FR3142893A1 - Process for treating keratin materials using a compound resulting from the condensation of poly(thi)ol and acetoacetate and a crosslinking agent - Google Patents

Abstract

Title: Process for treating keratin materials using a compound resulting from the condensation of poly(thi)ol and acetoacetate, and a crosslinking agent. The present invention relates more particularly to the cosmetic field of keratin materials, and in particular to that care and/or makeup of the skin and/or lips and/or eyelashes and/or eyebrows. It thus aims to propose a process using on keratin materials in one or more steps i) at least one compound of formula (I) resulting from the condensation of poly(thi)ol and acetoacetate (ACAC) and ii) at least one crosslinking agent. The invention also relates to a composition comprising ingredients i) and ii) as well as a kit comprising i) and ii).

Description

Process for treating keratin materials using a compound resulting from the condensation of poly(thi)ol and acetoacetate and a crosslinking agent

The present invention relates more particularly to the cosmetic field of keratin materials, and in particular to that of care and/or makeup of the skin and/or lips and/or eyelashes and/or eyebrows. It thus aims to propose a process using on keratin materials in one or more steps i) at least one compound of formula (I) resulting from the condensation of poly(thi)ol and acetoacetate (ACAC) and ii) at least one crosslinking agent. The invention also relates to compositions comprising ingredients i) and ii) as well as a kit comprising i) and ii).

Cosmetic products typically 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 lip makeup, it is particularly expected that the deposit formed does not transfer upon contact with fingers or clothing.

It must also have good resistance to contact with water, in particular rain or when showering or even perspiration as well as sebum, or even in contact with fatty substances in foods including edible oils when this deposit is formed on the lips. Furthermore, 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 more particularly in their organic and notably oily phases, dispersions of polymer particles of nanometric size, as a film-forming agent. Thus, document EP 749 747 proposes to use, in hydrocarbon oils, dispersions of acrylic polymers stabilized with polystyrene/copoly(ethylene-propylene) diblock copolymers. Document FR 1 362 795 describes the use of dispersion of surface-stabilized polymer particles in hydrocarbon oils. As for document WO 2010/046229, it proposes dispersions in isododecane of acrylic polymers stabilized by stabilizing polymers.

Furthermore, document US 2006/0079599 describes a tissue adhesive based on polymers for medical use including polyvinyl alcohol polymers with ACAC groups associated with polyamines in the form of hydrogel. This document does not describe the use of poly(thi)ol ACAC associated with crosslinkers and possibly cosmetic active ingredients intended for application on keratin materials to produce a deposit on said materials, non-sticky, which transfers little, shiny, comfortable, and persistent.

There remains a need for cosmetic compositions intended for application to the skin and/or lips and/or eyelashes and/or eyebrows which make it possible to obtain a non-sticky deposit, which transfers little, if at all, gloss, comfortable, and persistent.

There also remains a need for compositions that are resistant to water and fats, in particular sebum.

There also remains a need for compositions that provide qualities of shine and transparency.

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

These problems are solved by implementing a process for treating keratin materials by applying to said materials:

i) at least one compound of formula (I) resulting from the condensation of poly(thi)ol and acetoacetate (ACAC) as well as its optical isomers, geometric isomers, its salts, and its solvates such as hydrates:

[Chem. 1]:

• R¹représente un radical polyvalent hydrocarboné en C₂à C₁₄, particulièrement en C₃à C₁₂, linéaire ou ramifié, saturé ou insaturé, conjugué ou non, acyclique ou cyclique, aromatique ou non,

R¹étant en outre :
Formula (I) in which:

• R ¹ represents a versatile hydrocarbon radical in C ₂ to C ₁₄ , particularly in C ₃ to C ₁₂ , linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not,

R ¹ being furthermore:

a) optionally substituted by one or more hydroxy OH, amine -N(R) ₂ groups with R representing a (C ₁ -C ₄ ) alkyl group such as methyl, carboxy -C(O)-OH, a vinyl group, and /Or

• R²représente un radical monovalent hydrocarboné en C₁à C₆, linéaire ou ramifié, saturé ou insaturé, de préférence un groupe (C₁-C₄)alkyle tel que méthyle outert-butyle plus préféretiellement méthyle ;
• R^a, et R^b, identiques ou différents représentent un atome d’hydrogène ou un groupe (C₁-C₄)alkyle, de préférence hydrogène ;
• X est un hétéroatome ou groupe choisi parmi O, S, N(R’) ou , -S-CH₂-C(O)-O- , -O-C(O)-CH₂-S-, -O-C(O)-N(R’)-, -N(R’)-C(O)-O-, -N(R’)-C(O)-N(R’)-, de préférence X représente O ;
• n désigne un nombre entier allant de 2 à 10, particulièrement de 3 à 8; et

ii) au moins un agent réticulant ; et
b) optionally interrupted by one or more heteroatoms or groups chosen from O, S, carbonyl -C(O)-, amine -N(R'), or their associations such as ester -C(O)-O-, -OC (O)-, amide -C(O)-N(R')-, -N(R')-C(O)-, urethane -N(R')-C(O)-O- or -OC (O)-N(R')-, urea -N(R')-(CO)-N(R')-, or carbonate -OC(O)-O-, in which R' represents an atom of hydrogen, an alkyl group having 1 to 4 carbon atoms optionally substituted by at least one hydroxyl group (OH), or optionally substituted by -XC(O)-C(R _a )(R _b )-C(O)- R ² preferably R' represents a hydrogen atom, a (C ₁ -C ₄ ) alkyl group;

• R ² represents a monovalent C ₁ to C ₆ hydrocarbon radical, linear or branched, saturated or unsaturated, preferably a (C ₁ -C ₄ ) alkyl group such as methyl or tert -butyl, more preferably methyl;
• R ^a , and R ^b , identical or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group, preferably hydrogen;
• _{- ​} -N(R')-, -N(R')-C(O)-O-, -N(R')-C(O)-N(R')-, preferably X represents O;
• n designates an integer ranging from 2 to 10, particularly from 3 to 8; And

ii) at least one crosslinking agent; And

iii) optionally at least one cosmetic active ingredient.

The inventors have thus noted, surprisingly, that the application to the keratin materials of ingredients i), ii) and possibly iii), makes it possible to provide a persistence of the keratin materials treated with this association, particularly with regard to the bodies liquid fats such as oils and water.

• Par «Actif cosmétique» : on entend un composé organique ou organosilicié, ou un composé minéral pouvant être intégré à une composition cosmétique pour apporter un effet sur les matières kératiniques, que cet effet soit immédiat ou apporté par des applications répétées. A titre d’exemples d’actif cosmétique on peut citer les composés colorés ou non, fluorescents ou non tels que les azurants optiques, ou les filtres UVA et/ou UVB, les actifs anti-âges ou destinés à apporter un bénéfice sur la peau tels que les actifs ayant une action sur la fonction barrière, les actifs déodorants, les actifs antitranspirants, les actifs desquamants, les actifs antioxydants, les actifs hydratants, les actifs régulateurs de sébum, les actifs destinés à lutter contre les effets de la pollution, les actifs antimicrobiens ou bactéricides, les parfums, et les matières colorantes telles que les colorants directs ou les pigments, de préférence les pigments.

Préférentiellement les actifs cosmétiques sont choisis parmi a) les matières colorantes choisies parmi les pigments, les colorants directs, et leurs mélanges, b) les actifs de soin des matières kératiniques, de préférence de la peau, c) les filtres UV, et d) leurs mélanges.

• Par «corps gras», on entend, au sens de la présente invention, un composé organique insoluble dans l'eau à température ordinaire (25 °C) et à pression atmosphérique (760 mm de Hg) (solubilité inférieure à 5 %, et de préférence à 1%, encore plus préférentiellement à 0,1 %) ; en outre, les corps gras sont solubles dans les solvants organiques dans les mêmes conditions de température et de pression, comme par exemple dans les solvants halogénés tel que le chloroforme, le dichlorométhane, les alcools inférieurs tels que l’éthanol ou les solvants aromatiques tels que le benzène ou le toluène.
• Par «(hétéro)aryle» on entend les groupes aryle ou hétéroaryle ;
• Par «(hétéro)cycloalkyle» on entend les groupes cycloalkyle ou hétérocycloalkyle;
• Les radicaux «aryle» ou «hétéroaryle» ou la partie aryle ou hétéroaryle d’un radical peuvent être substitués par au moins un substituant porté par un atome de carbone, choisi parmi :

• un radical (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 (-NR-COR’) dans lequel le radical R est un atome d’hydrogène,
• un radical alkyle en C₁-C₄et le radical R’ est un radical alkyle en C₁-C₄; un radical carbamoyle ((R)₂N-CO-) dans lequel les radicaux R, identiques ou non, représentent un atome d’hydrogène, un radical alkyle en C₁-C₄;
• un radical alkylsulfonylamino (R’SO₂-NR-) dans lequel le radical R représente un atome d’hydrogène, un radical alkyle en C₁-C₄et le radical R’ représente un radical alkyle en C₁-C₄, un radical phényle ;
• un radical aminosulfonyle ((R)₂N-SO₂-) dans lequel les radicaux R, identiques ou non, représentent un atome d’hydrogène, un radical alkyle en C₁-C₄;
• un radical carboxylique sous forme acide ou salifiée (de préférence avec un métal alcalin ou un ammonium, substitué ou non) ;
• un groupement cyano (CN) ;
• un groupement polyhalogéno(C₁-C₄)alkyle, préférentiellement le trifluorométhyle (CF₃) ;

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

• hydroxy,
• alcoxy en C₁-C₄, (poly)hydroxyalcoxy en C₂-C₄,
• alkylcarbonylamino ((RCO-NR’-) dans lequel le radical R’ est un atome d’hydrogène, un radical alkyle en C₁-C₄et le radical R est un radical alkyle en C₁-C₂, amino substitué par un ou deux groupements alkyle identiques ou différents en C₁-C₄;
• alkylcarbonyloxy ((RCO-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 ((RO-CO-) 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;

• un radical cyclique, hétérocyclique, ou une partie non aromatique d’un radical aryle ou hétéroaryle, peut également être substitué par un ou plusieurs groupements oxo ;
• une chaîne hydrocarbonée est insaturée lorsqu’elle comporte une ou plusieurs liaisons doubles et/ou une ou plusieurs liaisons triples ;
• un radical «aryle» représente un groupement mono ou polycyclique hydrocarboné, condensé ou non, comprenant de 6 à 14 atomes de carbone, et dont au moins un cycle est aromatique ; préférentiellement le radical aryle est un phényle, biphényle, naphtyle, indényle, anthracényle, ou tétrahydronaphtyle ;
• un radical «hétéroaryle» représente un groupement mono ou polycyclique, condensé ou non, comprenant de 5 à 14 chaînons, de 1 à 6 hétéroatomes choisis parmi l’atome d’azote, d’oxygène, de soufre et de sélénium, et dont au moins un cycle est aromatique ; préférentiellement un radical hétéroaryle est choisis parmi acridinyle, benzimidazolyle, benzobistriazolyle, benzopyrazolyle, benzopyridazinyle, benzoquinolyle, benzothiazolyle, benzotriazolyle, benzoxazolyle, pyridinyle, tetrazolyle, dihydrothiazolyle, imidazopyridinyle, imidazolyle, indolyle, isoquinolyle, naphthoimidazolyle, naphthooxazolyle, naphthopyrazolyle, oxadiazolyle, oxazolyle, oxazolopyridyle, phénazinyle, phénooxazolyle, pyrazinyle, pyrazolyle, pyrilyle, pyrazoyltriazyle, pyridyle, pyridinoimidazolyle, pyrrolyle, quinolyle, tétrazolyle, thiadiazolyle, thiazolyle, thiazolopyridinyle, thiazoylimidazolyle, thiopyrylyle, triazolyle, xanthylyle;
• un radical «cyclique» ou «cycloalkyle» est un radical hydrocarboné cyclique non aromatique, mono ou polycyclique, condensé ou non, contenant de 5 à 14 atomes de carbone, pouvant comporter de 1 à plusieurs insaturations, de préférence le cycloalkyle est un groupe cyclohexyle;
• un radical «hétérocyclique» ou «hétérocycloalkyle» est un radical cyclique non aromatique mono ou polycyclique, condensé ou non, contenant de 3 à 9 chaînons, comportant de 1 à 4 hétéroatomes choisis parmi l’atome d’azote, d’oxygène, de soufre et de sélénium, de préférence l’hétérocycloalkyle est choisi parmi epoxyde, pipérazinyl, pipéridinyl, morpholinyl, ou dithiolane ;
• un radical «alkyle» est un radical hydrocarboné saturé, linéaire ou ramifié, en particulier en en C₁-C₆, de préférence en C₁-C₄;
• un radical «alcoxy» est un radical alkyl-oxy pour lequel le radical alkyle est un radical hydrocarboné, linéaire ou ramifié, en C₁-C₆préférentiellement en C₁-C₄;
• un radical « (poly)(hydroxy)alkyle » désigne un radical alkyle en C₁-C₆, de préférence en C₁-C₄éventuellement substitué par un ou plusieurs radicaux hydroxy, de préférence substitué par de 1 à 4 groupes hydroxy, plus particulièrement entre 1 et 3 ;
• un radical «sucre», est un radical monosaccharide, ou disaccharide, ,. On peut citer comme radical sucre : le sucrose (ou saccharose), le glucose, le galactose, le ribose, le fucose, le maltose, le fructose, le mannose, l'arabinose, le xylose, ou le lactose ;
• par «monosaccharide», on entend un sucre mono-osidique comprenant au moins 5 atomes de carbone de formule C_x(H₂O)_x, avec x un entier supérieur ou égal à 5, de préférence x est supérieur ou égal à 6, en particulier x est compris inclusivement entre 5 et 7, de préférence x = 6, ils peuvent être de configuration D ou L, et d’anomère alpha ou béta, ainsi que leurs sels et leurs solvates tels que les hydrates ;
• par «disaccharide», on entend un sucre di-osidique qui est un composé constitué de deux oses liés entre eux par des liaisons O-osidiques lesdits composés étant constitués de deux monosaccharides (également appelées mono-osidiques) tels que définis précédemment lesdits unités monosaccharidique comprenant au moins 5 atomes de carbone, de préférence 6, particulièrement les unités mono-osidiques sont reliées entre elles en 1,4 ou 1,6 en anomère α (alpha) ou β(beta), chaque unité osidique pouvant être de configuration L ou D, ainsi que ses sels et ses solvates tels que les hydrates desdits monosaccharides ; il s’agit plus particulièrement de polymères formés de deux oses (ou monosaccharides) ayant pour formule générale : -[C_x(H₂O)_y)]₂- ou -[(CH₂O)_x]₂-, avec x un entier supérieur ou égal à 5, de préférence x est supérieur ou égal à 6, en particulier x est compris inclusivement entre 5 et 7, de préférence x = 6, et y un entier qui représente x - 1;
• par «polysaccharide», on entend un sucre poly-osidique qui est un polymère constitué de plusieurs oses liés entre eux par des liaisons O-osidiques lesdits polymères étant constitués d’unités monosaccharides (également appelées mono-osidiques) telles que définies précédemment lesdites unités monosaccharidique comprenant au moins 5 atomes de carbone, de préférence 6, particulièrement les unités mono-osidiques sont reliées entre elles en 1,4 ou 1,6 en anomère α (alpha) ou β(beta), chaque unité osidique pouvant être de configuration L ou D, ainsi que ses sels et ses solvates tels que les hydrates desdits monosaccharides ; il s’agit plus particulièrement de polymères formés d'un certain nombre d'oses (ou monosaccharides) ayant pour formule générale : -[C_x(H₂O)_y)]_w- ou -[(CH₂O)_x]_w-, avec x un entier supérieur ou égal à 5, de préférence x est supérieur ou égal à 6, en particulier x est compris inclusivement entre 5 et 7, de préférence x = 6, et y un entier qui représente x - 1, et w est un entier supérieur ou égal à 2, particulièrement compris inclusivement entre 3 et 3000, plus particulièrement entre 5 et 2500, préférentiellement entre 10 et 2300, particulièrement compris inclusivement entre 15 et 1000, plus particulièrement entre 20 et 500, préférentiellement entre 25 et 200 ;
• par «sel d'acide organique ou minéral», on entend plus particulièrement a) les sels d’addition avec un acide organique ou minéral en particulier choisis parmi un sel dérivé i) d’acide chlorhydrique HCl, ii) d'acide bromhydrique HBr, iii) d'acide sulfurique H₂SO₄, iv) d'acides alkylsulfoniques : Alk-S(O)₂OH tels que d'acide méthylsulfonique et d’acide éthylsulfonique ; v) d'acides arylsulfoniques : Ar-S(O)₂OH tel que d'acide benzène sulfonique et d’acide toluène sulfonique ; vi) d’acides alkoxysulfiniques : Alk-O-S(O)OH tels que d'acide méthoxysulfinique et d'acide éthoxysulfinique ; vii) d’acides aryloxysulfiniques tels que d'acide toluèneoxysulfinique et d'acide phénoxysulfinique ; viii) d'acide phosphorique H₃PO₄; ix) d'acide triflique CF₃SO₃H et x) d'acide tétrafluoroborique HBF₄; xi) d’acides organiques carboxyliques R°-C(O)-OH (I’z) formule (I’z) dans laquelle R° représente un groupe (hétéro)aryle tel que phényle, (hétéro)aryl(C₁-C₄)alkyle tel que benzyle, ou (C₁-C₁₀)alkyle ledit groupe alkyle étant éventuellement substitué de préférence par un ou plusieurs groupes hydroxy, radicaux amino, ou carboxy, R° désignant de préférence un groupe (C₁-C₆)alkyle éventuellement substitué par 1, 2 ou 3 groupes hydroxy, ou carboxy plus préférentiellement les acides de formule (I’z) monocarboxyliques sont choisis parmi choisis parmi l’acide acétique l’acide glycolique, l'acide lactique, et leurs mélanges, et plus particulièrement parmi l’acide acétique et l’acide lactique ; et les acides polycarboxyliques sont choisis parmi l’acide tartrique, l'acide succinique, l’acide fumarique, l’acide citrique et leurs mélanges ; et xii) les acides aminés comportant plus de radicaux acides carboxyliques que de groupes amino tels que l’acide gamma-carboxyglutamique, l’acide aspartique, l’acide glutamique, en particulier l’acide gamma-carboxyglutamique ; ou b) les sels d’addition avec une base organique ou minérale telle que les hydroxydes de métaux alcalins, alcalinoterreux, les carbonates de métaux alcalins ou alcalinoterreux, les bicarbonates de métaux alcalins ou alcalinoterreux, les sels d’addition avec les acides aminés dits basiques tels que l’arginine, la lysine, les sels d’addition avec des amines éventuellement hydroxylées ;
• un «contre-ion anionique» est un anion ou un groupement anionique associé à la charge cationique; plus particulièrement le contre-ion anionique est choisi parmi i) les halogénures tels que le chlorure, le bromure ; ii) les nitrates ; iii) les sulfonates parmi lesquels les C₁-C₆alkylsulfonates : Alk-S(O)₂O^-tels que le méthylsulfonate ou mésylate et l’éthylsulfonate ; iv) les arylsulfonates : Ar-S(O)₂O^-tel que le benzènesulfonate et le toluènesulfonate ou tosylate ; v) le citrate ; vi) le succinate ; vii) le tartrate ; viii) le lactate ; ix) les alkylsulfates : Alk-O-S(O)O^-tels que le méthylsulfate et l’éthylsulfate ; x) les arylsulfates : Ar-O-S(O)O^-tels que le benzènesulfate et le toluènesulfate ; xi) les alcoxysulfates : Alk-O-S(O)₂O^-tel que le méthoxy sulfate et l’éthoxysulfate ; xii) les aryloxysulfates : Ar-O-S(O)₂O^-, xiii) le phosphate ; xiv) l'acétate ; xv) le triflate ; et xvi) les borates tels que le tétrafluoroborate.
• Les «solvates» représentent les hydrates ainsi que l’association avec des alcools linéaires ou ramifiés en C₁-C₄linéaire ou ramifié tels que l’éthanol, l’isopropanol, le n-propanol ;
• Par «chromophore» on entend un radical issu d’un composé incolore ou coloré capable d’absorber dans le rayonnement UV et/ou visible à une longueur d’onde λ_abscomprise entre 250 et 800 nm ; De préférence le chromophore est coloré i.e. qu’il absorbe les longueurs d’onde dans le visible i.e. de préférence entre 400 et 800 nm. De préférence les chromophores apparaissent colorés à l’œil; particulièrement entre 400 et 700 nm (Ullmann’s Encyclopedia, 2005, Wiley-VcH, Verlag « Dyes, General Survey », § 2.1 Basic Principle of Color) ;
• Par «filtre UV-A» on entend un chromophore issu de composé qui filtre (ou absorbe) les rayons ultraviolets UV-A à une longueur d’onde comprise entre 320 et 400 nm. On peut distinguer les filtres UV-A courts (absorbant les rayons à une longueur d’onde comprise entre 320 et 340 nm), les filtres UV-A longs (absorbant les rayons à une longueur d’onde entre 340 et 400 nm).
• Par« filtre UV-B» on entend un chromophore issu de composé qui filtre (ou absorbe) les rayons ultraviolets UV-B à une longueur d’onde comprise entre 280 et 320 nm.
• Par «anhydre» on entend une quantité inférieure à 5 % en poids d’eau, préférentiellement inférieure à 3 % en poids d’eau, mieux inférieure à 1 % en poids d’eau, par rapport au poids total de la composition en question C1, C2, C3 ou C4 encore plus préférentiellement la composition est exempte d’eau.
• Les termes « agent colorant » et matière colorante » sont équivalents ;

