FR3142898A1 - Process for treating keratin materials using at least one polysaccharide compound with acetoacetate functions - Google Patents

Abstract

Process for treating keratin materials using at least one polysaccharide compound with acetoacetate functions The present invention relates to a process for treating keratin materials, comprising the application to said keratin materials, in one or more successive steps, of at least i) one or more compounds of formula (I) as well as their optical, geometric isomers , their acid or base salts, and/or solvates, such as hydrates, or a composition containing them: (I) formula (I) in which X, R1, R2, Ra, Rb, and n are as defined in the description, optionally ii) at least one crosslinking agent, iii) optionally water. Figure for abstract: None

Description

Process for treating keratin materials using at least one polysaccharide compound with acetoacetate functions

The present invention relates more particularly to the cosmetic field of keratin materials, and in particular to that of the care and/or makeup of the skin and/or lips and/or eyelashes and/or eyebrows, and that of the care, styling and/or coloring of keratin fibers and preferably of the hair.

It thus aims to propose in particular new treatment processes, in particular cosmetic ones, comprising the application to keratin materials of an oligosaccharide/polysaccharide compound with acetoacetate functions, and possibly a crosslinking agent, which are particularly interesting with regard to their technical performances, in particular in terms of the resistance of the deposits which they allow to be obtained, and the sensory sensations which they provide to the user.

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

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

It must also have good resistance to contact with water, particularly rain or showering, or even perspiration, as well as sebum, or even contact with fatty substances in foods, particularly cooking oils when this deposit is formed on the lips. In addition, this deposit must be comfortable. Depending on the applications or consumer requests, we are also looking for deposits for which the appearance can be varied from shiny to matte.

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

However, the compositions of the prior art have a resistance over time, in particular styling, which is not always satisfactory.

There is also a significant demand from consumers for the use of more natural compositions, using compounds of natural origin that may have been modified.

Furthermore, in the hair sector, a new range of products called hair make-up or "Hair Make-up" has recently been developed. These products guarantee temporary hair coloring that lasts after 1 to 3 shampoos.

They therefore constitute an alternative, particularly attractive for consumers, to permanent coloring, provided of course that the color effect is effectively guaranteed to last in contact with water and a few shampoos.

This requirement is also notably met thanks to the implementation of effective film-forming agents.

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

Thus, document FR 2 741 530 proposes for this purpose, for the temporary coloring of keratin fibers, the use of a dispersion of film-forming polymer particles comprising at least one acid function and at least one pigment dispersed in the continuous phase of said dispersion. The colorings obtained by this coloring method nevertheless have the disadvantage of being easily removed by shampooing.

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

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

Also known from WO 2020/026143 are processes for preparing compositions comprising modified polysaccharides. 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 a hydrogel. US3342806 and US 3361585 describe acetoacetylated starch compounds.

In general, the processes and treatments described above do not allow access to deposits, both on keratin fibres and on the skin and lips, which satisfy all of the aforementioned requirements, namely very good resistance to water, in particular to hair shampoos, and/or to fatty substances, in particular for the lips, which are also comfortable to wear for users, which allow adjustment of shine or matt or invisibility qualities and which, in the case of hair use, provide very satisfactory styling hold or colour persistence while meeting the need for naturalness expressed by certain consumers and/or formulations where the presence of a fatty phase is not desired.

There is therefore a need for a treatment process, particularly cosmetic, intended for application to the skin which makes it possible to obtain a non-sticky deposit, which transfers little, if at all, shiny or matt, comfortable, long-lasting and the implementation of which does not necessarily require the presence of an oily phase, while being of natural origin.

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

There also remains a need for a treatment process, particularly cosmetic, to provide deposits with qualities of shine, and/or mattness, and/or invisibility.

There also remains a need for a treatment process, particularly cosmetic, coloring and intended for hair application, which makes it possible to provide deposits with good resistance to water and shampoos to guarantee color retention over time comparable to direct coloring.

There is also a need for a treatment process, in particular cosmetic, in particular non-coloring, intended for hair application which provides styling properties, in particular curl hold, which are resistant to water.

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, comprising the application to said keratin materials, in one or more successive steps, of at least:

(i) one or more compounds of formula (I) and their optical or geometric isomers, their acid or base salts, and/or solvates, such as hydrates, or a composition containing it or them:

(I)

formula (I) in which:

- R ¹ represents a multivalent, linear or cyclic polysaccharide radical, preferably linear, consisting of at least 3 monosaccharide units, each comprising at least 5 carbon atoms, particularly between 7 and 9 carbon atoms, preferably at least 6 carbon atoms, more particularly between 6 and 8 carbon atoms, and more preferentially 6 carbon atoms, and of which one or more of the hydroxy (-OH), carbonyl (-C(O)), carboxy (-C(O)-OH) or amino -NH ₂ groups, of all or part of at least one of the monosaccharide units, are optionally substituted by one or more R ³ groups;

- 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, more preferably methyl;

- R ³ , identical or different, represents a group chosen from:

