X)-(X’’)_b-R_has, with X, X’ and X’’, identical or different, representing an oxygen atom, sulfur atom, or an N(R) group_b), a and b being 0 or 1, preferably the sum of a and b being 1, R_hasand R_b, identical or different, representing a hydrogen atom, a group (C₁-C₆)alkyl, or an aryl group(C₁-C₄)alkyl, in particular benzyl, preferably R_hasand R_brepresent a hydrogen atom, and R_cand R_d, identical or different, represent a group (C₁-C₆)alkyl, aryl(C₁-C₄)alkyl or (C₁-C₆)alkoxy,
- R^erepresents a hydrogen atom or a group (C₁-C₄)alkyl, in particular methyl, preferably R^erepresents a hydrogen atom, and
- Y represents an oxygen atom or an amino group -N(H)-, preferably an oxygen atom,
preferably Y is an oxygen atom and R^eis a hydrogen atom, preferably L represents a di or trivalent, preferably trivalent, hydrocarbon chain comprising from 1 to 8 carbon atoms, q is 2 or 3, preferably 3, and
more preferably the compounds of formula (XIV) are trimethylolpropane triacrylate. Treatment method according to any one of the preceding claims, in which iv) at least one cosmetic active ingredient is additionally applied to keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows. Treatment method according to the preceding claim, in which the cosmetic agent(s) iv) are chosen from:
(a) colouring matters other than Rhodamine B, in particular chosen from pigments, direct dyes, anionic, cationic, zwitterionic or neutral, non-fluorescent or fluorescent, but other than Rhodamine B, and mixtures thereof,
b) active ingredients for the care of keratin materials, preferably skin,
c) UV filters, and
(d) their mixtures;
preferably the cosmetic agent(s) iv) are chosen from a) coloring materials other than Rhodamine B, preferably chosen from pigments, direct dyes, anionic, cationic, zwitterionic or neutral, non-fluorescent or fluorescent, but different from Rhodamine B, and mixtures thereof, more preferably the pigment(s) are chosen from carbon black, iron oxides, in particular yellow, red and black and micas coated with iron oxide, triarylmethane pigments, in particular blue and violet, in particular BLUE 1 LAKE, azo pigments, in particular red, more particularly D&C RED 7, the alkali metal salt of lithol red, in particular the calcium salt of lithol red B, and even more preferably from red iron oxides, yellow iron oxides and azo pigments, in particular red, more especially the D&C RED 7. Treatment method according to any one of the preceding claims, in which v) at least one fatty substance, in particular at least one oil, preferably at least one volatile oil, is additionally used. Treatment method according to the preceding claim, in which v) at least one fatty substance chosen from volatile oils chosen from:
- hydrocarbon oils having from 8 to 16 carbon atoms, in particular branched C ₈ -C ₁₆ alkanes, in particular isoalkanes, more particularly isoalkanes (also called isoparaffins), preferably C ₁₃ -C ₁₆ Isoparaffin, isododecane, isodecane, isohexadecane, for example oils sold under the trade names Isopars or Permetyls, alone or in mixtures, preferably isododecane (also called 2,2,4,4,6-pentamethylheptane), linear alkanes, in particular C ₁₁ -C ₁₆ , alone or in mixtures, in particular hexane, decane, undecane, tridecane, isoparaffins in particular n-dodecane (C ₁₂ ) and n-tetradecane (C ₁₄ ), the undecane-tridecane mixture, mixtures of n-undecane (C ₁₁ ) and n-tridecane (C ₁₃ ), and mixtures thereof as well as mixtures of n -undecane (C ₁₁ ) and n -tridecane (C ₁₃ ), and volatile non-aromatic cyclic C ₅ -C ₁₂ alkanes;
- short-chain esters having 3 to 8 carbon atoms in total, in particular ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate;
- carbonate hydrocarbon oils of structure R' ₁ -OC(O)-O-R' ₂ in which R' ₁ and R' ₂ independently denote a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably a C ₄ -C ₈ alkyl group, advantageously, more preferentially chosen from dibutylcarbonate or dipentylcarbonate;
- ether oils of formula R ₁ -OR ₂ , in which R ₁ and R ₂ denote, independently of one another, a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably a C ₄ -C ₈ alkyl group;
- silicone oils, in particular comprising from 2 to 7 silicon atoms, and optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms, in particular dimethicones with a viscosity of 5 and 6 cSt, cyclopentadimethylsiloxane, dodecamethylpentasiloxane, cyclohexadimethylsiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof;
more preferably the volatile oil(s) v) are chosen from C ₈ -C ₁₆ alkanes, in particular branched, preferably isododecane. Process for the treatment, in particular cosmetic, of keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, according to any one of the preceding claims, for the care and/or makeup of keratin materials, in particular the skin, the lips, the eyelashes and/or the eyebrows, comprising the application to the keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows of at least:
- a composition, called “C1”, comprising i) at least one (co)polymer according to any one of claims 1 to 5 and ii) water, and optionally iv) at least one cosmetic active ingredient, in particular according to claim 9;