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

• By “ Cosmetic Active ”: we mean an organic or organosilicon compound, or a mineral compound that can be integrated into a cosmetic composition to provide an effect on keratin materials, whether this effect is immediate or provided by repeated applications. As examples of cosmetic active ingredients, we can cite compounds that are colored or not, fluorescent or not, such as optical brighteners, or UVA and/or UVB filters, anti-aging active ingredients or those 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, and coloring materials such as direct dyes or pigments, preferably pigments.

Preferably the cosmetic active ingredients are chosen from a) coloring materials chosen from pigments, direct dyes, and mixtures thereof, b) active ingredients for the care of keratin materials, preferably the skin, c) UV filters, and d) their mixtures.

• By “ fatty substance ” is meant, for the purposes of the present invention, an organic compound insoluble in water at ordinary temperature (25°C) and at atmospheric pressure (760 mm Hg) (solubility less than 5%, and preferably at 1%, even more preferably at 0.1%); in addition, fatty substances are soluble in organic solvents under the same conditions of temperature and pressure, such as for example in halogenated solvents such as chloroform, dichloromethane, lower alcohols such as ethanol or aromatic solvents such as than benzene or toluene.
• By “ (hetero)aryl ” we mean the aryl or heteroaryl groups;
• By “ (hetero)cycloalkyl ” is meant cycloalkyl or heterocycloalkyl groups;
• The “ aryl ” or “ heteroaryl ” radicals or the aryl or heteroaryl part of a radical can be substituted by at least one substituent carried by a carbon atom, chosen from:

• a (poly)(hydroxy)alkyl radical, C ₁ -C ₆ , 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 (poly)-hydroxyalkoxy C ₂ -C ₄ 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 (-NR-COR') 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 N-CO-) in which the R radicals, identical or not, represent a hydrogen atom, a C ₁ -C ₄ alkyl radical;
• an alkylsulfonylamino radical (R'SO ₂ -NR-) in which the radical R represents a hydrogen atom, a C ₁ -C ₄ alkyl radical and the radical R' represents a C ₁ -C ₄ alkyl radical, a phenyl radical;
• an aminosulfonyl radical ((R) ₂ N-SO ₂ -) in which the R radicals, identical or not, represent a hydrogen atom, a C ₁ -C ₄ alkyl radical;
• a carboxylic radical in acidic 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 );

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

• hydroxy,
• C ₁ -C ₄ alkoxy, (poly)hydroxyC ₂ -C ₄ alkoxy,
• alkylcarbonylamino ((RCO-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 a or two identical or different C ₁ -C ₄ alkyl groups;
• alkylcarbonyloxy ((RCO-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;
• alkkoxycarbonyl ((RO-CO-) 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;

• 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 phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl;
• a “ heteroaryl ” radical represents a mono or polycyclic group, condensed or not, comprising from 5 to 14 members, from 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, and of which at least the less aromatic a ring is; preferably a heteroaryl radical is chosen from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridinyl, tetrazolyl, dihydrothiazolyl, imidazopyridinyl, imidazolyl, isoquinolyl, , naphthoimidazolyl, naphthooxazolyl, naphthopyrazolyl, oxadiazolyl, oxazolyl, oxazolopyridyl , phenazinyl, phenooxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, the;
• a “ cyclic ” or “ cycloalkyl ” radical is a non-aromatic cyclic hydrocarbon radical, mono or polycyclic, condensed or not, 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 atom of nitrogen, oxygen, sulfur and selenium, preferably the heterocycloalkyl is chosen from epoxide, piperazinyl, piperidinyl, morpholinyl, or dithiolane;
• an “ alkyl ” radical is a saturated hydrocarbon radical, linear or branched, in particular in C ₁ -C ₆ , preferably in 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 “(poly)(hydroxy)alkyl” radical designates a C ₁ -C ₆ alkyl radical, preferably C ₁ -C ₄ alkyl 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. We can cite as sugar radical: sucrose (or sucrose), 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 = 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-saccharide sugar which is a compound consisting of two oses linked together by O-saccharide bonds, said compounds being made up of two monosaccharides (also called mono-saccharides) as defined above, said monosaccharide units comprising at least 5 carbon atoms, preferably 6, particularly the mono-saccharide units are linked together at 1.4 or 1.6 in an α (alpha) or β(beta) anomer, each saccharide unit being able to be of configuration L or D, as well as its salts and 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 = 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-saccharide bonds, said polymers being made up of monosaccharide units (also called monosaccharides) as defined above, said units monosaccharide comprising at least 5 carbon atoms, preferably 6, particularly the monosaccharide units are linked together at 1.4 or 1.6 in an α (alpha) or β(beta) anomer, each saccharide unit being able to be of L or D configuration, as well as its salts and 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 = 6, and y an integer which represents x - 1, and w is an integer greater than or equal to 2, particularly included inclusively between 3 and 3000, more particularly between 5 and 2500, preferably between 10 and 2300, particularly included inclusively between 15 and 1000, more particularly between 20 and 500, preferably between 25 and 200;
• by “ organic or mineral acid salt ”, we mean more particularly a) the addition salts with an organic or mineral acid in particular chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr , iii) sulfuric acid H ₂ SO ₄ , iv) alkylsulfonic acids: Alk-S(O) ₂ OH such as methylsulfonic acid and ethylsulfonic acid; v) arylsulfonic acids: Ar-S(O) ₂ OH such as benzene sulfonic acid and toluene sulfonic acid; vi) alkoxysulfinic acids: Alk-OS(O)OH such as methoxysulfinic acid and ethoxysulfinic acid; vii) aryloxysulfinic acids such as tolueneoxysulfinic acid and phenoxysulfinic acid; viii) phosphoric acid H ₃ PO ₄ ; ix) triflic acid CF ₃ SO ₃ H and x) tetrafluoroboric acid HBF ₄ ; xi) organic carboxylic acids R°-C(O)-OH (I'z) formula (I'z) in which R° represents a (hetero)aryl group such as phenyl, (hetero)aryl(C ₁ - C ₄ ) alkyl such as benzyl, or (C ₁ -C ₁₀ ) alkyl said alkyl group being optionally substituted preferably by one or more hydroxy groups, amino radicals, or carboxy, R° preferably designating a group (C ₁ -C ₆ ) alkyl optionally substituted by 1, 2 or 3 hydroxy, or carboxy groups, more preferably the monocarboxylic acids of formula (I'z) are chosen from acetic acid, glycolic acid, lactic acid, and mixtures thereof , and more particularly among acetic acid and lactic acid; and the polycarboxylic acids are chosen from tartaric acid, succinic acid, fumaric acid, citric acid and mixtures thereof; and xii) amino acids containing more carboxylic acid radicals than amino groups such as gamma-carboxyglutamic acid, aspartic acid, glutamic acid, in particular gamma-carboxyglutamic acid; or b) addition salts with an organic or mineral base such as hydroxides of alkali or alkaline earth metals, carbonates of alkali or alkaline earth metals, bicarbonates of alkali or alkaline earth metals, addition salts with the so-called amino acids basic such as arginine, lysine, addition salts with optionally hydroxylated amines;
• 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 including C₁-VS₆alkylsulfonates: 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) alkyl sulfates: Alk-O-S(O)O^-such as methyl sulfate and ethyl sulfate; x) arylsulfates: Ar-O-S(O)O^-such as benzenesulfate and toluenesulfate; 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.
• The “ solvates ” represent the hydrates as well as the association with linear or branched linear or branched C ₁ -C ₄ alcohols such as ethanol, isopropanol, n-propanol;
• By “ chromophore ” is meant a radical originating from a colorless or colored compound capable of absorbing UV and/or visible radiation at a wavelength λ _abs of between 250 and 800 nm; Preferably the chromophore is colored ie it absorbs wavelengths in the visible ie preferably between 400 and 800 nm. Preferably 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 “ UV-A filter ” we mean a chromophore derived from a compound which filters (or absorbs) UV-A ultraviolet rays at a wavelength between 320 and 400 nm. We can distinguish 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 “ anhydrous ” we mean a quantity 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. C1, C2, C3 or C4, even more preferably the composition is free of water.
• The terms “coloring agent” and coloring matter” are equivalent;

Unless otherwise indicated, the limits delimiting the extent of a range of values are included in this range of values.

Unless otherwise indicated, the quantities indicated are expressed as a mass percentage.

Process for treating keratin materials

The first object of the invention is a process in one or more stages using on keratin materials, in particular the skin:

i) at least one compound of formula (I) as defined above and below;

ii) at least one crosslinking agent as defined below; And

iii) optionally at least one cosmetic active ingredient as defined above.

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

According to another particular embodiment of the invention, the process comprises at least 2 steps in which the ingredients i), and ii) and optionally iii), (the latter ingredient being able to be found together with the ingredient i) and/or with ingredient(s) ii)) are applied in separate, successive steps to the keratin materials.

According to a particular embodiment, the ingredient(s) i) are applied to the keratin materials, then the ingredient(s) ii) are applied to the keratin materials, it being understood that the ingredient(s) iii) when present can be applied together with i) and/or ii).

According to another particular embodiment, the ingredient(s) ii) are applied to the keratin materials, then the ingredient(s) i) are applied to the keratin materials, it being understood that the ingredient(s) iii) when present can be find applied together with i) and/or ii).

According to a particular embodiment of the invention, the process for treating keratin materials is a process for making up the skin, lips, eyelashes and/or eyebrows, preferably making up the skin and lips.

According to another embodiment of the invention, the process for treating keratin materials is a skin care process.

According to one aspect of the invention, the process for treating keratin materials of the invention using ingredients i), ii) and optionally iii), is a treatment for skin care.

According to another aspect of the invention, the process for treating keratin materials of the invention using ingredients i), ii) and optionally iii), is a process for making up the skin, lips, eyelashes and /or eyebrows.