1) sulfonate -SO ₃ ^- , Cat ⁺ ,

2) (C ₁ -C ₂₂ )alkyl, linear or branched, and

3) (C ₁ -C ₂₂ )alkylcarbonyl, linear or branched,

the (C ₁ -C ₂₂ )alkyl group being optionally interrupted by one or more heteroatoms or X groups as defined below; and/or

the group (C₁-C₂₂)alkyl being optionally substituted by one or more groups chosen from: a) hydroxy (-OH); b) sulfonate -SO₃ ^-, Cat⁺ ; c) sulfate -O-SO₃ ^-, Cat⁺; d) -(CH₂-CH₂-O)_p-R⁴ ; e) –O-(CH₂-CH₂-O)_p-R⁴ ; f) -C(O)-R⁴ ; g) -C(O)-O-R⁴ ; h) -O-C(O)-R⁴ ; i) -C(O)-N(R’)-R⁴ ; j) -N(R’)-C(O)-R⁴ ; k) ammonium -N⁺R’’₃; An^-and l) their mixtures;

- R⁴represents a hydrogen atom, a group (C₁-C₈)alkyl, linear or branched _,preferably R⁴represents a hydrogen atom or a group (C₁-C₆) linear or branched alkyl, more preferably a group (C₁-C₄) linear or branched alkyl, in particular methyl;

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

- X is a heteroatom or group selected from -O-, -S-, -N(R’)-, and combinations thereof such as -C(O)-O-, -O-C(O)-, -C(O)-N(R’)-, -N(R’)-C(O)-, -N(R’)-C(O)-O-, -N(R’)-C(O)-N(R’)-, preferably X represents -O-;

- R', identical or different, represents a hydrogen atom, a (C ₁ -C ₆ )alkyl group, linear or branched, optionally substituted by at least one hydroxyl group (OH), preferably R' represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, in particular methyl, more preferably R' represents a hydrogen atom;

- R'', identical or different, represents a hydrogen atom or a linear or branched (C ₁ -C ₆ )alkyl group, preferably a (C ₁ -C ₄ )alkyl group, in particular methyl;

- n denotes an integer ranging from 2 to 3000, in particular from 5 to 2500, more particularly from 10 to 2300, preferably from 15 to 1000, preferentially from 20 to 500, and more preferentially from 25 to 200;

- p denotes an integer ranging from 0 to 3;

- An ^- represents an anionic counterion;

- Cat ⁺ represents a cationic counterion;

ii) optionally at least one crosslinking agent; and

iii) optionally water, preferably water, or optionally water mixed with a polar organic solvent, preferably chosen from (C ₂ -C ₆ )alkanol, more preferably ethanol.

According to a preferred embodiment, the treatment method according to the invention comprises the application of at least iii) water.

According to a preferred embodiment, the treatment method according to the invention further comprises the application of at least iv) a cosmetic active ingredient, to said keratin materials.

According to a preferred embodiment, the method according to the invention comprises the application i) of at least one compound of formula (I), its optical, geometric isomers, its acid or base salts, and/or its solvates, such as hydrates, or of a composition containing it or them, optionally the application ii) of at least one crosslinking agent, iii) optionally water and the application iv) of at least one cosmetic active agent, on said keratin materials.

According to one embodiment, the method comprises the application of i), optionally ii) and optionally iv) to the damp or wet keratin materials.

The inventors have thus found, surprisingly, that the application to keratin materials of ingredients i), and optionally ii), iii) and iv), makes it possible to provide deposits on the skin having good resistance to external aggressions such as for example water, oils, particularly food oils, sweat and/or sebum and therefore having very good resistance over time. Advantageously, the deposits obtained with the methods according to the invention are also very comfortable. They do not stick and do not transfer. The application to keratin materials of ingredients i), and optionally ii), iii) and iv), also makes it possible to provide deposits on keratin fibers having good resistance to shampoos and water.

The application to keratin materials of ingredients i), and possibly ii), iii) and iv), also makes it possible to obtain shiny or matt deposits depending on the nature of the ingredients i) used.

DEFINITIONS

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

- by "multivalent" we mean a radical that is at least divalent; the valence of the radical R ₁ is equal to n as defined above, the radical R ₁ thus being "n-valent". For example, when n is equal to 3, the radical R ₁ is trivalent;

- By “keratin materials” for the purposes of the present invention, we mean in particular the lips, the skin, the nails and the keratin fibers, in particular the eyelashes, the eyebrows and the hair, preferably the lips and/or the hair.

- By "cosmetic active ingredient": 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. Examples of cosmetic active ingredients include colored or non-colored, fluorescent or non-colored compounds such as optical brighteners, or UVA and/or UVB filters, anti-aging active ingredients or active ingredients intended to provide a benefit to the skin such as active ingredients having an action on the barrier function, deodorant active ingredients, antiperspirant active ingredients, desquamating active ingredients, antioxidant active ingredients, moisturizing active ingredients, sebum-regulating active ingredients, active ingredients intended to combat the effects of pollution, antimicrobial or bactericidal active ingredients, perfumes, 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 their mixtures, b) active ingredients for caring for keratin materials, preferably the skin, c) UV filters, and d) their mixtures.

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

- By “alkyl” we mean a saturated, linear or branched hydrocarbon radical.

- By “a (C _x -C _y )alkyl group” we mean an alkyl radical containing x to y carbon atoms.