- a composition, called “C2”, comprising i) at least one (co)polymer according to any one of claims 1 to 5, ii) water, iii) at least one crosslinking agent, in particular according to any one of claims 6 or 7, and optionally iv) at least one cosmetic active agent, in particular according to claim 9; preferably the composition “C2” does not comprise iv) a cosmetic active agent;
- a composition, called “C3”, comprising i) at least one (co)polymer according to any one of claims 1 to 5, ii) water, iii) at least one crosslinking agent, in particular according to any one of claims 6 or 7, and iv) at least one cosmetic active agent, in particular according to claim 9;
- a composition, called “C4”, comprising iii) at least one crosslinking agent, in particular according to any one of claims 6 or 7, optionally ii) water, and optionally iv) at least one cosmetic active ingredient, in particular according to claim 9;
- a composition, called “C5”, comprising iv) at least one cosmetic active ingredient, in particular according to claim 9, and optionally ii) water; preferably the composition “C5” does not comprise i) at least one (co)polymer according to any one of claims 1 to 5 and does not comprise iii) at least one crosslinking agent;
it being understood that:

• the process uses together or separately i) at least one (co)polymer according to any one of claims 1 to 5, ii) water, and iii) at least one crosslinking agent, in particular according to any one of claims 6 or 7, and optionally iv) at least one cosmetic active ingredient, in particular according to claim 9; and
• the compositions “C1”, “C2”, “C3”, “C4” and “C5” may further comprise one or more fatty substances v), in particular according to any one of claims 10 or 11.

Treatment method according to the preceding claim, characterized in that it comprises a single step of applying the composition “C3” to said keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows. Treatment method according to claim 12, characterized in that it comprises two successive steps of application to said keratin materials, in particular the skin and/or the lips and/or the eyelashes and/or the eyebrows, of two different compositions, preferably composition “C1” then composition “C4”, preferably at least one of the compositions used comprises iv) at least one cosmetic active ingredient, in particular according to claim 9. Cosmetic treatment process for the care and/or make-up of keratin materials, in particular the skin, lips, eyelashes and/or eyebrows, comprising the successive application of at least:
- a composition, called “C1”, comprising i) at least one (co)polymer according to any one of claims 1 to 5, ii) water, and optionally iv) at least one cosmetic active ingredient, in particular according to claim 9; then
- a composition, called “C4”, comprising iii) at least one crosslinking agent, in particular according to any one of claims 6 or 7, optionally ii) water, and optionally iv) at least one cosmetic active ingredient, in particular according to claim 9;
at least one of the compositions “C1” and/or “C4” containing at least one coloring matter other than rhodamine B, in particular according to claim 9, preferably at least one pigment, and more preferably the composition “C1” comprises at least one pigment. Composition “C3” comprising i) at least one (co)polymer according to any one of claims 1 to 5, ii) water, iii) at least one crosslinking agent, in particular according to any one of claims 6 or 7, and iv) at least one cosmetic active ingredient other than Rhodamine B, in particular according to claim 9, preferably at least one coloring matter other than Rhodamine B, and more preferably at least one pigment. Cosmetic use of the composition “C3” according to claim 16, for the treatment of keratin materials, in particular the skin and/or lips and/or eyelashes and/or eyebrows. Kit, particularly cosmetic, with several compartments comprising:
- at least one compartment containing at least i) at least one (co)polymer according to any one of claims 1 to 5, ii) water, and optionally iv) at least one cosmetic active ingredient, in particular according to claim 9, in particular comprising the composition “C1” according to claim 12;
- at least one compartment distinct from that which contains i) and containing iii) at least one crosslinking agent, in particular according to any one of claims 6 or 7, optionally ii) water, and optionally iv) at least one cosmetic active ingredient, in particular according to claim 9, in particular comprising the composition “C4” according to claim 12; and
- optionally, at least one compartment distinct from those which contain i) and iii), and containing iv) at least one cosmetic active ingredient, in particular according to claim 9, identical or different from that/those possibly contained in the compartments comprising i) and iii), preferably at least one of the compartments contains iv) at least one cosmetic active ingredient different from Rhodamine B.