• une composition, dite « C1 », comprenant i) au moins un composé de formule (I) ou (Ia) tel que défini précédemment et ci après et éventuellement iii) au moins un actif cosmétique tel que défini précédemment et ci après ; de préférence la composition C1 ne comprend pas d’agent réticulant ;
• une composition, dite « C2 », comprenant i) au moins un composé de formule (I) ou (Ia) tel que défini précédemment et ci après et ii) au moins un agent réticulant tel que défini ci après et éventuellement iii) au moins un actif cosmétique tel que défini précédemment précédemment et ci après ;
• une composition, dite « C3 », comprenant i) au moins un composé de formule (I) ou (Ia) tel que défini précédemment et ci-après, ii) au moins un agent réticulant tel que défini ci après et iii) au moins un actif cosmétique tel que défini précédemment ; et/ou
• une composition « C4 » comprenant ii) au moins agent réticulant tel que défini ci après et éventuellement iii) au moins un actif cosmétique tel que défini précédemment et ci après ; de préférence la composition C4 ne comprend pas de composé de formule (I) ou (Ia) ;
• une composition « C5 » comprenant iii) au moins un actif cosmétique tel que défini précédemment et ci après ; de préférence la composition C5 ne comprend pas i) de composé de formule (I) ni ii) d’agent réticulant tel que défini ci-après ;

étant entendu que :

• le procédé met en œuvre ensemble ou séparément i) au moins un composé de formule (I) ou (Ia) tel que défini précédemment et ci-après et ii) au moins un agent réticulant tel que défini ci-après; et
• les compositions C1, C2, C3, C4 et C5 peuvent être anhydres, aqueuses telles qu’ hydroalcooliques et/ou comprendre un ou plusieurs corps gras iv) notamment une ou plusieurs huiles de préférence volatiles tels que définies ci après.

According to one embodiment of the invention, the process for treating keratin materials involves:

• a composition, called “C1”, comprising i) at least one compound of formula (I) or (Ia) as defined above and below and optionally iii) at least one cosmetic active ingredient as defined above and below; preferably composition C1 does not comprise a crosslinking agent;
• a composition, called “C2”, comprising i) at least one compound of formula (I) or (Ia) as defined above and below and ii) at least one crosslinking agent as defined below and optionally iii) at least a cosmetic active ingredient as defined above and below;
• a composition, called “C3”, comprising i) at least one compound of formula (I) or (Ia) as defined above and below, ii) at least one crosslinking agent as defined below and iii) at least a cosmetic active ingredient as defined above; and or
• a “C4” composition comprising ii) at least one crosslinking agent as defined below and optionally iii) at least one cosmetic active ingredient as defined above and below; preferably composition C4 does not comprise a compound of formula (I) or (Ia);
• a “C5” composition comprising iii) at least one cosmetic active ingredient as defined above and below; preferably composition C5 does not comprise i) a compound of formula (I) nor ii) a crosslinking agent as defined below;

Being heard that :

• the process uses together or separately i) at least one compound of formula (I) or (Ia) as defined above and below and ii) at least one crosslinking agent as defined below; And
• the compositions C1, C2, C3, C4 and C5 may be anhydrous, aqueous such as hydroalcoholic and/or comprise one or more fatty substances iv) in particular one or more preferably volatile oils as defined below.

According to one aspect of the invention, the process for treating keratin materials and in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows of the invention uses a composition, called “C1”, comprising i) as defined above and below and optionally iii) at least one cosmetic active ingredient as defined below, in particular chosen from a) coloring agents such as pigments, direct dyes, and mixtures thereof , b) active ingredients for the care of keratin materials, preferably the skin, c) UV filters, and d) their mixtures, and in particular at least one coloring agent, more particularly at least one pigment.

According to another aspect, the process for treating keratin materials and in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows of the invention uses a composition, called “C2 », comprising i) at least one compound of formula (I) as defined above and below and ii) at least one crosslinking agent as defined below and optionally iii) at least one cosmetic active ingredient as defined above.

According to another aspect, the process for treating keratin materials and in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows of the invention uses a composition, called “C3 », comprising i) at least one compound of formula (I) as defined above and below, ii) at least one crosslinking agent as defined below and iii) at least one cosmetic active ingredient as defined above.

According to another aspect, the process for treating keratin materials and in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows of the invention uses a composition called “C1” and a composition called “C4”, said composition “C1” comprising i) at least one compound of formula (I) as defined above and below and optionally iii) at least one cosmetic active ingredient as defined above, and said composition “ C4” comprising ii) at least one crosslinking agent as defined below and optionally iii) at least one cosmetic active ingredient as defined above.

According to another variant of the process of the invention, the ingredient(s) i) and optionally iii) are applied together (ie simultaneously) to the keratin materials during a ^first step, then during a subsequent step the ingredient(s). ii) and optionally iii) are applied to said materials. According to a particular embodiment of the process during the ^1st step, the composition “C1” is applied to the keratin materials, then a composition “C4” comprising ii) at least crosslinking agent and optionally iii) at least one cosmetic active ingredient such as defined previously is applied to said materials.

According to yet another variant of the process of the invention, the ingredient(s) ii) and optionally iii) is(are) applied to the keratin materials, then the ingredient(s) i) and optionally iii) at least one cosmetic active ingredient as defined above are applied to said materials. Particularly, composition C4 is applied to keratin materials then composition C1 is applied.

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

The compositions C1, C2, C3, C4 and/or C5 of the process according to the invention can therefore be applied directly as such to the target keratin materials or even be formed there directly on the surface of these keratin materials.

According to the invention, there are thus 3 implementation modes known as “1 gesture application mode”, “2 gesture application mode” and “3 gesture application mode”.

According to one embodiment of the process of the invention, the process is carried out in one step by application to the keratin materials of composition C2 or C3 as defined above.

By “1-step application mode” is meant the direct application to the target keratin materials of a single composition conforming to the invention, namely composition C2 or C3.

After application of composition C2 or C3, a residual and non-sticky deposit is advantageously obtained. The deposit obtained is also resistant to edible oils, water, sebum, and friction.

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

The term “2-step application mode” means the successive application, to the target keratin material, of two different compositions, for example C1 and C4, or C2 and C4, or C3 and C4. Preferably C1 then C4, C2 then C4, or C3 then C4.

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

By “3 gesture application mode” we mean the sequential application of 3 distinct compositions C1 to C5. According to this mode of application, we carry out for example, according to one embodiment the successive application on the keratin materials, α) of a composition C1, then β) of a composition C4, then γ) of a composition C5, preferably C1 then C4 respectively C5 or C5 respectively C4. According to another option, the sequential application to keratin materials, α) of a composition for example C4, and β) of a composition C1 or C2, and again γ) of a composition C5, preferably the composition C4 is applied before composition C1.

In the 2 or 3-step application modes, the composition applied first, for example C1, is conventionally referred to as a “base coat” and the composition(s) which are superimposed on it, generally referred to as a “top coat”.

After application of the different compositions C1 to C5, a residual and non-sticky deposit is advantageously obtained. The deposit obtained is also resistant to edible oils, water and shampoos.

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

According to a particular embodiment, the keratin materials are dried after application of compositions C1 to C5, in particular after application of each different composition.

According to one aspect, the present invention relates to a method of making up the skin, in particular the lips, eyelashes, eyebrows, comprising a step of applying to the skin or said lips or the eyelashes or eyebrows, a composition C2 or C3, in particular containing at least one coloring material as defined above and more particularly at least one pigment.

According to another of its aspects, the present invention relates to a process for making up keratin materials, in particular the skin, in particular the lips, eyelashes or eyebrows, comprising at least the sequential application:

- a composition C1 as defined above; Then
- a C4 composition as defined above;

it being understood that compositions C1 and/or C4 contain at least one coloring material as defined below, preferably at least one pigment. Preferably composition C1 comprises at least one pigment.

According to another of its aspects, the present invention relates to a process for making up keratin materials, in particular the skin, in particular the lips, eyelashes or eyebrows, comprising at least the sequential application:

- a composition C1 as defined above; Then
- a C4 composition as defined above; Then

- a C5 composition as defined above;

it being understood that the compositions C1 and/or C4 and/or C5 contain at least one coloring material as defined below, preferably at least one pigment. Preferably composition C5 comprises at least one pigment.

• d’une composition C2 ou C3 telle que définie précédemment ; et
• d’une composition C4 telle que définie précédemment ;

étant entendu que les compositions C2 ou C3 contiennent au moins iii) une matière colorante telle que telle que définie ci après, et/ou la composition C4 contient au moins une matière colorante telle que définie ci après, de préférence la composition C2 ou C3 comprend au moins un pigment.According to another of its aspects, the present invention relates to a process for making up keratin materials, in particular the skin, in particular the lips, eyelashes or eyebrows, comprising at least the sequential application:

• a composition C2 or C3 as defined above; And
• a C4 composition as defined above;

it being understood that compositions C2 or C3 contain at least iii) a coloring material as defined below, and/or composition C4 contains at least one coloring material as defined below, preferably composition C2 or C3 comprises at least one pigment.

i) Compound of formula (I)

The first ingredient(s) i) of the process of the invention is(are) chosen from the compounds of formula (I) as defined above.

According to a particular embodiment of the invention, the ingredient(s) i) is(are) chosen from those of formula (Ia) as well as their optical isomers, geometric isomers, their salts, and their solvates such as hydrates:

[Chem. 2]:

(Ia)

• R¹est tel que défini précédemment, particulièrement représente un radical polyvalent hydrocarboné en C₂à C₁₄, de particulièrement en en C₃-C₁₂, de préférence en C₄-C₁₀, linéaire ou ramifié, saturé ou insaturé, conjugué ou non, acyclique ou cyclique, aromatique ou non, R¹étant en outre :

a) éventuellement substitué par un ou plusieurs groupes hydroxy OH, et/ou
Formula (Ia) in which:

• R ¹ is as defined above, particularly represents a versatile hydrocarbon radical in C ₂ to C ₁₄ , particularly in C ₃ -C ₁₂ , preferably in C ₄ -C ₁₀ , linear or branched, saturated or unsaturated, conjugated or no, acyclic or cyclic, aromatic or not, R ¹ being in addition:

a) optionally substituted by one or more hydroxy OH groups, and/or

• R²est tel que défini précédemment, de préférence R²représente un groupe (C₁-C₆)alkyle, linéaire ou ramifié, de préférence un groupe (C₁-C₄)alkyle tel que méthyle ou t-Butyle de préférence méthyle; et
• n étant tel que défini précédemment, de préférence n désigne un nombre entier allant de 2 à 8.

b) optionally interrupted by one or more heteroatoms or groups chosen from O, S, -N(R'), preferably interrupted by one or more oxygen atoms, in which R' is as defined in formula (I) ;

• R ² is as defined above, preferably R ² represents a (C ₁ -C ₆ ) alkyl group, linear or branched, preferably a (C ₁ -C ₄ ) alkyl group such as methyl or t-Butyl, preferably methyl ; And
• n being as defined above, preferably n designates an integer ranging from 2 to 8.

According to one embodiment, the compounds of formula (I) and (Ia) are such that R ¹ represents a versatile C ₆ to C ₈ hydrocarbon radical, linear or branched, unsaturated monocyclic or bicyclic, preferably monocyclic, and aromatic such as phenyl.

According to another embodiment, the compounds of formula (I) and (Ia) are such that R ¹ represents a versatile C ₅ to C ₁₂ hydrocarbon radical, saturated monocyclic or bicyclic, optionally interrupted by one or more heteroatoms one or more heteroatoms or groups chosen from O, S, -N(R')-, in which R' represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, preferably interrupted by one or more oxygen atoms . Preferably R ¹ represents a mono-saccharide or polysaccharide unit, in particular disaccharide on which n hydroxy groups have been substituted by n groups -OC(O)-CH ₂ -C(O)-R ² with R ² as defined previously and n as defined previously.

Suitable monosaccharides according to the invention include, but are not limited to, ribose, glucose, mannose, galactose, fructose, sorbose.

According to one embodiment the disaccharides are chosen from cellobiose, maltose, lactose, raffinose, sucrose, trehalose, melibiulose, melibiose, mannobiose, kojibiose, nigerose, isomaltose, rutinose, rutinulose, xylobiose

According to another preferred embodiment of the invention, the compounds of formula (I) and (Ia) are such that R ¹ represents a polyvalent acyclic hydrocarbon radical in C ₂ to C ₁₂ , preferably in C ₃ -C ₁₀ , linear or branched, saturated or unsaturated, preferably saturated.

According to a particular embodiment of the invention, the compounds of formula (I) and (Ia) are such that n designates an integer ranging from 2 to 8, more particularly n designates an integer ranging from 3 to 6, more particularly from 3 to 5. According to one embodiment the compounds of formula (I) and (Ia) are such that n is 2. According to another embodiment the compounds of formula (I) and (Ia) are such that n is 3. According to another embodiment the compounds of formula (I) and (Ia) are such that n is 4. According to another embodiment the compounds of formula (I) and (Ia) are such that n is 5. According to another embodiment, the compounds of formula (I) and (Ia) are such that n is 6.

In a variant of the invention, the compound of formula (I) or (Ia) as defined above is a mixture of (poly)acetoacetylated compounds of different structures.

More particularly the compound(s) of formula (I) and (Ia) are chosen from the following compounds, as well as their optical isomers, their salts, and the solvates such as the hydrates:

in which R1 identical or different represents a hydrogen atom or a -C(O)-CH group₂-C(O)-CH_3,it being understood that at least two radicals R1 represent -C(O)-CH₂-C(O)-CH₃, preferably at least three radicals R1 represent -C(O)-CH₂-C(O)-CH₃,

More preferably the compounds chosen from (18), (21), (41) and (44) and better still (21), (41) and (44).

The compound(s) of formula (I) or (Ia) as defined above are preferably present in a mass ratio of 0.2% to 100%, particularly from 0.5% to 60%, more particularly from 5% to 100%. 40% relative to the total weight of composition C1, C2 or C3 containing them. In particular, the crosslinking agent(s) and the compound(s) of formula (I) or (Ia) are preferably present in a mass ratio of 7 to 35% relative to the total weight of the composition comprising them.

The compound(s) of formula (I) or (Ia) can be obtained by (poly)condensation(s) of n equivalents of dicarbonyl reagent with a nucleophilic reagent R ¹ (XH) _n comprising n equivalents of nucleophilic functions -XH according to the following diagram:

[Chem 3]:

• R¹, R², R^a, R^bet n sont tels que définis pour le composé de formule (I) et ;
• R³représente un atome d’hydrogène, un groupe (C₁-C₄)alkyle tel que méthyle, éthyle, isobutyle, t-butyle, ou un groupe électrofuge tel que CHal₃, ou Hal₃C-SO₂- comme triflate, avec Hal, identique ou différent, représentant un atome d’halogène ;
• X’ représente un atome d’oxygène, ou de soufre, de préférence O.

Scheme in which:

• R ¹ , R ² , R ^a , R ^b and n are as defined for the compound of formula (I) and;
• R ³ represents a hydrogen atom, a (C ₁ -C ₄ )alkyl group such as methyl, ethyl, isobutyl, t-butyl, or an electrorepellent group such as CHal ₃ , or Hal ₃ C-SO ₂ - such as triflate , with Hal, identical or different, representing a halogen atom;
• X' represents an oxygen or sulfur atom, preferably O.

These (poly)condensation methods are known to those skilled in the art, we can cite for example “From rigid and flexible foams to elastomers via Michael addition chemistry”, Polymer , 106, 128-139, (2016), “Dynamic Curing Agents for Amine-Hardened Epoxy Vitrimers with Short (Re)processing Times”, Macromolecules , 53(7), 2485-2495 (2020), “Super photo-base initiated organic-inorganic hybrid coatings by plural-cure mechanisms”, Progress in Organic Coatings , 127, 222-230 (2019) or patent application PL159100: Method for manufacturing acetylacetate esters.

According to a particular embodiment of the invention R ¹ (XH) _n is chosen from the acyclic polyols R ¹ (OH) _n chosen in particular from glycerol, trimethylolpropane, ethylene glycol, di ethylene glycol, tri ethylene glycol, tetra ethylene glycol , propylene glycol, dipropylene glycol, butylene glycol, trimethylolethane, pentamethylene glycol, trimethylpentanediol, pentyl glycol, isosorbide, pentaerythritol, dipentaerythritol, hexamethylene glycol, hexylene glycol, hexanediol, neopentyl glycol, 1,2-propanediol; 1,3-propanediol; 1,2 butanediol, 1,3-butane diol, 2,3-butanediol, 1,4-butanediol; 2,4-butanediol, 3,4-butanediol; 1,4-Pentanediol; 1,5-pentanediol, 2,2,4-Trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,2 octanediol, 1,8 octane diol, 1,10-decanediol, 2-methyl-1,3 -propane diol, hexylene glycol, isoprene glycol.