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

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

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

- a C ₁ -C ₆ (poly)(hydroxy)alkyl radical, preferably C ₁ -C ₄ ;

- a halogen atom such as chlorine, fluorine or bromine;

- a hydroxy group;

- a C ₁ -C ₂ alkoxy radical; a C ₂ -C ₄ (poly)-hydroxyalkoxy radical;

- an amino radical;

- an amino radical substituted by one or two alkyl radicals, identical or different, in C ₁ -C ₆ , C ₁ -C ₆ , preferably in C ₁ -C ₄ ;

- an acylamino radical (-N(R)-C(O)-R’) in which the radical R is a hydrogen atom,

- a C ₁ -C ₄ alkyl radical and the radical R' is a C ₁ -C ₄ alkyl radical; a carbamoyl radical ((R) ₂ NC(O)-) in which the radicals R, identical or not, represent a hydrogen atom, a C ₁ -C ₄ alkyl radical;

- an alkylsulfonylamino radical (R'-S(O) ₂ -N(R)-) in which the radical R represents a hydrogen atom or a C ₁ -C ₄ alkyl radical and the radical R' represents a C ₁ -C ₄ alkyl radical or a phenyl radical;

- an aminosulfonyl radical ((R) ₂ NS(O) ₂ -) in which the radicals R, identical or not, represent a hydrogen atom, a C ₁ -C ₄ alkyl radical;

- a carboxylic radical in acid or salified form (preferably with an alkali metal or an ammonium, substituted or not);

- a cyano group (CN);

- a polyhalo( _C1 - _C4 )alkyl group, preferably trifluoromethyl ( _CF3 ).

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

- hydroxy,

- C ₁ -C ₄ alkoxy, (poly)hydroxyalkoxy C ₂ -C ₄ ,

- alkylcarbonylamino ((RC(O)-N(R')-) in which the radical R' is a hydrogen atom, a C ₁ -C ₄ alkyl radical and the radical R is a C ₁ -C ₂ alkyl radical, amino substituted by one or two identical or different C ₁ -C ₄ alkyl groups;

- alkylcarbonyloxy ((RC(O)-O-) in which the radical R is a C ₁ -C ₄ alkyl radical, amino substituted by one or two identical or different C ₁ -C ₄ alkyl groups;

- alkoxycarbonyl ((R-O-C(O)-) in which the radical R is a C alkyl radical₁-C₄, amino substituted by one or two identical or different C alkyl groups₁-C₄ ;

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

- A hydrocarbon chain is unsaturated when it contains one or more double bonds and/or one or more triple bonds, which may or may not be conjugated.

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

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

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

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

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

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

- A “(poly)(hydroxy)alkyl” radical denotes a _C1 - _C6 alkyl radical, preferably _C1 - _C4 , optionally substituted by one or more hydroxy radicals, preferably substituted by 1 to 4 hydroxy groups, more particularly between 1 and 3.

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

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

- By "monosaccharide unit" we mean a mono, di or polyvalent monosaccharide radical.

- By “polyvalent radical” we mean a radical that is at least divalent such as a divalent, trivalent or tetravalent radical, preferably divalent or trivalent.

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

- By "polysaccharide" is meant a polysaccharide radical which is a polymer consisting of at least two oses, identical or different from each other, preferably at least 3 oses, linked together by O-osidic bonds, said polymers being composed of monosaccharide units (also called mono-osidic) as defined above, said monosaccharide units each comprising at least 5 carbon atoms, particularly between 7 and 9 carbon atoms, preferably at least 6 carbon atoms, more particularly between 6 and 8 carbon atoms, and more preferably 6 carbon atoms, particularly the mono-osidic units are linked together in 1,4 or 1,6 in α (alpha) or β (beta) anomer, each osidic unit possibly being of L or D configuration, as well as its salts and its solvates such as the hydrates of said monosaccharides; these are more particularly polymers formed from at least three oses (or monosaccharides) having the general formula: -[C _x (H ₂ O) _y )] _w - or -[(CH ₂ O) _x ] _w -, with x an integer greater than or equal to 5, preferably x is greater than or equal to 6, in particular x is inclusively between 5 and 7, preferably x is equal to 6, and y an integer which represents x - 1, and w is an integer greater than or equal to 2, particularly inclusively between 3 and 3000, more particularly between 5 and 2500, preferentially between 10 and 2300, particularly inclusively between 15 and 1000, more particularly between 20 and 500, preferentially between 25 and 200. These oses may optionally carry one or more anionic radicals such as the radicals -C(O)-OH, -SO ₃ H, -O-SO ₃ H or their salts -C(O)O ^- Cat ⁺ , -SO ₃ ^- Cat ⁺ , -O-SO ₃ ^- Cat ⁺ with Cat ⁺ as defined previously.

- By the groups “hydroxy (-OH), carbonyl (-C(O)), carboxy (-C(O)-OH) or amino NH₂, are optionally substituted by one or more R groups.³" we mean that the hydrogen atom of the group in question -OH, -C(O)-H, -C(O)-OH or -NH₂can be substituted by an R group³to lead to -O-R³, -C(O)-R³, -C(O)-OR³, or -N(H)-R³; preferably when R³represents a -SO group₃ ^-, Cat⁺then the substitution is carried out on a hydroxy group to lead to the group -O-SO₃ ^-, Cat⁺.

- By "linear polysaccharide radical" is meant a polysaccharide whose monosaccharide ends are not linked together; as examples of linear polysaccharide radicals, mention may be made of radicals derived from cellulose, starch, amylose, alginates, pectin, hyaluronic acid, dextrans, inulins, guar gums, glucans, carrageenans, pullulans, and their derivatives; preferably pullulans and their derivatives such as myristoylpullulan.

- By “cyclic polysaccharide radical” we mean a polysaccharide whose monosaccharide ends are linked together by O-saccharide bonds; examples of cyclic polysaccharide radicals include cyclodextrin radicals.