In a variant, R ¹ (XH) _n is chosen from the cylic polyols R ¹ (OH) _n in particular chosen from monosaccharides and disaccharides, as defined above, alone or in mixture.

Preferably R ¹ (XH) _n is chosen from the polyols R ¹ (OH) _n alone or in mixture, in particular from trimethylolethane, glycerol, trimethylolpropane, pentaerythritol, glycerol, glucose, sucrose and sorbitol.

According to another variant R ¹ (XH) _n is chosen from the diamines R ¹ (NH ₂ ) ₂ in particular hydroxyalkylated aliphatic diamines such as o,o′-bis(diethanolaminomethyl)-p-nonylphenol, N,N, N,N′-tetra(2-hydroxypropyl)ethylenediamine (Quadrol L, available from BASF) and N,N,N,N-tetra(2-hydroxyethyl)ethylenediamine, and their mixture.

According to another advantageous variant, the compound(s) of formula (I) or (Ia) are obtained by (poly)condensation(s) of n equivalent of propylenedioxy carbonyl reagent with a polyamine nucleophilic reagent R ¹ (NH) _n comprising n equivalents of -NH ₂ nucleophilic functions according to the following diagram:

[Chem. 4]:

• R¹, R², R^a, et n sont tels que définis pour le composé de formule (I)
• R¹-NH₂est notamment choisi parmi l’ethylènediamine, 1,3-diaminopropane, cadavérine, hexaméthylènediamine, 1,2-diaminopropane, 1,2-diaminocyclohexane, phénylènediamine ; et
• R^b’, et R^c’, identiques ou différents, représentent un atome d’hydrogène, un groupe (C₁-C₄)alkyle.

Scheme in which:

• R ¹ , R ² , R ^a , and n are as defined for the compound of formula (I)
• R ¹ -NH ₂ is in particular chosen from ethylenediamine, 1,3-diaminopropane, cadaverine, hexamethylenediamine, 1,2-diaminopropane, 1,2-diaminocyclohexane, phenylenediamine; And
• R ^b' , and R ^c ', identical or different, represent a hydrogen atom, a (C ₁ -C ₄ ) alkyl group.

This type of synthesis process according to diagram 2 is known to those skilled in the art, we can for example cite “Acetoacetylation with 2,2,6-trimethyl-4H-1,3-dioxin-4-one: a convenient alternative to diketene”, Journal of Organic Chemistry , 50(14), 2431-5, (1985) or “Synthesis of new Biginelli polycondensates: renewable materials with tunable high glass transition temperatures”, Polymer International , 70(5), 506-513 (2021).

According to another advantageous variant, the compound(s) of formula (I) or (Ia) are obtained by (poly)condensation(s) of n equivalent of diketene reagent with a nucleophilic reagent R ¹ (X) _n comprising n equivalents of nucleophilic functions -XH according to the following diagram:

Scheme in which:

R ¹ , and n are as defined for the compound of formula (I)

X’ represents an atom of oxygen, or sulfur, or N(R’) with R’=H

This type of process is known to those skilled in the art. We can for example cite “Acetoacetamides, 2-hydroximinoacetoacetamides, and 2,3-bis(hydroximino)-butyramides”, Journal fur Praktische Chemie (Leipzig), 323(2), 337-44, (1981) or Angewandte Makromolekulare Chemie , 9, 96-105, (1969).

ii) Cross-linking agent

• au moins une liaison covalente,
• au moins une liaison de type donneur-accepteur (dative), et/ou
• au moins une liaison de coordination,

et ainsi de réticuler le composé de formule (I) ou (Ia).The process of the invention uses ii) one or more crosslinking agents. For the purposes of the invention, the term "crosslinking agent", also known as R, designates a compound capable of establishing with at least one ACAC function of the compound of formula (I) or (Ia):

• at least one covalent bond,
• at least one donor-acceptor type bond (dative), and/or
• at least one coordination link,

and thus to crosslink the compound of formula (I) or (Ia).

Preferably, the term crosslinking agent designates a compound capable of establishing at least one covalent bond with an ACAC function of the compounds of formula (I) or (Ia).

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

Compositions C2, C3 and C4 contain at least one 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. Composition C4 may be an aqueous composition.

According to one aspect, the process of the invention uses a composition called "C3", in particular cosmetic for keratin materials, and in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows and/or for care, comprising i) at least one compound of formula (I) as defined above, ii) at least one crosslinking agent and iii) at least one cosmetic active ingredient as defined above, and in particular at least a coloring agent, more particularly at least one pigment.

The crosslinking agent(s) as defined above are preferably present in a mass ratio of 0.2% to 60%, particularly 0.5% to 40%, more particularly 5% to 40% relative to the total weight of the composition containing them. In particular, the crosslinking agent(s) and the compound(s) of formula (I) or (Ia) are preferably present in a mass ratio of 7% to 35% relative to the total weight of the composition comprising them.

More specifically, the crosslinking agent(s) R suitable for the invention can be chosen from compounds with amine, thiol, acrylate and/or carbonyl functions such as a ketone or aldehyde function. A crosslinking agent R can also designate a metal alkoxide.

Thus, according to a particular embodiment, the crosslinking agent R is chosen from (poly)amino, (poly)thiolated, (poly)carbonyl, (poly)acrylate, and/or metal alkoxide compounds (and their mixtures, and preferably chosen from (poly)amino, (poly)thiolated and (poly)acrylate compounds and mixtures thereof.

1. Les composés (poly)aminés

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

1. (Poly)amino compounds

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

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

The (poly)amine 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, represents a (C ₁ -C ₄ ) alkyl group such as methyl, and R'' represents a hydrogen atom or a group (C ₁ -C ₄ ) alkyl, preferably hydrogen.

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

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

According to a particular embodiment of the invention, the (poly)amino compound(s) are monoamines, ie contain a single primary and/or secondary, preferably primary, amine group (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' ₁ is a C ₁ -C ₆ hydrocarbon chain, linear or branched, saturated or unsaturated, cyclic or acyclic substituted by a group chosen from the primary NH ₂ or secondary amine groups -N(H)R with R representing a C ₁ -C ₄ alkyl, aryl, benzyl substituted by an amino group or by a C ₁ -C ₄ aminoalkyl group; R' ₁ can be interrupted in its chain by a heteroatom (O, S, NH) or a C(O) carbonyl group, R' ₁ being linked to the silicon atom directly via a carbon atom,

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

- z designates an integer ranging from 1 to 3, and

- x designates an integer ranging from 0 to 2,

with z + x = 3.

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

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

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

In particular, the (poly)amino 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)amino 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).

The (poly) amine compound can also be chosen from amine polymers, in particular having a weight average molecular weight ranging from 500 g.mol ^-1 to 1000000 g.mol ^-1 , preferably ranging from 500 g.mol ^-1 to 500,000 g.mol ^-1 , and preferably 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 monoamines 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 group (C ₁ -C ₄ ) alkyl such as methyl, and R' ₄ represents a (C ₁ -C ₆ ) alkyl group, linear or branched, preferably C ₄ such as n-butyl, does not represent an integer greater than or equal to 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), we can cite 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 diamined ie contain two primary and/or secondary amine groups, preferably primary (NH ₂ ). More particularly of formula chosen from the compounds of formulas (V) and (VI):

ALK[(O-ALK') _m -NH ₂ ] ₂ (V) 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 that propyl R', identical or different, represents a (C ₁ -C ₄ ) alkyl group such as methyl, m representing 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 . As examples of compounds of formula (VI), mention may be made of those sold under the names “DMS-A11”, “DMS-A12”, “DMS-A15”, “DMS-A21”, “DMS-A31”, “DMS -A32” and “DMS-A35” by the company Gelest.

The (poly)amino 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 (C ₁ -C ₆ )alkylene group, linear or branched, and m representing an integer greater than or equal to 0, such as 4,7,10-trioxa-1,13-tridecanediamine or the compounds ; in particular known under the reference Jeffamine from the Hunstman company; and more particularly polyethylene glycol and/or polypropylene glycol α, ω-diamine (with amine function at the end of the chain) such as those sold under the names Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED-9000, ED-2003.

According to a particular embodiment of the invention, the (poly)amino compound(s) are triaminated , i.e. contain three primary and/or secondary, preferably primary (NH ₂ ) amine groups. More particularly triamine polyethers in particular of formula ALK'''[(O-ALK') _m -NH ₂ ] ₃ with n and ALK' as defined above and and ALK''', representing a trivalent group (C ₁ -C ₆ )alkylene, linear or branched, and does not represent an integer greater than or equal to 0.

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

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

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

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

According to this variant, the (poly)amino compound(s) are in particular chosen from amino, 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 presenting 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; polyvinyl amino 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 one embodiment, the polydimethylsiloxanes comprising primary amine groups at the end of the chain and/or on side chains are chosen from the following formulas (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₎ group )alkyl such as methyl, ALK ¹ represents a (C ₁ -C ₆ )alkylene group, linear or branched, optionally interrupted by a group N(H), 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 an advantageous variant, 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 molecular weight average weight of polydimethylsiloxane ranges from 1000 g.mol ^-1 to 55,000 g.mol ^-1 . As examples of polydimethylsiloxanes of formula (VI), we can cite those sold under the names “AMS-132”, “AMS-152”, “AMS-162”, “AMS-163”, “AMS-191” and “AMS -1203” by the Gelest company.

According to another variant, 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, polytetrahydrofuran (or polytetramethylene glycol) α, ω-diamine, polybutadienes α, ω-diamine may also be cited.

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

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

1. Les composés (poly)thiolés

More preferably, the composition according to the invention 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, and even more preferably chosen from poly(D- Glucosamine), 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N -(2-aminoethyl)-3-aminopropyltriethoxysilane and polydimethylsiloxanes comprising terminal aminopropyl groups at the end of the chain, and even more preferably is 3-aminopropyl triethoxysilane (APTES).

1. (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 siliconed, that is to say it comprises one or more thiol groups, it also comprises at least one siloxane chain.

In a particular embodiment, the (poly)thiolated compound is inorganic. We can cite, for example, polythiol silicones.

The (poly)thiolated compound used in a composition according to the invention can in particular be chosen from non-polymeric (poly)thiolated compounds.

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

According to one embodiment of the invention, the (poly)thiolated compound(s) is organic and non-polymeric and is 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 n is inclusively between 2 and 10, preferably between 2 and 5;

- L designates a multivalent group (at least divalent), in particular comprising between 1 and 500 carbon and/or silicon atoms, more particularly between 2 and 40 carbon and/or silicon atoms, even more particularly between 3 and 30 carbon and/or silicon atoms, preferably between 6 and 20 carbon atoms, linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated;
L being optionally interrupted and/or terminated by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their associations such as –O-, –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, represent an atom of oxygen, sulfur, or a group N(R _b ); a, and b worth 0 or 1, preferably the sum of a + b is worth 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 p is an integer included inclusively between 2 and 10, preferably between 2 and 5.

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

Preferably, L designates a multivalent C ₈ -C ₁₈ radical, in particular linear. Preferably, the lipid-soluble polythiol is a C ₈ -C ₁₈ dithiol, in particular linear. Advantageously, the C ₈ -C ₁₈ chain is a hydrocarbon chain, that is to say formed of carbon and hydrogen. In particular, the lipid-soluble 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, 1,14-tetradecanedithiol, preferably 1,12-dodecanedithiol are used.

According to another particular embodiment of the invention, the (poly)thiolated compound(s) is 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 the groups:

- thiol, 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 atoms, preferably from 1 to 4 carbon atom(s) such as methyl,

● z designates an integer ranging from 1 to 3, and

● x designates 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, preferably linear, alkyl group comprising from 1 to 4 carbon atoms such as methyl or ethyl.

Preferably, R' ₁ is an acyclic chain, particularly 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 group thiol.

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

R' ₃ represents an alkyl group comprising 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; and t is an integer between 1 and 4, preferably 2;

● R ¹ represents a (C ₁ -C ₆ ) alkyl radical;

• un groupe (C₁-C₆)alkyle, en particulier en C₁-C₄tel que méthyle ;
• un groupe (C₁-C₆)alcoxy, en particulier (C₁-C₄₎alcoxy tel que méthoxy ;

● R⁴et R’⁴, identiques ou différents, représentent un atome d’hydrogène, ou un groupe (C₁-C₆)alkyle tel que méthyle ;
● 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;
• 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 designates a (C ₁ -C ₆ ) alkyl radical;

● R' ² and R' ³ , identical or different, preferably identical, are chosen from:

- a (C ₁ -C ₆ )alkoxy group, in particular C ₁ -C ₄ ;

- a (C ₁ -C ₆ ) alkyl radical;

● R ⁵ represents a hydrogen atom or a C ₁ -C ₄ alkyl group optionally substituted by an amino, thiol or hydroxy group;

● R ⁴ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, in particular methyl;
● L ² represents a divalent hydrocarbon group, linear or branched saturated at 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 chosen from 4-(trimethoxysilyl)-1-butanol, 3-(trimethoxysilyl)-1-propanol, 3-(triethoxysilyl)-1-propanol, 11-(trimethoxysilyl) -1-undecanethiol, 4-(trimethoxysilyl)-2-butanethiol, 2-(triethoxysilyl)-ethanethiol, 3-(triethoxysilyl)-1-propanethiol, 2-(trimethoxysilyl)-ethanethiol, 3-(trimethoxysilyl) )-1-propanethiol and 3-(dimethoxymethylsilyl)-1-propanethiol.

More preferably, the 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.

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

As an example, we can cite the polymers described in the following scientific articles: Polymers containing groups of biological activity, CG Overberger et al, Polytechnic Institute of Brooklyn ,

https://pac.iupac.org/publications/pac/pdf/1962/pdf/0402x0521.pdf; EP 1 247 515 A2; U.S. 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 designates 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 associations such as –O-, –OC(X)-, -N(R)-C( X)-, -Si(R _c )(R _d )-O- with R representing a hydrogen atom or a (C ₁ -C ₆ )alkyl group such as methyl; and or

POLY being optionally substituted by one or more halogen atoms, or a group chosen from R _a (R _b )N- and -(X') _a -C(X)-(X'') _b -R _a ;

- X, X' and X'', identical or different, represent an atom of oxygen, sulfur,

or a group N(R _b );

- a, and b worth 0 or 1, preferably the sum of a + b is worth 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 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 modes of preparation of the (poly)thiolated polymeric compounds used according to the invention are known to those skilled in the art, several modes are reported below in a non-limiting manner. The (poly)thiolated polymeric 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 (poly)thiolated polymeric 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 polymer radical, preferably silicone, POLY which may also contain one or more heteroatoms chosen from O, N, S and/or one or more functions chosen from the functions, (thio) esters, (thio) ketones, (thio) amides, (thio) ureas, (thio )carbamates, and/or be substituted by one or more (C ₁ -C ₁₀ )alkyl groups, linear or branched, (C ₁ -C ₁₀ )alkoxy, linear or branched, 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 400,000 g.mol ^-1 , preferably between 500 and 150,000 g.mol ^-1 . According to a particular embodiment of the invention, the polythiolated compounds are chosen from 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 between 500 and 55,000 g.mol ^-1 ; particularly n is an integer comprised from 1 to 100, preferably comprised from 5 to 50, and preferably comprised 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 group, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylenoxy or oxy(C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene, preferably a (C ₁ -C ₆ )alkylene group, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene, or (C ₁ -C ₆ )alkylene -oxy(C ₁ -C ₆ )alkylene.

Preferably, the (poly)thiolated compounds are polythiolated polyorganosiloxanes, more preferably polythiolated polydimethylsiloxanes, in particular 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 previously in formula (XI), in particular L ⁴ and L ⁵ represent a (C ₁ -C ₆ ) alkylene group, (C ₁ -C ₆ ) alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene, or (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene, more preferably a divalent group chosen from –R ₂ –, –O–R ₂ –, –R ₂ –O–, –R ₂ –O–R ₂ –, preferably –R ₂ –O–R ₂ –, with R ₂ representing a linear or branched (C ₂ -C ₆ )alkylene group, preferably linear , such as ethylene or propylene, preferably n-propylene; And
● n is as defined in formula (XI).

As polythiolated compounds of formula (XII), mention may be made of mercaptosiloxane 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 group ( C ₁ -C ₆ ) alkyl such as methyl,

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

● ALK ₁ represents a divalent hydrocarbon chain comprising 1 to 100 carbon atoms, saturated or unsaturated, linear or branched, optionally cyclic, optionally interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen (in particular O), a group (thio)carbonyl C(X) with X representing O, or S, or their associations such as –O–, –OC(O)– or –C(O)-O–, preferably ALK ₁ represents a group (C ₁ -C ₆ )alkylene, more preferably (C ₁ -C ₄ )alkylene such as propylene;
● n and m, identical or different, representing an integer greater than 2 and more particularly the values of m and n are such that the weight average molecular weight of said polyorganosiloxane is between 1000 and 55000 g.mol ^-1 .

As examples of polythiolated compounds of formula (XIII), we can cite those sold by the company Genesee Polymers under the names GP-367, GP-71-SS, GP-800 and GP-710s, preferably GP-367 marketed by the Genesee Polymers company.

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.

1. Les composés (poly)carbonylés

As a reference, 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).

1. (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-(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 non-ionic or anionic oxidized polysaccharides such as oxidized inulins, in particular those of formula (II) such as defined below. Particularly the (poly)carbonyl compounds comprise a C ₅ -C ₇ 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 terephthaldehyde.

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 nonionic or anionic oxidized polysaccharides according to the invention can be represented by the following formula (II): P–(CHO) _m (COOQ) _n (II)

• P représente une chaîne polysaccharidique de préférence constitués de monosaccharides comprenant 5 atomes de carbone ou plus de 5 atomes de carbone, de préférence 6 ou plus de 6 atomes de carbone et plus particulièrement 6 atomes de carbone ;
• Q est choisi parmi un atome d’hydrogène, les ions issus d'un métal alcalin ou alcalino terreux tels que sodium, potassium, l'ammoniaque, les amines organiques comme la monoéthanolamine, la diéthanolamine, la triéthanolamine et l'amino-3 propanediol-1,2 et les aminoacides basiques tels que la lysine, l'arginine, la sarcosine, l'ornithine, la citrulline,
• m + n est supérieur ou égal à 1,
• m est tel que le degré de substitution du polysaccharide par un ou plusieurs groupements aldéhydes (DS(CHO)), est compris dans l'intervalle allant de 0,001 à 2, de préférence de 0,005 à 1,5.
• n est tel que le degré de substitution du polysaccharide par un ou plusieurs groupements carboxyliques (DS(COOX)), est compris dans l'intervalle allant de 0 à 2, de préférence de 0,001 à 1,5.

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 from an alkali or alkaline earth metal such as sodium, potassium, ammonia, organic amines such as monoethanolamine, diethanolamine, triethanolamine and 3-amino propanediol -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 in 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 in 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, we mean the ratio between the number of carbons oxidized to an aldehyde or carboxylic group for all the repeating units and the number of elementary monosaccharides (even open 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 take place in 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 we mean 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 process known in the art, for example according to the process 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).

1. Les composés (poly)acrylates

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).

1. (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 group (C ₁ -C ₄ )alkyl such as methyl, preferably R ^e represents a hydrogen atom, and Y representing an oxygen atom or an amino group -N(H)-, preferably O.

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, being as defined in formula (VIII); Y and R ^e being as defined above, 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 hydrocarbon chain, preferably trivalent, 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:

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, 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; And
● 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 previously, preferably O.

More particularly, the (poly)acrylate compound may be chosen from 1,3-butanedioldiacrylate, 1,4-butanedioldiacrylate, di(trimethylolpropane) tetraacrylate, glycerol 1,3-diglycerolate diacrylate, glycerol propoxylate (1PO/OH ) triacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol ethoxylate diacrylate, hydroxypivalyl hydroxypivalate, neopentyl glycol diacrylate, neopentyl glycol propoxylate (1PO/OH) diacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, poly(propylene glycol) diacrylate, tricyclo[5.2.1.02,6]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 can 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).

1. Les alcoxydes métalliques

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 copolymer of dimethylsiloxane and acryloxypropyl)methylsiloxane.

1. Metal alkoxides

According to another particular embodiment, the crosslinking agent R is a compound chosen from metal alkoxides of formulas (XIV_has), (XIV_b), (XIV_vs) and (XIVd) following and their mixtures: M-(OR ₁ ) _n (XIV _a ) RM-(OR ₁ ) _n-1 (XIV _b ) (R ₁ O) _n-1 -M-R''-M'-(OR ₁ ') _n'-1 (XIV _c ) RM(R')-(OR ₁ ) _n-2 (XXIV _d ) Formulas (XIV_has), (XIV_b), (XIV_vs) and (XIV_d) in which:

- M and M', identical or different, represent an atom chosen from alkaline earth metals, transition metals, metals of the lanthanide family, post-transition metals such as aluminum or tin and metalloids such as boron; preferably transition metals such as Ti and post-transition metals such as aluminum;

- n and n' respectively represent the valences of the atoms represented by M and M';

- R ₁ and R ₁ ', identical or different, represent a hydrocarbon group, linear or branched, saturated or unsaturated, having from 1 to 30 carbon atoms, preferably from 1 to 6 carbon atoms, said hydrocarbon group being optionally interrupted by 1 to 20 heteroatoms chosen from O, N, S and P, in particular O or N; and/or said hydrocarbon group being optionally substituted by one or more hydroxy or carbonyl groups; ;
- R and R', identical or different, represent a hydrogen atom or a hydrocarbon group, linear, branched, acyclic or cyclic, saturated or unsaturated, having from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms carbon, optionally interrupted by 1 to 20 heteroatoms chosen from O, N, S and/or P, in particular O or N and/or said hydrocarbon group optionally being substituted by one or more hydroxy or carbonyl groups;

- R" represents -O-, -N(R2)-, -S- or a divalent hydrocarbon group, linear, cyclic or branched, saturated or unsaturated, having from 1 to 30 carbon atoms, preferably from 2 to 20 atoms of carbon, optionally interrupted by 1 to 20 heteroatoms chosen from O, N, S and P in particular O or N, with R2 representing a hydrocarbon group, linear, cyclic or branched, saturated or unsaturated, having from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms.

Preferably, M and M', identical or different, represent an atom chosen from transition metals such as titanium, or zirconium or alkaline earth metals such as magnesium, more preferably chosen from transition metals such as than titanium or zirconium, even more preferably titanium.

Preferably, the organometallic compound(s) are chosen from the alkoxides of formula (XIV _a ) as defined above. According to this preferred embodiment, the organometallic compound(s) are more particularly chosen from the alkoxides of formula (XIV _a ), in which:

- M represents an atom chosen from transition metals, metals of the lanthanide family, post-transition metals such as aluminum, tin, metalloids such as boron, or alkaline earth metals such as magnesium or calcium;
- n represents the valence of the atom represented by M;
- R ₁ , represents a hydrocarbon group, linear or branched, saturated, having from 1 to 30 carbon atoms, preferably from 1 to 6 carbon atoms.

According to another more preferred embodiment, the organometallic compound(s) are chosen from alkoxides of formula (XIV _a ), in which M represents an atom chosen from transition metals such as zirconium or titanium, metals of the lanthanide family, post-transition metals such as aluminum, tin, metalloids such as boron, and alkaline earth metals such as magnesium, preferably M represents an atom of titanium; n represents the valency of the atom represented by M, in particular 1, 2, 3 or 4, in particular 4; R ₁ represents a methyl, ethyl, 2-ethylhexyl, propyl, isopropyl, n-butyl, isobutyl or t-butyl group. According to an even more preferred embodiment, the organometallic compound(s) are chosen from zirconium ethoxide (Zr(OC ₂ H ₅ ) ₄ ), zirconium propoxide (Zr(OCH ₂ CH ₂ CH ₃ ) ₄ ), zirconium isopropoxide (Zr(OCH(CH ₃ ) ₂ ) ₄ ), zirconium butoxide Zr(OCH ₂ CH ₂ CH ₂ CH ₃ ) ₄ , zirconium tert-butoxide (Zr( OC(CH ₃ ) ₃ ) ₄ ), titanium ethoxide (Ti(OC ₂ H ₅ ) ₄ ), titanium propoxide (Ti(OCH ₂ CH ₂ CH ₃ ) ₄ ), titanium isopropoxide (Ti (OCH(CH ₃ ) ₂ ) ₄ ), titanium butoxide (Ti(OCH ₂ CH ₂ CH ₂ CH ₃ ) ₄ ), titanium tert-butoxide (Ti(OC(CH ₃ ) ₃ ) ₄ ), 2-ethylhexyloxide of titanium (Ti(OCH ₂ CH(C ₂ H ₅ )(CH ₂ ) ₃ CH ₃ ) ₄ ), and their mixtures, more preferably chosen from zirconium propoxide, titanium propoxide, butoxide titanium and their mixtures. More preferably, the crosslinking agent R is a compound of formula (XXIV _a ) preferably in which M represents an atom chosen from transition metals, in particular titanium such as titanium butoxide.

According to a preferred embodiment, the crosslinking agent is chosen from the compounds A) (poly) amines, B) (poly) thiolates, C) (poly) carbonyls, D) (poly) acrylates, and preferably from the compounds A) (poly)amines and B) (poly)thiolates.

In particular said (poly)amino compounds A) are chosen from a) chitosans such as poly(D-Glucosamine), b) polyether diamines, particularly polyethylene glycol α, ω-diamine (with an amine function at the end of the chain) and 4,7,10-Trioxa-1,1-tridecanediamine, c) polyether triamines such as Polyetheramine (or jeffamine), d) aminoalkoxysilanes such as APTES, e) polydialkylsiloxanes comprising primary amine groups at the end of the chain or on side chains, particularly polidimethylsiloxanes comprising primary amine groups such as poly(dimethoxysiloxane) terminated by bis(3-aminopropyl) (PDMS-diNH2) and amodimethicones comprising amine groups on side chains such as bis-cetearyl amodimethicone.

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, preferably polydimethysiloxanes comprising thiol groups on the chain lateral (such as mercaptopropyl) in particular those of formula (XIII)

In particular, said (poly)acrylate compounds D) 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, preferably trimethylolpropane triacrylate.

iii) Cosmetic active ingredient

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

More particularly in the process of 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) of the invention is(are) chosen from a) coloring materials (or coloring agents) chosen from pigments, direct dyes and mixtures thereof, b) material care active ingredients keratin, preferably from the skin, c) UV filters, and d) their mixtures.

According to a particular embodiment, the at least one cosmetic agent is chosen from coloring materials, preferably chosen from pigments, direct dyes and their mixtures, more preferably pigments.

Of course, those 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 substantially not, altered by the addition envisaged.

Coloring materials

According to a particular embodiment, the process of the invention uses one or more coloring materials.

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 material, particulate or not, water-soluble or not, and preferably in an amount of at least less 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 the specialist. art.

Preferably, at least one of the compositions C1, C2, C3, C4 or C5 comprises at least one coloring material chosen from pigments, direct dyes and mixtures thereof, 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 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 notably reds such as D&C RED 7.

Pigments

By “ pigment ”, within the meaning of the invention, is meant any compound capable of providing color to keratin materials. These compounds have a solubility in water at 25°C and 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 which are described in the Kirk-Othmer encyclopedia of chemical technology and in the encyclopedia of industrial chemistry of Ullmann. These pigments can be synthetic or natural. These pigments can be in the form of powder or pigment paste. They can be coated or uncoated. These pigments can for example be chosen from mineral pigments, organic pigments, lacquers, pigments with special effects such as pearls or flakes, and their mixtures.

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

By “ mineral pigment ” we mean any pigment which meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Mention may be made, among the mineral pigments useful in the present invention, of manganese violet, ultramarine blue, chromium hydrate, ferric blue and the oxides or dioxides of titanium, zirconium or cerium, as well as the oxides of zinc, iron or chromium.

It may also be a pigment having a structure which may for example be of the sericite/brown iron oxide/titanium dioxide/silica type. Such a pigment is sold for example under the reference Coverleaf NS or JS by the company Chemicals And Catalysts and has a contrast ratio close to 30. It can also be pigments having a structure which can be, for example, of type silica microspheres containing iron oxide. 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 can be chosen from organic pigments.

By “ organic pigment ” we mean any pigment which meets the definition of the Ullmann encyclopedia in the organic pigment chapter. Mention may be made, among the organic pigments useful in the present invention, of the compounds nitroso, nitro, azo, xanthene, pyrene, quinoline, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, of the metal complex type, isoindolinone, isoindoline, quinacridone, perinone. , perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone. In particular, the white or colored organic pigments can be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 74100, 74160, yellow pigments codified in the Color Index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, green pigments codified in the Color Index under references CI 61565, 61570, 74260, orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 5 , 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, pigments obtained by oxidative polymerization of indole derivatives, as described in the FR patent 2,679,771.

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

The pigments according to the invention can also be in the form of composite pigments such as described in patent EP 1 184 426. These composite pigments can be composed in particular of particles comprising an inorganic core, at least one binder ensuring the fixation of the organic pigments on the core, and at least one organic pigment covering at least partially the core.

The organic pigment can also be a lacquer.

By “ lacquer ” is meant the dyes adsorbed on insoluble particles, the assembly thus obtained remaining insoluble during use.

The inorganic substrates on which the dyes are adsorbed are for example alumina, silica, calcium and sodium borosilicate or calcium and aluminum borosilicate, and aluminum. Among the dyes adsorbed on organic substrates, we can cite carminic acid. We can also cite the dyes known under the following names: D & C Red 21 (CI 45 380), D & C Orange 5 (CI 45 370), D & C Red 27 (CI 45 410), D & C Orange 10 (CI 45 425), D & C Red 3 (CI 45 430), D & C Red 4 (CI 15 510), D & C Red 33 (CI 17 200), D & C Yellow 5 (CI 19 140), D & C Yellow 6 (CI 15 985), D & C Green (CI 61 570), D & C Yellow 1 O (CI 77 002), D & C Green 3 (CI 42 053), D & C Blue 1 ( CI 42 090), FDC Red 4, D & C Red 6, D & C Red 22, D & C Red 28, D & C Red 30, D & C Orange 4, D & C Yellow 8, D & C Green 5 , D & C Red 17, D & C Green 6, D & C Yellow 11, D & C Violet 2, Sudan red, carotenes (β-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein) , palm oil, Sudan brown, quinoline yellow, annatto, curcumin, betanin (beetroot), carmine, copper chlorophyllin, methylene blue, anthocyanins (enocianin, black carrot, hibiscus, elderberry ), caramel, riboflavin, beet juice and caramel.

As examples of lacquers, we can cite the product known under the following name: D & C Red 7 (CI 15 850:1).

The pigment can also be a special effect pigment.

By “ special effect pigments ” we mean pigments which generally create a colored appearance (characterized by a certain nuance, a certain vividness and a certain clarity) that is non-uniform and changes depending on the observation conditions (light , temperature, observation angles, etc.). They are therefore opposed to colored pigments which provide a classic 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 pearlescent, interference pigments or glitter.