- By "anionic counterion" is meant an anion or an anionic group associated with the cationic charge; more particularly the anionic counterion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates among which C₁-C₆alkylsulfonates: Alk-S(O)₂O^-such as methylsulfonate or mesylate and ethylsulfonate; iv) arylsulfonates: Ar-S(O)₂O^-such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkylsulfates: Alk-O-S(O)O^-such as methyl sulfate and ethyl sulfate; x) aryl sulfates: Ar-O-S(O)O^-such as benzene sulfate and toluene sulfate; xi) alkoxy sulfates: Alk-O-S(O)₂O^-such as methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfates: Ar-O-S(O)₂O^-, (xiii) phosphate; (xiv) acetate; (xv) triflate; and (xvi) borates such as tetrafluoroborate, mixtures thereof. The anionic counterion is chosen so that it ensures the electroneutrality of the compounds of formula (I); when z cationic charges are to be neutralized, it is thus possible to use z anions of charge (-1) or z/2 anions of charge (-2).

- By "cationic counterion" is meant a cation or a cationic group associated with the anionic charge; more particularly the cationic counterion is preferably chosen from alkali or alkaline earth metal salts such as sodium, potassium, calcium salts and their mixtures. The cationic counterion(s) may also be organic such as ammonium tri(C ₁ -C ₄ )(alkyl)ammonium or trihydroxy(C ₁ -C ₄ )alkylammonium.

It is understood that when the compound(s) of formula (I) comprise SO ₃ ^- or -O-SO ₃ ^- and ammonium -N ⁺ R'' ₃ groups, the counterions Cat ⁺ and An ^- respectively are present or absent, to ensure the electroneutrality of the molecule (I).

Thus, for example, the cationic counterion is chosen such that it ensures the electroneutrality of the compounds of formula (I); and when z' anionic charges are to be neutralized, it is thus possible to use z' cations of charge (+1) or z'/2 cations of charge (+2).

- “Solvates” represent hydrates as well as the association with linear or branched _C2 - _C6 alcohols also called ( _C2 - _C6 )alkanol such as ethanol, isopropanol, n-propanol.

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

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

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

Throughout the description, including the claims, the expression “comprising a” should be understood as being synonymous with “comprising at least one” or synonymous with “comprising one or more”, unless otherwise specified.

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

- by “homopolymer” we mean a polymer resulting from the repetition of polymeric or monomeric units, of which said monomers are all identical, i.e. of the same chemical nature (for example -A-A-A-A-…-A-A-),

- by “copolymer” is meant a polymer resulting from the repetition of polymeric or monomeric units, of which at least two repeating monomers are different, i.e. of different chemical natures (for example -A-B-A-A-…-B-A-, it being understood that A is different from B); preferably, the (co)polymer(s) of the invention are copolymers.

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

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

Detailed description

PROCESS FOR TREATING KERATIN MATERIALS

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

(i) at least one compound of formula (I) as well as their optical, geometric isomers, their organic or mineral acid or base salts, and/or solvates, such as hydrates, as defined above and below, or a composition containing it(them);

ii) optionally at least one crosslinking agent, in particular as defined below;

iii) possibly water; and

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

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

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

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, if present, it being understood that the ingredient iii), if present, can be applied with i) and/or with ii) and/or with iv), when iv) is present, and that the ingredient(s) iv), when present, can be applied together with i) and/or ii) and/or iii), preferably 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 iii), when it is present, can be applied with i) and/or with ii) and/or with iv), when iv) is present, and that the ingredient(s) iii), when they are present, can be applied together with i) and/or ii).

According to a particular embodiment of the invention, the process for treating keratin materials is a process, in particular a cosmetic process, for treating keratin materials, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows and/or for the care, styling and/or coloring of keratin fibers, preferably hair.

According to a particular embodiment of the invention, the process for treating keratin materials is a cosmetic process for the care, styling and/or coloring of keratin fibers, preferably hair.

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

According to another embodiment of the invention, the method for treating keratin materials is a method for making up the skin, lips, eyelashes, eyebrows. According to this embodiment, the method comprises at least one cosmetic active ingredient chosen from coloring materials, preferably pigments.

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

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

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

- a composition, called “C1”, comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, as defined previously and below, optionally iii) water, and optionally iv) at least one cosmetic active ingredient, in particular as defined previously and below;

- a composition, called “C2”, comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, as defined previously and below, optionally ii) at least one crosslinking agent, in particular as defined previously and below, optionally iii) water, and optionally iv) at least one cosmetic active ingredient, in particular as defined previously and below;

- a composition, called “C3”, comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, as defined above and below, ii) at least one crosslinking agent, in particular as defined above and below, iv) at least one cosmetic active ingredient, in particular as defined above and below, and optionally iii) water;

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

- a composition, called “C5”, comprising iv) at least one cosmetic active ingredient, in particular as defined above and below, and optionally iii) water;

it being understood that the compositions “C1”, “C2”, “C3”, “C4” and “C5” may be anhydrous, aqueous, and/or comprise one or more fatty substances v), in particular as defined below.

According to one aspect of the invention, the process for treating keratin materials, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows and/or for the care, styling and/or coloring of keratin fibers, preferably hair, uses a composition, called "C1", comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, as defined above and below, optionally iii) water and optionally iv) at least one cosmetic active ingredient, in particular 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) mixtures thereof, and in particular at least one coloring agent, more particularly at least a pigment.