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

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

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 cling physically or chemically to the surface of pigments. These dispersants also present at least one functional group that is compatible or soluble in the continuous medium. In particular, esters of 12-hydroxystearic acid in particular and of C ₈ to C ₂₀ fatty acid and polyols such as glycerol, diglycerin, such as poly(12-hydroxystearic acid stearate) are used. ) with a molecular weight of approximately 750 g/mol such as that sold under the name Solsperse 21 000 by the company Avecia, polygyceryl-2 dipolyhydroxystearate (name CTFA) sold under the reference Dehymyls PGPH by the company Henkel or even polyhydroxystearic acid such as that sold under the reference Arlacel P100 by the company Uniqema and their mixtures. As another dispersant which can be used in the compositions of the invention, mention may be made of quaternary ammonium derivatives of polycondensed fatty acids such as Solsperse 17 000 sold by the company Avecia, mixtures of poly dimethylsiloxane/oxypropylene such as those sold by the company Dow Corning under the references DC2-5185, DC2-5225 C. The pigments used in the composition can be surface treated with an organic agent. 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 treated on the surface 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.

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

By “ direct dye ” we mean natural and/or synthetic dyes, different from oxidation dyes. These are dyes which will diffuse superficially on the fiber. They can be ionic 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; porphyrin dyes; phthalocyanine dyes and natural direct dyes, alone or in the form of mixtures.

The direct dyes are preferably cationic direct dyes. We can mention the cationic hydrazono dyes of formulas (A) and (B) below and the cationic azo dyes of formulas (C) and (D) below: Hét ⁺ -C(Ra)=NN(Rb)-Ar, Q ^- Hét ⁺ -N(Ra)-N=C(Rb)-Ar, Q ^- (HAS) (B) Het ⁺ -N=N-Ar, Q ^- Ar ⁺ -N=N-Ar'', Q ^- (VS) (D) Formulas (A) to (D) in which:

- Hét ⁺ represents a cationic heteroaryl radical, preferably with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally preferentially substituted 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 donor groups such as (C ₁ -C ₈ ) optionally substituted alkyl, (C ₁ -C ₈ ) optionally substituted alkoxy, (di)(C ₁ -C ₈ )(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxyl group, aryl(C ₁ -C ₈ )alkylamino, and N-(C ₁ -C ₈ )alkyl-N-aryl(C ₁ - C ₈ ) optionally substituted alkylamino or Ar represents a julolidine group;

- Ar'' represents an optionally substituted (hetero)aryl group such as optionally substituted phenyl or pyrazolyl, preferably by one or more (C ₁ -C ₈ )alkyl, hydroxyl, (di)(C ₁ -C ₈ )(alkyl) groups )amino, (C ₁ -C ₈ )alkoxy or phenyl;

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

or the Ra substituent with a Het ⁺ substituent and/or Rb with an Ar substituent 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 mineral anionic counterion such as a halide or an alkyl sulfate.

In particular, we can cite the direct dyes with cationic endocyclic azo and hydrazono charges of formula (A) to (D) as defined above. More particularly, the cationic direct dyes with endocyclic cationic charges described in patent applications WO 95/15144, WO 95/01772 and EP-714954. Preferably the following direct dyes of 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 donor group such as (C ₁ -C ₈ ) optionally substituted alkyl, (C ₁ -C ₈ ) optionally substituted alkoxy, (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 halide such as chloride or an alkyl sulfate such as methyl or mesytyl sulfate.

Particularly, the dyes of formula (E) and (F) are chosen from Basic Red 51, Basic Yellow 87 and Basic Orange 31 or their derivatives with Q- an anionic counterion as defined previously, particularly halide such as chloride or a alkyl sulfate such as methyl sulfate or mesytyl. The direct dyes can be chosen from anionic direct dyes. The anionic direct dyes of the invention are dyes commonly called “acid” direct dyes for their affinity with alkaline substances.

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

The anionic direct dyes can be chosen from acid nitrate direct dyes, acid azo dyes, acid azinic dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and acidic natural dyes.

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

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

The coloring materials, preferably 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%. 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 of the total weight of the composition, preferably from 0.005% to 5% by weight of the total weight of the composition which contains them.

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

Care assets

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

More particularly in the process 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 in an amount 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 a lipophilic active ingredient, and preferably a hydrophilic care active ingredient.

The term “hydrophilic active ingredient” means a water-soluble or water-dispersible active ingredient 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 tocopherol acetate), ascorbic acid (vitamin C) and its derivatives; b) humectants, in particular urea, hydroxyureas, glycerol, polyglycerols, glycerolglucoside, diglycerolglucoside, polyglycerylglucosides, and xylitylgiucoside, and in particular glycerol; c) C-glycoside compounds; d) antioxidant compounds; e) anti-aging active ingredients, 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 the sodium salt of 3-hydroxy-2-pentylcyclopentyl)acetic acid; f) skin care agents selected from allantoin, panthenol and protein hydrolysates g) polyphenols, including escin, ruscus, diosmin, hesperidin, resveratrol, and h) mixtures thereof .

According to a particular form of the invention, the process of the invention, at least one of the compositions C1, C2, C3, C4 or C5 implemented comprises a moisturizing agent (also called humectant agent). 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(ies), in a content ranging from 0.01% to 30% by weight, relative to the weight of the composition, and preferably 0.02%. at 25% by weight.

UV filters

According to one embodiment of the invention, the method of the invention, at least one of the compositions C1, C2, C3, C4 or C5 implemented comprises, as a cosmetic active ingredient, at least one UV filter. The UV filter(s) is a UV filter usually used in cosmetics. It can be chosen from the positive list contained in Annex VI of Regulation (EC) No. 1223/2009, which specifies the list of UV filters authorized in cosmetics. The UV filters suitable for the invention can be of different types. They can be lipophilic, hydrophilic or insoluble organic.

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

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

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

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

In particular, the UV filter(s) are chosen from bis-resorcinyl triazine derivatives, dibenzoylmethane derivatives, benzylidene camphor derivatives, and mixtures thereof. Organic UV filters can also be chosen from anthranilics; cinnamic derivatives; salicylic derivatives; benzophenone derivatives; phenyl benzotriazole derivatives; benzalmalonate derivatives, in particular those cited in US patent 5,624,663; phenyl benzimidazole derivatives; imidazolines; 4,4-diarylbutadiene 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; merocyanine derivatives other 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 according to the invention varies from 1% to 50%, preferably from 1% to 40% by weight, and again for example ranges from 5% to 35%. by weight, relative to the total weight of the composition.

The UV filter(s) may be mineral UV 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, 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, the compositions C1 to C5 according to the invention are devoid of mineral UV filters.

According to a particular embodiment, the quantity of the mineral UV filter(s), present in the compositions according to the invention, can range from 0.01% to 20% by weight, relative to the total weight of the composition C1 to C5 which contain 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 according to the invention further comprises one or more organic UV filters and one or more mineral UV filters.

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

Preferably the process for treating keratin materials, in particular the skin, and the compositions C1, C2, C3, C4 or C5 use or include one or more coloring materials chosen from pigments, direct dyes and mixtures thereof, 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 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 notably reds such as D&C RED 7.

Advantageously, the process for treating keratin materials is a makeup process, particularly for the skin, in particular a process for lip makeup, mascara, eyeliner, eye shadow, foundation.

iv) Fat phase – fatty substance

According to a particular embodiment, the process of the invention uses one or more fatty substances, particularly one or more preferably volatile oils.

More particularly in the process of the invention at least one of the compositions C1, C2, C3, C4 or C5 used in the process of the invention contains a fatty phase.

Particularly at least one of the compositions used in process C1, C2, C3, C4 or C5 comprises one or more fatty substances, particularly one or more preferably volatile oils.

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

By “ hydrocarbon oil ” is meant an oil formed essentially, or even made up, of carbon and hydrogen atoms, and possibly of oxygen or nitrogen atoms, and not containing any silicon or carbon atoms. fluorine. It may contain alcohol, ester, ether, carboxylic acid, amine and/or amide groups.

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

* hydrocarbon oils having 8 to 16 carbon atoms, and in particular:

- branched C ₈ -C ₁₆ alkanes such as isoalkanes such as iso-alkanes (also called isoparaffins) such as C ₁₃ -C ₁₆ Isoparaffin, isododecane, isodecane, isohexadecane, and 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), more preferably isododecane;

- linear alkanes for example C ₁₁ -C ₁₆ , alone or in mixtures, for example such as hexane, decane, undecane, tridecane, isoparaffins such as, or n-dodecane (C12) and n-tetradecane (C14), undecane-tridecane mixture, mixtures of n-undecane (C11) and n-tridecane (C13), and mixtures thereof as well as mixtures of n -undecane (C11) and n -tridecane (C13);

- cyclic, non-aromatic, C ₅ -C ₁₂ volatile alkanes;

* short-chain esters having 3 to 8 carbon atoms in total such as 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 designate a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably an alkyl group in C ₄ -C ₈ , advantageously chosen from dibutylcarbonate or dipentylcarbonate;

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

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

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

Particularly at least one of the compositions C1, C2, C3, C4 or C5 used in the process according to the invention comprises one or more non-volatile oil(s) in particular chosen from:

* non-volatile fluorinated oils chosen in particular from fluorinated polyethers, as well as from 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; as well as their mixtures.

* non-volatile non-polar 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 in C ₁₅ -C ₂₈ , such as 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) their mixtures;

* polar non-volatile hydrocarbon oils which can be chosen from:

i) fatty alcohols, saturated, unsaturated, linear or branched, C ₁₀ -C ₂₆ , preferably mono-alcohols; advantageously, the 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, such as in particular lauric, isostearyl, oleic alcohol, 2-butyloctanol, 2-undecyl pentadecanol, 2-hexyldecyl alcohol, isocetyl alcohol, octyldodecanol and mixtures thereof;

ii) triglycerides consisting of esters of fatty acids and 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; by way of 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, soy, sweet almond, palm, rapeseed, cotton, hazelnut, macadamia, jojoba, alfalfa, poppy, pumpkin, squash, blackcurrant, evening primrose, millet, barley, quinoa, rye, safflower, cancholy, passionflower, muscat rose, peanut, coconut, argan, passionflower, kaya; the liquid fraction of shea butter, and the liquid fraction of cocoa butter; as well as their mixtures;

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

iv) hydroxylated esters such as polyglycerol-2 triisostearate;

v) aromatic esters such as tridecyl trimellitate, C ₁₂ -C ₁₅ 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 such as pentaerythrityl tetrapelargonate;

vii) esters of fatty alcohol or C ₂₄ -C ₂₈ branched fatty acids such as triisoarachidyl citrate, pentaerythrityl tetraisononanoate, glyceryl triisostearate, glyceryl tri-decyl-2-tetradecanoate, glyceryl tetraisostearate pentaerythrityl, polyglyceryl-2 tetraisostearate or even pentaerythrityl tetradecyl-2 tetradecanoate;

viii) polyesters obtained by condensation of dimer and/or trimer of unsaturated fatty acid and diol such as those with the INCI name dilinoleic acid/butanediol copolymer, dilinoleic acid/propanediol copolymer; polyesters obtained by condensation of fatty acid dimer and dimer diol such as dilinoleyl dimer dilinoleate;

ix) synthetic ethers having 10 to 40 carbon atoms such as dicaprylyl ether;

x) di-alkyl carbonates, the two alkyl chains possibly being identical or different, such as dicaprylyl carbonate;

xi) vinylpyrrolidone copolymers such as vinylpyrrolidone/1-hexadecene copolymer; And

xii) their mixtures;

* the non-volatile carbonate oils can be chosen from the carbonates of formula R ₈ -OC(O)-OR ₉ , with R ₈ and R ₉ , identical or different, represent a C ₄ to C ₁₂ alkyl chain, and preferably of C ₆ to C ₁₀ , linear or branched; the carbonate oils can 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 designate 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 that R ₁ and R ₂ are 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, heptadecyl, octadecyl, nonadecyl, eicosyl, behenyl, docosyl, tricosyl and tetracosyl. As a branched alkyl group, mention may be made of 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- group dimethylbutyl, 1-(1-methylethyl)-2-methylpropyl group, 1,1,3,3-tetramethylbutyl group, 3,5,5-trimethylhexyl group, 1-(2-methylpropyl)-3- group methylbutyl, a 3,7-dimethyloctyyl group, and a 2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctyl group. As a cyclic alkyl group, mention may be made of 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 their mixtures;

more preferably c) the non-volatile oil(s) is(are) chosen from polyisobutenes, hydrogenated or not, preferably hydrogenated such as for example the non-volatile compounds from the Parléam® range; mixtures of C ₁₅ -C ₁₉ Alkane, and among 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.

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

Particularly the quantity of oil(s) in at least one of the compositions C1, C2, C3, C4 or C5 used in the process is between 1 and 99% by weight relative to the total weight of the composition, more particularly between 10% and 90% by weight, preferably between 25% and 75%, better still between 30% and 70% by weight relative to the total weight of the composition.

The essays :

According to one embodiment, the process for treating keratin materials uses water and the composition(s) C1 to C5 used in the process of the invention comprise water.

According to an advantageous variant C1 is aqueous or hydroalcoholic,

According to an advantageous variant C2 is aqueous or hydroalcoholic.

According to an advantageous variant C3 is aqueous or hydroalcoholic.

According to an advantageous variant C4 is aqueous or hydroalcoholic.

According to an advantageous variant C5 is aqueous or hydroalcoholic.

According to another particular embodiment of the invention C1 is an anhydrous composition. According to another variant C2 is anhydrous. According to another variant C3 is anhydrous. According to yet another variant C4 is anhydrous. According to another variant C5 is anhydrous. In particular C1 and/or C4 is(are) anhydrous. Particularly C4 is anhydrous and comprises at least one particularly volatile oil such as isododecane.

The compositions C1 to C5 used in the process of the invention may also comprise one or more organic solvents.

By “ organic solvent ” we mean an organic substance capable of dissolving another substance without chemically modifying it.

As an organic solvent, we can for example cite a) C ₂ -C ₆ alkanols, such as ethanol and isopropanol; b) 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; c) polyol ethers such as 2-butoxyethanol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as d) aromatic alcohols such as benzyl alcohol or phenoxyethanol, and mixtures thereof.

According to a particular embodiment, the composition further comprises one or more polyols, 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.

Particularly the compositions C1, C2, C3, C4 or C5 (preferably C2 or C3) are aqueous or hydroalcoholic (ethanol/water mixture in particular in volume ratio between 1/99 to 99/1, more particularly between 10/90 at 90/10, even more particularly between 20/80 and 80/20, preferably 40/60 to 60/40 such as 50/50).

Compositions C1, C2, C3, C4 or C5 can be in anhydrous form, water-in-oil emulsion or oil-in-water emulsion.

The additives

The compositions C1, C2, C3, C4 or C5 used in the process of the invention may further comprise one or more adjuvants chosen from perfumes, preservatives, fillers, anti-free radical agents, polymers, thickeners or film-forming agents, surfactants, trace elements, softeners, sequestrants, and propellants.

Another object of the invention is a composition C1, preferably aqueous or hydroalcoholic, which comprises i) at least one compound of formula (I) or (Ia) and iii) optionally at least one active ingredient as defined above, preferably at least one coloring material, such as at least one pigment as defined above; and optionally iv) one or more fatty substances as defined above.

Another object of the invention is a composition C2, preferably aqueous or hydroalcoholic, which comprises i) at least one compound of formula (I) or (Ia) as defined above, ii) at least one crosslinker as defined above and iii) possibly at least one asset as defined above; and optionally iv) one or more fatty substances as defined above.

Another object of the invention is a composition C3, preferably aqueous or hydroalcoholic, which comprises i) at least one compound of formula (I) or (Ia) as defined above, ii) at least one crosslinker as defined above and iii) at least one asset as defined above; and optionally iv) one or more fatty substances as defined above.

Another object of the invention is the cosmetic use of the composition C1 C2 or C3 which comprises iii) one or more cosmetic active(s) as defined(s) previously and optionally iv) one or more several fatty substances as defined above, in particular for the treatment of keratin materials, in particular for the makeup of keratin materials in particular the skin such as lips, eyelashes or eyebrows .