According to another aspect, the method for treating keratin materials according to the invention, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows and/or for the care, styling and/or coloring of keratin fibers, preferably hair, uses a composition, called "C2", comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, as defined above and below, optionally ii) at least one crosslinking agent, in particular as defined below, optionally iii) water, and optionally iv) at least one cosmetic active ingredient, in particular as defined above, preferably said composition "C2" comprising iii) water.

According to another aspect, the method for treating keratin materials according to the invention, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows and/or for the care, styling and/or coloring of keratin fibers, preferably hair, uses a composition, called “C3”, comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, as defined above and below, ii) at least one crosslinking agent, in particular as defined below, iv) at least one cosmetic active ingredient, in particular as defined above, and optionally iii) water.

According to another aspect, the method for treating keratin materials according to the invention, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows and/or for the care, styling and/or coloring of keratin fibers, uses a composition called "C1" and a composition called "C4", said composition "C1" comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, as defined above and below, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined above and below, and said composition "C4" comprising ii) at least one crosslinking agent, in particular as defined above and below, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular as defined above and below, below.

According to another variant of the process of the invention, the ingredient(s) i), optionally iii), and optionally iv) are applied together, namely simultaneously, to the keratin materials during a first step, then during a subsequent step, the ingredient(s) ii), optionally iii), and optionally iv) are applied to said materials.

According to a particular embodiment, the method according to the invention comprises two successive steps of application to said keratin materials of two different compositions.

According to a particular embodiment of the method, during the first step a composition “C1” is applied to the keratin materials, then a composition “C4” is applied to said keratin materials.

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

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

According to a particular embodiment of the method, during the first step a composition “C2” is applied to the keratin materials, then a composition “C4” is applied to said keratin materials.

According to another variant of the method according to the invention, a composition “C2” containing i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, optionally ii) at least one crosslinking agent, optionally iii) water, and optionally iv) at least one cosmetic active agent, is applied, and sequentially a composition “C4” containing ii) at least one crosslinking agent, optionally iii) water, and optionally at least one cosmetic active agent iv), preferably the composition “C2” being applied before the composition “C4”, and it being understood that the possible crosslinking agent(s) contained in the composition “C2” may be identical to or different from the crosslinking agent(s) contained in the composition “C4”, preferably the crosslinking agent(s) are different.

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

The 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 directly on the surface of these keratin materials.

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

According to one embodiment of the method of the invention, the method is carried out in one step by applying to the keratin materials the composition “C1”, “C2” or “C3”, as defined above.

Thus, according to one embodiment, the treatment method according to the invention comprises a single step of applying the composition “C1” or the composition “C2” or the composition “C3” to said keratin materials.

The term “1-step application method” means the direct application to the target keratin materials of a single composition in accordance with the invention, namely composition “C1” or “C2” or “C3”.

After applying the composition “C1”, “C2” or “C3”, a permanent and non-sticky deposit is advantageously obtained. The deposit obtained is also resistant to cooking oils, water, sebum and friction.

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

The term “2-step application method” means the successive application, on 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.

The term “3-step application mode” means the sequential application of 3 distinct compositions “C1” to “C5”. According to this application mode, for example, according to one embodiment, the successive application to the keratin materials is carried out: 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 embodiment, the sequential application to the keratin materials is carried out, 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 the composition “C1” or “C2”.

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

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

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

According to a particular embodiment, the compositions are applied to damp or wet keratin materials, that is to say to keratin materials containing water on the surface.

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 treatment, in particular cosmetic, of keratin materials, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows and/or for the care, styling and/or coloring of keratin fibers, preferably hair, comprising a step of application to the skin or said lips or eyelashes or eyebrows, of a composition "C1", "C2" or "C3", in particular containing at least one coloring material, in particular as defined above, and more particularly at least one pigment.

According to another of its aspects, the present invention relates to a cosmetic treatment process for the care, styling and/or coloring of keratin fibers, preferably hair, comprising the successive application of at least:

- a composition, called “C1”, comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, as defined previously and below, optionally iii) water, and optionally iv) at least one cosmetic active ingredient, in particular as defined previously and below; then

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

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

According to another of its aspects, the present invention relates to a cosmetic treatment process for the care, styling and/or coloring of keratin fibers, preferably hair, comprising the successive application of at least:

- 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 matter, in particular as defined below, preferably at least one pigment. Preferably, the composition “C5” comprises at least one pigment.

According to another of its aspects, the present invention relates to a cosmetic treatment process for the care, styling and/or coloring of keratin fibers, preferably hair, comprising the successive application of at least:

- a composition “C2” or “C3” as defined above; and

- a “C4” composition as defined above;

it being understood that the compositions “C2” or “C3” contain at least iv) one coloring matter, in particular as defined below, and/or the composition “C4” contains at least one coloring matter, in particular as defined below, preferably the composition “C2” or “C3” comprises at least one pigment.

COMPOUNDS OF FORMULA (I)

As indicated above, the treatment method according to the invention comprises the application to the keratin materials of at least one or more compounds chosen from the oligosaccharides or polysaccharides having acetoacetate functions of formula (I) as well as their optical, geometric isomers, their salts of organic or mineral acid or base, and/or solvates, such as hydrates, or a composition containing it/them.