Kit

According to yet another of its aspects, the present invention also aims at a kit or device with several compartments, in particular cosmetic ones, for keratin materials, in particular for the care and/or makeup of the skin and/or lips, eyelashes, eyebrows including:

- at least one compartment containing at least one ingredient i) of formula (I) or (Ia) as defined above and optionally at least iii) a cosmetic active ingredient, in particular comprising composition C1 as defined above;

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

- optionally, at least one compartment distinct from those which contain i) and ii) and containing iii) at least one cosmetic active ingredient, identical or different from that/those possibly contained in the compartments comprising i) and ii) and such as defined previously, in particular containing the composition C5.

The invention is illustrated in more detail in the following examples. Quantities are indicated in weight percentage.

Examples

Compound 1: KLEX 7301 marketed by KING industry

[Chem. 5]:

Compound 2 Glucose with acetoacetate function (5eq)

Compound 2 was synthesized according to the following scheme:

[Chem. 6]:

Scheme in which R1, identical or different, represents a hydrogen atom or a -methylcarbonylmethylcarbonyl group -C(O)-CH ₂ -C(O)-CH ₃ , it being understood that at least two radicals R1 represent -C(O) -CH ₂ -C(O)-CH ₃ .

In a 1 liter three-necked bottle equipped with mechanical stirring and a distillation column, 100 g of D-glucose and 482.90 g of tert-butyl acetoacetate are introduced. The reaction medium is heated using an oil bath (oil bath temperature 140°C-150°C) for 5 h. After 5 h, NMR confirms the grafting of the acetoacetate function. The reaction medium is then concentrated in a rotavapor at 150°C under continuous vacuum. A very viscous dark brown liquid is obtained, corresponding after analysis to the expected product.

Compound 3 Mannose with acetoacetate function (5 eq)

Scheme in which R1, identical or different, represents a hydrogen atom or a group -C(O)-CH ₂ -C(O)-CH _3, it being understood that at least two radicals R1 represent -C(O)-CH ₂ -C(O)-CH ₃ .

In a 1-liter three-necked bottle equipped with mechanical stirring and a distillation column, 100 g of D-mannose and 482.90 g of tert-butyl acetoacetate are introduced. The reaction medium is heated using an oil bath (oil bath temperature 140°C-150°C) for 5 h. After 5 h, NMR confirms the grafting of the acetoacetate function. The reaction medium is then concentrated in a rotavapor at 150°C under continuous vacuum. We obtain a viscous yellow liquid corresponding after analysis to the expected product.

Compound 4 Xylitol with acetoacetate function (5eq)

Scheme in which R1, identical or different, represents a hydrogen atom or a group -C(O)-CH ₂ -C(O)-CH _3, it being understood that at least two radicals R1 represent -C(O)-CH ₂ -C(O)-CH ₃ .

In a 500 ml three-necked bottle equipped with mechanical stirring and a distillation column, 25 g of xylitol and 142.69 g of tert-butyl acetoacetate are introduced. The reaction medium is heated using an oil bath (oil bath temperature 140°C-150°C) for 5 h. After 5 h, NMR confirms the grafting of the acetoacetate function. The reaction medium is then concentrated in a rotavapor at 150°C under continuous vacuum. A very viscous brown liquid is obtained, corresponding after analysis to the expected product.

Compound No. 5 Sorbitol with acetoacetate function (6eq)

Scheme in which R1, identical or different, represents a hydrogen atom or a group -C(O)-CH ₂ -C(O)-CH _3, it being understood that at least two radicals R1 represent -C(O)-CH ₂ -C(O)-.

In a 1-liter three-necked bottle equipped with mechanical stirring and a distillation column, 100 g of sorbitol and 573.20 g of tert-butyl acetoacetate are introduced. The reaction medium is heated using an oil bath (oil bath temperature 140°C-150°C) for 5 h. After 5 h, NMR confirms the grafting of the acetoacetate function. The reaction medium is then concentrated in a rotavapor at 150°C under continuous vacuum. An orange-yellow viscous liquid is obtained, corresponding after analysis to the expected product.

Compound No. 6 Sorbitol with acetoacetate function (3eq)

Scheme in which R1, identical or different, represents a hydrogen atom or a group -C(O)-CH ₂ -C(O)-CH _3, it being understood that at least two radicals R1 represent -C(O)-CH ₂ -C(O)-CH ₃ .

In a 1-liter three-necked bottle equipped with mechanical stirring and a distillation column, 100 g of sorbitol and 260.54 g of tert-butyl acetoacetate are introduced. The reaction medium is heated using an oil bath (oil bath temperature 140°C-150°C) for 5 h. After 5 h, NMR confirms the grafting of the acetoacetate function. The reaction medium is then concentrated in a rotavapor at 150°C under continuous vacuum. A yellow viscous liquid is obtained, after analysis, corresponding to the expected product.

Implementation of the invention

Implementation in 1 gesture:

The compounds of formula (I) 1 to 6 with acetoacetate functions and the crosslinking agents 1 to 10 are mixed together before application to Bioskin synthetic skin from Maprecos (Bioskin plate #10) (equivalent elastomer skin support). The system remains fluid long enough to allow application to the substrate. After application to a sample of Bioskin synthetic skin and evaporation of the volatile solvents, non-transferable, non-sticky deposits resistant to edible oils, sebum and water are obtained for application on said synthetic skin.

Implementation in 2 steps: application of base coat A then top coat A or application of base coat B then top coat B

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

A composition, of the “top coat” type, containing a crosslinking compound is then applied. After 24 hours of drying, the deposits obtained are evaluated

Base coat A: deposit of a compound 1 to 6 with acetoacetate functions alone or diluted in volatile solvents such as ethanol, water, isododecane or an isododecane/Ethanol or Ethanol/water mixture. Optionally a crosslinker can be introduced in this phase to carry out pre-crosslinking.

OR

Base Coat B: deposit of a crosslinking agent 1 to 10.

Top coat A: deposit with a crosslinking agent 1 to 10.

OR

Top coat B: deposit of a compound 1 to 6 with acetoacetate functions alone or diluted in volatile solvents such as ethanol, water, isododecane or an isododecane/Ethanol or Ethanol/water mixture.

The base coat compositions comprising the compound(s) 1 to 6 with acetoacetate functions (base coat A) or the crosslinking agent(s) 1 to 10 (base coat B) were applied to an in vitro support of the Bioskin type using a film draw (wet thickness 100µm). The deposit is left to dry for 24 hours.

The new material generated makes it possible to obtain, after evaporation of volatile solvents, non-transferable, non-sticky deposits that are resistant to edible oils, sebum and water for skin application.

Tape resistance

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 an object slide in order to clearly observe the result. The adhesion of the film to the support is thus evaluated.

Resistance to olive oil/water/sebum

0.5 mL of olive oil or water is applied to the formulation film. After 5 minutes, the olive oil, water and sebum are removed using 15 passes with a cotton pad. We thus look at the deterioration of the film following contact with the drop of attackers.

Fragmentation test of formulations on Bioskin

As with the olive oil and tape resistance tests, films are applied to a sample of Bioskin. After a day of drying, the bioskin plate is stretched 10 times by hand.

Then the result can be observed on the formulation film (fragmentation or not).

For each combination, evaluations were carried out for the base coat alone after drying and on the [Base coat] + [Top coat] system after drying.

The evaluation is done as follows:

+++: Cosmetic property evaluated as very efficient

++: Cosmetic property rated as moderately efficient

+: Cosmetic property rated poorly performing

0: Cosmetic property assessed as non-performing

Resistance to olive oil, sebum and water

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

Resistance is evaluated according to the following scale:
+++: no attack on the deposit which is as originally;
++: a little transfer but the deposit is as originally;
+: the deposit is a little altered and a little transfer is noted;
0: the deposit is completely degraded and there is a lot of transfer to the cotton.

Example 1: Compound 1 with ACAC functions with the amine crosslinker 1 in ethanol – 1 step

[Table 1]: Ingredients Composition A° (% ma*) Composition A (% ma*) Compound 1 with ACAC function 10 10 Crosslinker 1 amine - 10 Pigment: iron oxide 3 3 Ethanol 87 77 * active ingredient

Result after application in 1 gesture:

[Table 2]: Properties Fragmentation Resistance
Olive oil Water Resistance Sebum resistance Comp. HAS 0 0 0 0 Comp. HAS' +++ +++ +++ +++

It appears that the application of composition A according to the process of the invention makes it possible to significantly improve the persistence with respect to olive oil, sebum and water. In addition, the fragmentation test is significantly better than that obtained with the reference composition A°.

Example 2: Molecule 1 crosslinked with amino compound 1 in isododecane/ethanol – 1 action

[Table 3]: Ingredients Composition B (% ma*) Compound 1 with ACAC function 20 Crosslinker 1 amine 20 Pigment: iron oxide 3 Isododecane 15 Ethanol 42 * active ingredient

Result after application in 1 gesture:

[Table 4]: Properties Fragmentation Resistance
Olive oil Water Resistance Sebum resistance Comp. B +++ +++ +++ +++

It appears that the application of composition B according to the process of the invention makes it possible to obtain very effective cosmetic performances.

Example 3: Compound 1 with amine crosslinker 2 in hydroalcoholic solvent – 1 step

[Table 5]: Ingredients Composition C (% ai) Compound 1 with ACAC function 20 APTES 2-amino crosslinker 20 Pigment: iron oxide 3 Water (pH = 1) 6 Ethanol 51 Result after application in 1 gesture:

[Table 6]: Properties Resistance
Olive oil Water Resistance Sebum resistance Comp. VS +++ +++ +++

It appears that the application of composition C according to the process of the invention makes it possible to obtain very effective persistence with water, olive oil and sebum.

Example 4: Compound 6 with ACAC function with crosslinker 8 Polyacrylate + catalyst – 1 step

[Table 7]: Ingredients Composition D° (% ma*) Composition D (% ma*) ACAC-functioning compound 6 25 25 Crosslinker 8 polyacrylate - 17 Pigment: iron oxide yellow 5 5 1,8-Diazabicyclo-[5.4.0]undec-7-ene - 0.5 water/ethanol 50/50 v/v 70 52.5 * active ingredient,

Result after application in 1 gesture:

[Table 8]: Properties Tape test Fragmentation Resistance
Olive oil Water Resistance Comp. D° 0 0 0 0 Comp. D +++ +++ +++ +++

It appears that the application of composition D according to the process of the invention makes it possible to significantly improve the persistence with respect to olive oil and water. In addition, the tape and fragmentation tests are significantly better than those obtained with the reference composition D°.

Example 5: Compound 6 with dicarbonyl crosslinker 9 + catalyst – 1 step

[Table 9]: Ingredients Composition E° (% ma*) Composition E (% ma*) ACAC-functioning compound 6 25 25 Crosslinker 9 dicarbonyl - 11.6 1,8-Diazabicyclo[5.4.0]undec-7-ene - 0.5 Pigment: iron oxide yellow 5 5 Water/ethanol 50/50 v/v 70 57.9 * active ingredient,

Result after application in 1 gesture:

[Table 10]: Properties Tape test Fragmentation Resistance
Olive oil Resistance
Water Comp. E° 0 0 0 0 Comp. E +++ +++ +++ +++

It appears that the application of composition E according to the process of the invention makes it possible to obtain a very efficient persistence of olive oil, and the scotch and fragmentation tests are also very efficient.

Example 6: Compound 3 with ACAC function with amine crosslinker 3 then with amine crosslinker 6 – 2 steps

[Table 11]: Ingredients Composition F° (% g ai*) Composition F (% g ai*) ACAC-functioning compound 3 25 25 D&C Red 7 5 5 3 amine crosslinker - 5 Solvent: Water/ethanol 70 65 * active ingredient

[Table 12]: Ingredients Composition G (% ma*) ^2nd GESTURE 6 amine crosslinker 5 Isododecane 95 * active ingredient

Result after application in 1 or 2 steps: Properties Tape test Fragmentation Resistance
sebum Composition F then G (2 gestures) +++ ++ ++ F° composition (1 gesture) 0 + 0 It appears that the application of composition F then G in 2 steps according to the process of the invention makes it possible to obtain a very effective afterglow with olive oil and sebum. The same goes for the tape and fragmentation tests which are efficient.

Example 7: Compound 3 with ACAC function with amine crosslinker 3 then amine crosslinker 4 – 2 steps

[Table 13]: Ingredients Composition F (% g ai*) ^1st GESTURE ACAC-functioning compound 3 25 D&C Red 7 5 3 amine crosslinker 5 Solvent: Water/ethanol 65

[Table 14]:

[Table 15]: Ingredients H composition (% ma*) ^2nd GESTURE 4 amine crosslinker 5 Water 95 * active ingredient

Result after application in 2 steps:

[Table 16]: Properties Fragmentation Resistance
Olive oil Resistance
sebum Composition F then H ++ +++ ++ It appears that the application of composition F then H in 2 steps according to the process of the invention makes it possible to obtain a high-performance persistence of olive oil and sebum. The same goes for the fragmentation test.

Example 8: Compound 3 with ACAC function with amine crosslinker 3 then thiolated crosslinker 7 – 2 steps

The process was carried out as in Example 7 with a first gesture carried out with composition F except that the second gesture was carried out with composition I instead of composition H.

[Table 17]: Ingredients Composition I (% ma*) ^2nd GESTURE Thiolated crosslinker 7 5 Isododecane 95 * active ingredient

Result after application in 2 steps:

[Table 18]: Properties Tape test Fragmentation Resistance
Olive oil Resistance
sebum Resistance
water Composition F then I +++ ++ +++ +++ +++ Example 9: Compound 1 with ACAC functions with amine crosslinker 3 then then amine crosslinker 3 – 2 steps

[Table 19]: Ingredients Composition J° (% g ai*) Compound 1 with ACAC function 25 D&C Red 7 5 Solvent: Water/ethanol 70

[Table 20]: Ingredients Composition J (% g ai*) ^1st GESTURE Compound 1 with ACAC function 25 D&C Red 7 5 3 amine crosslinker 12 Water/ethanol 63

[Table 21]: Ingredients Composition K (% ma*) ^2nd GESTURE 3 amine crosslinker 5 Water 95 * active ingredient

Result after application in 1 gesture and 2 gestures:

[Table 22]: Properties Tape test Fragmentation Resistance
olive oil Resistance
sebum Water resistance Compositions J then K
(2 gestures) +++ +++ ++ +++ ++ Composition J° 0 0 0 0 0 It appears that the application of composition J then K in 2 steps according to the process of the invention makes it possible to obtain a persistence of olive oil, sebum and water that is significantly more efficient than the process in a gesture implementing the composition J°. The same goes for fragmentation and tape tests.

Remanence of shine

Gloss retention test

The compositions comprising a compound with acetoacetate functions, a crosslinker and a solvent are applied using a wet 100 μm thick applicator on a lénéta plate. Using a gloss meter, we measure the gloss at 20° (angle of incidence) of the card then the gloss of the deposit 2 hours after application, 24 hours after application, then on the deposit 0.5 ml of water are deposited for 5 minutes then we rub with a cotton pad (15 passes) we measure the shine on the attacked area.

Example 10: Compound 1 with ACAC functions with an amine crosslinker 3

[Table 23]: Composition L % my Compound 1 with ACAC functions 20 3 amine crosslinker 17 Ethanol 63 * my active ingredient

[Table 24]: Composition
L Leneta card shine (UB) Shine after 2H (UB) Shine after 24 hours (UB) Shine after rubbing (UB) Result 45.2 65.3 64.4 62.2 Vs. Gloss Scale Weakly shiny Bright Bright Bright (UB) = Unit of brilliance

We notice a persistence of the shine of the film after attack with water, or after rubbing is effective.