Thus, the treatment method according to the invention comprises the application to keratin materials of at least one or more compounds of formula (I) as well as their optical, geometric isomers, their organic or mineral acid or base salts, and/or solvates, such as hydrates, or a composition containing it/them:

(I)

formula (I) in which:

- R ¹ represents a multivalent, linear or cyclic polysaccharide radical, preferably linear, consisting of at least 3 monosaccharide units, each comprising at least 5 carbon atoms, particularly between 7 and 9 carbon atoms, preferably at least 6 carbon atoms, more particularly between 6 and 8 carbon atoms, and more preferentially 6 carbon atoms, and of which one or more of the hydroxy (-OH), carbonyl (-C(O)), carboxy (-C(O)-OH) or amino -NH ₂ groups, of all or part of at least one of the monosaccharide units, are optionally substituted by one or more R ³ groups;

- 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, more preferably methyl;

- R ³ , identical or different, represents a group chosen from:

1) sulfonate -SO ₃ ^- , Cat ⁺ ,

2) (C ₁ -C ₂₂ )alkyl, linear or branched, and

3) (C ₁ -C ₂₂ )alkylcarbonyl, linear or branched,

the (C ₁ -C ₂₂ )alkyl group being optionally interrupted by one or more heteroatoms or groups X as defined below; and/or

the (C ₁ -C ₂₂ )alkyl group being optionally substituted by one or more groups chosen from: a) hydroxy (-OH); b) sulfonate -SO ₃ ^- , Cat ⁺ ; c) sulfate -O-SO ₃ ^- , Cat ⁺ ; d) -(CH ₂ -CH ₂ -O) _p -R ⁴ ; e) –O-(CH ₂ -CH ₂ -O) _p -R ⁴ ; f) -C(O)-R ⁴ ; g) -C(O)-OR ⁴ ; h) -OC(O)-R ⁴ ; i) -C(O)-N(R')-R ⁴ ; j) -N(R')-C(O)-R ⁴ ; k) ammonium -N ⁺ R''₃; An ^- and l) mixtures thereof;

- R ⁴ represents a hydrogen atom, a linear or branched (C ₁ -C ₈ )alkyl group _, preferably R ⁴ represents a hydrogen atom or a linear or branched (C ₁ -C ₆ )alkyl group, more preferably a linear or branched (C ₁ -C ₄ )alkyl group, in particular methyl;

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

- X is a heteroatom or group selected from -O-, -S-, -N(R’)-, and combinations thereof such as -C(O)-O-, -O-C(O)-, -C(O)-N(R’)-, -N(R’)-C(O)-, -N(R’)-C(O)-O-, -N(R’)-C(O)-N(R’)-, preferably X represents -O-;

- R', identical or different, represents a hydrogen atom, a (C ₁ -C ₆ )alkyl group, linear or branched, optionally substituted by at least one hydroxyl group (OH), preferably R' represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, in particular methyl, more preferably R' represents a hydrogen atom;

- R'', identical or different, represents a hydrogen atom or a linear or branched (C ₁ -C ₆ )alkyl group, preferably a (C ₁ -C ₄ )alkyl group, in particular methyl;

- n denotes an integer ranging from 2 to 3000, in particular from 5 to 2500, more particularly from 10 to 2300, preferably from 15 to 1000, preferentially from 20 to 500, and more preferentially from 25 to 200;

- p denotes an integer ranging from 0 to 3;

- An ^- represents an anionic counterion;

- Cat ⁺ represents a cationic counterion;

ii) optionally at least one crosslinking agent; and

iii) optionally water, preferably water, or optionally water mixed with a polar organic solvent, preferably chosen from (C ₂ -C ₆ )alkanol, more preferably ethanol.

According to a particular embodiment of the invention, R ¹ represents a multivalent, linear or cyclic polysaccharide radical, preferably linear, consisting of at least 3 monosaccharide units each comprising at least 5 carbon atoms, preferably at least 6 carbon atoms, particularly between 6 and 8 carbon atoms, and more preferably 6 carbon atoms, and of which none of the hydroxy (-OH), carbonyl (-C(O)), carboxy (-C(O)-OH) or amino -NH ₂ groups, of the monosaccharide units, are substituted.

According to another particular embodiment of the invention, the compounds of formula (I) are such that R ¹ represents a multivalent, linear or cyclic polysaccharide radical, preferably linear, consisting of at least 3 monosaccharide units each comprising at least 5 carbon atoms, preferably at least 6 carbon atoms, particularly comprising from 6 to 8 carbon atoms, and more preferably 6 carbon atoms, and of which one or more of the hydroxyl (-OH) or amino -NH ₂ groups, of all or part of at least one of the monosaccharide units, are substituted by one or more R ³ groups, identical or different, representing a (C ₁ -C ₂₂ )alkylcarbonyl group, the (C ₁ -C ₂₂ )alkyl group being:

- optionally interrupted by one or more atoms of oxygen, sulfur or -N(H)- preferably -O-, and/or

- optionally substituted by one or more groups selected from a) hydroxy (-OH); b) sulfonate -SO ₃ ^- , Cat ⁺ ; c) sulfate -O-SO ₃ ^- , Cat ⁺ ; d) -(CH ₂ -CH ₂ -O) _p -R ⁴ ; e) –O-(CH ₂ -CH ₂ -O) _p -R ⁴ ; f) -C(O)-R ⁴ ; g) -C(O)-OR ⁴ ; h) -OC(O)-R ⁴ ; i) -C(O)-N(R')-R ⁴ ; j) -N(R')-C(O)-R ⁴ ; k) ammonium -N ⁺ R'' ₃ , An ^- and l) mixtures thereof; with R ⁴ representing a hydrogen atom, or a (C ₁ -C ₆ )alkyl group, more preferably (C ₁ -C ₄ )alkyl, such as methyl, R'', An ^- and Cat ⁺ being as defined above. Preferably, R'' represents a (C ₁ -C ₄ )alkyl group, such as methyl.

According to a particular embodiment of the invention, the compounds of formula (I) are such that R ³ , identical or different, represents a (C ₁ -C ₂₂ )alkylcarbonyl group, the (C ₁ -C ₂₂ )alkyl group being optionally substituted by one or more groups chosen from a) hydroxy (-OH); h) ammonium -N ⁺ R'' ₃ , An ^- and i) mixtures thereof; with R'' representing a (C ₁ -C ₄ )alkyl group, such as methyl.

More preferably, the (C ₁ -C ₂₂ )alkyl(e) group of R ³ represents a group -CH ₂ -CH(OH)-CH ₂ -N ⁺ (CH ₃ ) _3, An ^- .

According to a particular variant of the invention, the compounds of formula (I) are such that R ¹ represents a multivalent, linear or cyclic polysaccharide radical, preferably linear, consisting of at least 3 monosaccharide units each comprising at least 5 carbon atoms, preferably at least 6 carbon atoms, and more preferably 6 carbon atoms, and of which one or more of the hydroxy groups, of all or part of at least one of the monosaccharide units, are substituted by one or more R ³ groups, identical or different, representing a sulfonate group -SO ₃ ^- , Cat ⁺ .

According to another variant of the invention, R ¹ represents a multivalent, linear or cyclic polysaccharide radical, preferably linear, consisting of at least 3 monosaccharide units each comprising at least 5 carbon atoms, preferably at least 6 carbon atoms, particularly between 6 and 8 carbon atoms, and more preferably 6 carbon atoms, and of which one or more of the hydroxy (-OH), carbonyl (-C(O)), carboxy (-C(O)-OH) or amino -NH ₂ groups, of all or part of at least one of the monosaccharide units, are substituted by one or more R ³ groups with R ³ , identical or different, representing a group chosen from:

1) sulfonate -SO ₃ ^- , Cat ⁺ ,

2) (C ₁ -C ₂₂ )alkyl, linear or branched, and

3) (C ₁ -C ₂₂ )alkylcarbonyl, linear or branched.

More preferably, R ¹ comprises one or more of the hydroxy (-OH) or amino -NH ₂ groups, of all or part of at least one of the monosaccharide units, substituted by one or more R ³ groups as defined above. In particular, the -OH group is substituted by a group 1), 2) or 3), more particularly by a group 1) or 3), preferably by a group 3). In particular, the -NH ₂ group is substituted by a group 2) or 3), more particularly by a group 3).

According to a particular embodiment, the compound(s) of formula (I) as well as their optical, geometric isomers, their organic or mineral acid or base salts, and/or solvates according to the invention are such that the polysaccharide radical represented by R ¹ is chosen from polysaccharide radicals derived from agarose, starch and its derivatives, cationic starch, alginate and its derivatives, hyaluronic acid, cellulose and its derivatives, in particular chosen from methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxypropylmethylcellulose and hydroxybutylcellulose, carrageenan, curdlan, dextran, glucan, guar gum, gellan, konjac, inulin, pectin, pullulan, scleroglucan, xanthan and their derivatives, preferably chosen from starch and its derivatives, cellulose and its derivatives and alginate and its derivatives, and more preferably chosen from pullulan and its derivatives, such as myristoyl pullulan.

By “derivatives” is meant compounds obtained by chemical modification of the compounds mentioned. In particular, these may be esters, amides, or ethers of said compounds.

The polysaccharide/oligosaccharide derivatives may for example be chosen from those described in the articles “Natural and modified polysaccharides”, Drug Targeting and Delivery (1997), 7, 275-289 and “Gums”, Kirk-Othmer Encyclopedia of Chemical Technology (2005), 13, 60-73.

The polysaccharide radicals R ¹ can also be chosen from radicals derived from fatty chain polysaccharide derivatives, in particular those described in the publication “Enzymatic synthesis of oligo- and polysaccharide fatty acid esters”, Carbohydrate Polymers, (2013), 93(1), 65-72, “Chemical Modification of Polysaccharides”, Hindawi, Orhanic Chemistry, Volume 2013, Article ID 417672, or even in patent application CA2087488.

According to a particular embodiment, the fatty chain polysaccharides at the origin of the radicals R ₁ are chosen from Myristoyl Pullulan, Stearoyl Inulin, Undecylenoyl Inulin and Palmitoyl Hydroxypropylcellulose, preferably from fatty chain esters, more preferably myristoyl pullulan.

The polysaccharide/oligosaccharide derivatives may also be selected from thiolated polysaccharides/oligosaccharides, in particular those described in the publication “Unsaturated and thiolated derivatives of polysaccharides as functional matrixes for tissue engineering and pharmacology: A review”, Carbohydrate Polymers, 2021, Volume 259, 117735.