Claims (20)

Process for treating keratin materials, in one or more stages by application to said materials of:
i) one or more compounds of formula (I) as well as its optical isomers, geometric isomers, its salts, and its solvates such as hydrates:

Formula (I) in which:

• R ¹ represents a versatile C ₂ to C ₁₄ hydrocarbon radical, linear or branched, saturated or unsaturated, conjugated or not, acyclic or cyclic, aromatic or not,

R¹being further:
a) optionally substituted by one or more hydroxy groups OH, amine -N(R)₂, with R representing a group (C₁-VS₄)alkyl such as methyl, or carboxy -C(O)-OH, a vinyl group, and/or
b) optionally interrupted by one or more heteroatoms or groups chosen from O, S, carbonyl -C(O)-, amine -N(R'), or their associations, in which R' represents a hydrogen atom, a group linear or branched alkyl having from 1 to 4 carbon atoms optionally substituted by at least one hydroxyl group (OH), or optionally substituted by -X-C(O)-C(R_has)(R_b)-HORN²;

• R ² represents a monovalent C ₁ to C ₆ hydrocarbon radical, linear or branched, saturated or unsaturated, preferably a (C ₁ -C ₄ ) alkyl group such as methyl or tert -butyl, more preferably methyl;
• R ^a , and R ^b , identical or different, represent a hydrogen atom or a (C ₁ -C ₄ ) alkyl group, preferably hydrogen;
• _- -N(R')-, -N(R')-C(O)-O-, -N(R')-C(O)-N(R')-;
• n designates an integer ranging from 2 to 10, particularly from 3 to 8; And

ii) at least one crosslinking agent; And
iii) optionally at least one cosmetic active ingredient. Process according to the preceding claim in which the compound(s) of formula (I) is(are) chosen from those of formula (Ia) as well as their optical isomers, geometric isomers, their salts, and their solvates such as hydrates :
(Ia)
Formula (Ia) in which:

• R ¹ is as defined in claim 1, particularly represents a versatile hydrocarbon radical in C ₂ to C ₁₄ , particularly in C ₃ -C ₁₂ , preferably in C ₄ -C ₁₀ , linear or branched, saturated or unsaturated , conjugated or not, acyclic or cyclic, aromatic or not, R ¹ also being:

a) optionally substituted by one or more hydroxy OH groups, and/or
b) optionally interrupted by one or more heteroatoms or groups chosen from O, S, -N(R’), preferably interrupted by one or more oxygen atoms in which R’ is as defined in claim 1;

• R ² is as defined in claim 1, preferably R ² represents a (C ₁ -C ₆ ) alkyl group, linear or branched, preferably a (C ₁ -C ₄ ) alkyl group such as methyl or t-Butyl preferably methyl; And
• n being as defined in claim 1, preferably n denotes an integer ranging from 2 to 8.

Process according to any one of the preceding claims in which the compound(s) of formula (I) or (Ia) is(are) such that:
R ¹ represents a versatile C ₆ to C ₈ hydrocarbon radical, linear or branched, unsaturated monocyclic or bicyclic, preferably monocyclic, and aromatic such as phenyl, or
R ¹ represents a versatile C ₅ to C ₁₂ hydrocarbon radical, saturated monocyclic or bicyclic, optionally interrupted by one or more heteroatoms, one or more heteroatoms or groups chosen from O, S, -N(R'), in which R' represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, preferably interrupted by one or more oxygen atoms; preferably R ¹ represents a mono-saccharide or polysaccharide unit, in particular disaccharide on which n hydroxy groups have been substituted by n groups -OC(O)-CH ₂ -C(O)-R ² with R ² and n as defined in any preceding claim, or
R ¹ represents a versatile acyclic hydrocarbon radical in C ₂ to C ₁₂ , preferably in C ₃ -C ₁₀ , linear or branched, saturated or unsaturated, preferably saturated;
preferably R ¹ represents a mono-saccharide or polysaccharide unit, in particular disaccharide on which n hydroxy groups have been substituted by n groups -OC(O)-CH ₂ -C(O)-R ² with R ² as defined previously and n as defined previously. Process according to any one of the preceding claims in which the compound(s) of formula (I) or (Ia) is(are) such that:
n designates an integer ranging from 2 to 8, more particularly n designates an integer ranging from 3 to 6, more particularly from 3 to 5. Process according to any one of the preceding claims in which the compound(s) of formula (I) or (Ia) is(are) chosen from:




















in which R1 identical or different represents a hydrogen atom or a group -C(O)-CH ₂ -C(O)-CH _3, it being understood that at least two radicals R1 represent -C(O)-CH ₂ -C(O)-CH ₃ , preferably at least three radicals R1 represent -C(O)-CH ₂ -C(O)-CH ₃ ,
More preferably the compounds chosen from (18), (41) and (44). Process according to any one of the preceding claims in which the crosslinking agent(s) ii) is(are) chosen from the compounds:
(poly) amines, (poly) thiolated, (poly) carbonyl, (poly) acrylates, and/or metal alkoxide, (and mixtures thereof, and preferably chosen from (poly) amine, (poly) thiolated and (poly) )acrylates and their mixtures. Process according to any one of the preceding claims in which the crosslinking agent(s) is(are) chosen from the compounds

• (poly) amines chosen from a) chitosans such as poly(D-Glucosamine), b) polyether diamines, particularly polyethylene glycol α, ω-diamine (with amine function at the end of the chain) and 4,7,10- Trioxa-1,1-tridecanediamine, c) polyether triamines such as Polyetheramine (or jeffamine), d) aminoalkoxysilanes such as APTES and e) polydialkylsiloxanes comprising primary amine groups at the end of the chain or on particularly side chains polidimethylsiloxanes comprising primary amine groups such as poly(dimethoxysiloxane) terminated by bis(3-aminopropyl) (PDMS-diNH ₂ ) and amodimethicones comprising amine groups on side chains such as bis-cetearyl amodimethicone; And
• (poly) thiols chosen from a) polydialkylsiloxanes with thiol functions, and b) alkoxysilanes with thiol functions, particularly are chosen from a) polydialkylsiloxanes with thiol functions preferentially and polydimethysiloxanes comprising thiol groups on the side chain (such as mercaptopropyl) in particular those of formula (XIII)

R^has-If(R^b)(R^d)-O-[Si(R^has)(R^b)-O]_m-[If(R^b)(ALK₁-SH)-O]_not-If(R^b)(R^d)-R^has(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 group (C ₁ -C ₆ )alkyl such as methyl,
• R ^d may also represent a (C ₁ -C ₆ ) alkyl group substituted by a (C ₁ -C ₄ ) alkylamino or amino group, or thiol, preferably (C ₁ -C ₄ ) alkyl such as methyl;
• ALK ₁ represents a divalent hydrocarbon chain comprising 1 to 100 carbon atoms, saturated or unsaturated, linear or branched, optionally cyclic, optionally interrupted by one or more heteroatoms such as oxygen, sulfur or nitrogen (in particular O), a group ( _thio )carbonyl C( _X ) with -C ₆ )alkylene, more preferably (C ₁ -C ₄ )alkylene such as propylene;
• n and m, identical or different, representing an integer greater than 2 and more particularly the values of m and n are such that the weight average molecular weight of said polyorganosiloxane is between 1000 and 55000 g.mol ^-1 ;

• (poly)acrylate 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, preferably n is inclusively between 2 and 10, preferably between 2 and 5;
• L designates a multivalent group (at least divalent), in particular comprising between 1 and 500 carbon and/or silicon atoms, more particularly between 2 and 40 carbon and/or silicon atoms, even more particularly between 3 and 30 atoms carbon and/or silicon, preferably between 6 and 20 carbon atoms, linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated;
  L being optionally interrupted and/or terminated by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their associations such as –O-, –OC(X)-, -N(R )-C(X)-, -Si(R _c )(R _d )-O- with R representing a hydrogen atom or a (C ₁ -C ₆ ) alkyl group such as methyl; and or

L being optionally substituted by one or more 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, represent an atom of oxygen, sulfur, or a group N(R_b) ; a, and b worth 0 or 1, preferably the sum of a + b is worth 1;
R_hasand R_b, identical or different, represent a hydrogen atom, or a group (C₁-VS₆)alkyl, or aryl(C₁-VS₄)alkyl such as benzyl, preferably R_hasand R_brepresent a hydrogen atom; and R_vsand R_d, identical or different, represent a group (C₁-VS₆)alkyl, aryl(C₁-VS₄)alkyl or (C₁-VS₆)alkoxy.

• R ^e representing a hydrogen atom or (C ₁ -C ₄ ) alkyl group such as methyl, preferably R ^e represents a hydrogen atom, and
• Y representing an oxygen atom or an amino group -N(H)-, preferably O being as defined above, preferably Y = O and R ^e = H, preferably L represents a di or trivalent hydrocarbon chain, preferably trivalent, comprising from 1 to 8 carbon atoms, q is 2 or 3, preferably 3, Y represents O, and R ^e represents a hydrogen atom;

preferably the compounds of formula (XIV) are trimethylolpropane triacrylate. Process according to any one of the preceding claims which uses iii) one or more cosmetic agent(s) chosen from a) coloring materials such as pigments, direct dyes and their mixtures, b) active ingredients for the care of keratin materials, preferably the skin, c) UV filters, and d) their mixtures; preferably the at least one cosmetic agent is chosen from coloring materials, preferably chosen from pigments, direct dyes and mixtures thereof, more preferably the pigment(s) of the invention are chosen from carbon black, oxides of iron 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 red lithol such as the calcium salt of lithol red B, even more preferably red iron oxides, yellow iron oxides and azo pigments, particularly red ones, such as D&C RED 7. Process according to any one of the preceding claims which uses iv) one or more fatty substances, particularly one or more preferably volatile oils. Process according to any one of the preceding claims which uses iv) one or more volatile oil(s) chosen from:
* hydrocarbon oils having 8 to 16 carbon atoms, and in particular:
- branched C ₈ -C ₁₆ alkanes such as isoalkanes such as iso-alkanes such as C ₁₃ -C ₁₆ Isoparaffin, isododecane, isodecane, isohexadecane, alone or in mixtures, preferably isododecane , more preferably isododecane;
- linear alkanes for example C ₁₁ -C ₁₆ , alone or in mixtures, for example such as hexane, decane, undecane, tridecane, isoparaffins such as, or n-dodecane (C12) and n-tetradecane (C14), undecane-tridecane mixture, mixtures of n-undecane (C11) and n-tridecane (C13), and mixtures thereof as well as mixtures of n -undecane (C11) and n -tridecane (C13);
- cyclic, non-aromatic, C ₅ -C ₁₂ volatile alkanes;
* short-chain esters having 3 to 8 carbon atoms in total such as 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 designate a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably an alkyl group in C ₄ -C ₈ , advantageously chosen from dibutylcarbonate or dipentylcarbonate;
* ether oils of formula R ₁ -OR ₂ in which R ₁ and R ₂ independently designate a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably a C ₄ -C ₈ alkyl group;
*silicone oils comprising in particular, from 2 to 7 silicon atoms, these silicone oils comprising, optionally, alkyl or alkoxy groups having from 1 to 10 carbon atoms, such as dimethicones with viscosity 5 and 6 cSt, cyclopentadimethylsiloxane , dodecamethylpentasiloxane, cyclohexadimethylsiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, do decamethyl pentasiloxane, and their mixtures;
more preferably the volatile oil(s) iv) are chosen from C ₈ -C ₁₆ alkanes, in particular branched, such as isododecane. Method according to any one of the preceding claims in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows which implements:

• a composition, called “C1”, comprising i) at least one compound of formula (I) or (Ia) as defined in any one of claims 1 to 5 and optionally iii) at least one cosmetic active ingredient as defined in any one claims 1 or 8;
• a composition, called “C2”, comprising i) at least one compound of formula (I) or (Ia) as defined in any one of claims 1 to 5 and ii) at least one crosslinking agent as defined in any one of claims 1, 6 or 7 and optionally iii) at least one active ingredient as defined in any one of claims 1 or 8;
• a composition, called “C3”, comprising i) at least one compound of formula (I) or (Ia) as defined in any one of claims 1 to 5, ii) at least one crosslinking agent as defined in any one of claims 1, 6 or 7 and iii) at least one cosmetic active ingredient as defined in any one of claims 1 or 8; and or
• a “C4” composition comprising ii) at least one crosslinking agent as defined as defined in any one of claims 1, 6 or 7 and optionally iii) at least one cosmetic active ingredient as defined in any one of claims 1 or 8;
• a “C5” composition comprising iii) at least one cosmetic active ingredient as defined in any one of claims 1 or 8 and below;

Being heard that :

• the process uses together or separately i) at least one compound of formula (I) or (Ia) as defined in any one of claims 1 to 5 and ii) at least one crosslinking agent as defined in any one of claims 1, 6 or 7; And
• the compositions C1, C2, C3, C4 and C5 may be anhydrous, aqueous such as hydroalcoholic and/or comprise one or more fatty substances iv) as defined in claims 9 or 10.

Method according to claim 11 which is carried out in one step by application of composition C2 or C3 as defined in claim 11 to keratin materials. Process according to claim 11 which is carried out in two steps by successive application, on keratin materials, of two different compositions for example C1 and C4, or C2 and C4, or C3 and C4, preferably C1 then C4, C2 then C4 , or C3 then C4 as defined in claim 11. Method according to claim 11 which is carried out in three steps by successive applications, on keratin materials,

• either α) of a composition C1, then β) of a composition C4, then γ) of a composition C5 as defined in claim 11, preferably C1 then C4 respectively C5 then C5 respectively C4;
• either α) of a composition C4, and β) of a composition C1 or C2, and then γ) of a composition C5 as defined in claim 11, preferably the composition C4 is applied before the composition C1.

Method according to claim 11 or 13 which is a process for making up keratin materials, in particular the skin, in particular the lips, eyelashes or eyebrows, comprising the sequential application:
- a composition C1 as defined in claim 11; Then
- a C4 composition as defined in claim 11;
it being understood that compositions C1 and/or C4 contain at least one coloring material as defined in claim 8, preferably at least one pigment. more preferably composition C1 comprises at least one pigment;
Or
- a composition C1 as defined in claim 11; Then
- a C4 composition as defined in claim 11; Then
- a C5 composition as defined in claim 11;
it being understood that compositions C1 and/or C4 and/or C5 contain at least one coloring material as defined in claim 8, preferably at least one pigment, more preferably composition C5 comprises at least one pigment. Composition C1, as defined in claim 11, preferably aqueous or hydroalcoholic, which comprises i) at least one compound of formula (I) or (Ia) as defined in any one of claims 1 to 5 and iii) optionally at at least one active ingredient as defined in claim 1 or 8, preferably at least one coloring material, such as at least one pigment; and optionally iv) one or more fatty substances as defined in claim 9 or 10. Composition C2, as defined in claim 11, preferably aqueous or hydroalcoholic, which comprises i) at least one compound of formula (I) or (Ia) as defined in any one of claims 1 to 5, ii) at least a crosslinker as defined in any one of claims 1, 6 or 7 and iii) optionally at least one active ingredient as defined in claim 1 or 8; and optionally iv) one or more fatty substances as defined in claim 9 or 10. Composition C3 as defined in claim 11, which comprises iii) one or more cosmetic active ingredient(s) as defined in claim 1 or 8 and optionally iv) one or more fatty substances such as (s) as defined in claim 9 or 10. Cosmetic use of the composition C1, C2 or C3 according to claim 16 to 18, in particular for the treatment of keratin materials, in particular for the makeup of keratin materials in particular the skin such as lips, eyelashes or eyebrows. Kit with several compartments, particularly cosmetic, including:
- at least one compartment containing at least one ingredient i) of formula (I) or (Ia) as defined in any one of claims 1 to 5 and optionally at least iii) a cosmetic active ingredient as defined in any one of claims 1 or 8, in particular comprising composition C1 as defined in claim 11;
- at least one compartment distinct from that which contains i) and containing ii) at least one crosslinking agent as defined in any one of claims 1, 6, and 7 optionally iii) at least one cosmetic active ingredient as defined in any one of claims 1 or 8, in particular containing composition C4 as defined in claim 11; And
- optionally, at least one compartment distinct from those which contain i) and ii) and containing iii) at least one cosmetic active ingredient as defined in any one of claims 1 or 8, identical to or different from that/those possibly contained) in the compartments comprising i) of formula (I) or (Ia) as defined in any one of claims 1 to 5 and ii) at least one crosslinking agent as defined in any one of claims 1, 6, and 7.