According to a particular embodiment, the compounds of formula (I) having acetoacetate functions are chosen from:

(a) cellulose, starch, amylose and their derivatives, of formula (II) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(II)

(b) alginate, pectin and their derivatives, of formula (III) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(III)

(c) hyaluronic acid and its derivatives, of formula (IV) and their isomers and solvates:

(IV)

(d) dextran and its derivatives, of formula (V) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(V)

(e) inulin and its derivatives, of formula (VI) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(VI)

(f) guar gum and its derivatives, of formula (VII) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(VII)

(g) glucan and its derivatives, of formula (VIII) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(VIII)

(h) carrageenan and its derivatives, in particular of formula (IX), as well as their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(IX)

in particular chosen from the derivatives γ-carrageenan, δ-carrageenan, μ-carrageenan, ν-carrageenan, λ-carrageenan, and their respective basic forms β-carrageenan, α-carragenene, κ-carrageenan, ι-carrageenan, θ-carrageenan, it being understood that the carragenans comprise at least one group of formula (XII), preferably at least two groups of formula (XII);

(i) cyclodextrin and its derivatives, of formula (X):

(X)

(j) pullulan and its derivatives, of formula (XI) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(XI)

• R⁶, identiques ou différents, représente -CH₂-OR⁷ou -C(O)-OR⁷,
• R⁷, identiques ou différents, représentent un atome d’hydrogène ou un groupe R³tel que défini dans la formule (I), de préférence un groupe (C₁-C₂₂)alkyle, éventuellement substitué par au moins un groupe hydroxy (-OH) ou un groupe -C(O)-R⁸, avec R⁸représente un groupe (C₁-C₂₂)alkyle, ou un groupe -CH₂-CH(OH)-CH₂-N⁺(CH₃)₃ An^-, ou un groupe R⁹de formule (XII), R^7’représente un radical R⁷ou un groupe -SO₃ ^-, Cat⁺, Cat⁺étant tel que défini précédemment, ou un groupe de formule (XII) :

formulas (II) to (XI) in which:

• R ⁶ , identical or different, represents -CH ₂ -OR ⁷ or -C(O)-OR ⁷ ,
• R⁷, identical or different, represent a hydrogen atom or an R group³as defined in formula (I), preferably a group (C₁-C₂₂)alkyl, optionally substituted by at least one hydroxy group (-OH) or one -C(O)-R group⁸, with R⁸represents a group (C₁-C₂₂)alkyl, or a -CH group₂-CH(OH)-CH₂-N⁺(CH₃)₃ Year^-, or a group R⁹of formula (XII), R^7'represents a radical R⁷or a -SO group₃ ^-, Cat⁺, Cat⁺being as defined above, or a group of formula (XII):

(XII)

• R¹⁰, identiques ou différents, représentent un atome d’hydrogène, un groupe (C₁-C₄)alkyle, tel que -CH₃ou un groupe R⁹tel que défini ci-dessus ;
• m désigne un nombre entier allant de 2 à 3000, en particulier de 5 à 2500, plus particulièrement de 10 à 2300, de préférence de 15 à 1000, préférentiellement de 20 à 500, et plus préférentiellement de 25 à 200 ;
• An^-étant tel que défini précédemment ;

formula (XII) in which R ^a , R ^b , and R ² are as defined above for the compounds of formula (I), preferably R ² denotes a methyl radical and R ^a and R ^b denote a hydrogen atom;

• R ¹⁰ , identical or different, represent a hydrogen atom, a (C ₁ -C ₄ )alkyl group, such as -CH ₃ or an R ⁹ group as defined above;
• m denotes an integer ranging from 2 to 3000, in particular from 5 to 2500, more particularly from 10 to 2300, preferably from 15 to 1000, preferentially from 20 to 500, and more preferentially from 25 to 200;
• An ^- being as defined above;

it being understood that formulas (II) to (XI) have at least one R ⁹ unit, and preferably at least two R ⁹ units, of formula (XII), in their structure.

According to a particular embodiment, the polysaccharides and/or oligosaccharides having acetoacetate functions are chosen from:

- alginic acid 3-oxobutanoate (CAS no.: 2135428-65-6);

- amylose 3-oxobutanoate (CAS no.: 106254-13-1);

- cellulose, 3-oxobutanoate, 2-hydroxyethyl ether (CAS number: 104708-71-6);

- cellulose, 3-oxobutanoate, carboxymethyl ether (CAS number: 105953-68-2);

- cellulose, 3-oxobutanoate, 2-hydroxypropyl ether (CAS number: 105953-69-3);

- cellulose, 3-oxobutanoate, methyl ether (CAS number: 105953-70-6);

- cellulose, tris(3-oxobutanoate) (CAS number: 119466-02-3);

- cellulose, 3-oxobutanoate (CAS number: 80619-14-3);

- cellulose, acetate 3-oxobutanoate (CAS number: 168608-38-6);

- cellulose, hexanoate 3-oxobutanoate (CAS number: 1696417-96-5);

- cellulose, 3-oxobutanoate propanoate (CAS number: 163381-45-1);

- cellulose, butanoate 3-oxobutanoate (CAS number: 163438-87-7);

- cellulose, 4-methoxy-3-oxobutanoate (CAS number: 2410687-10-2);

- cellulose, 3-oxobutanoate, 2-hydroxypropyl methyl ether (CAS number: 2223678-14-4);

- cellulose, acetate butanoate 3-ethoxypropanoate 3-oxobutanoate (CAS number: 334475-56-8);

- cellulose, 2-hydroxypropyl ether, 3-oxobutanoate (CAS number: 497932-47-5);

- cellulose, 3-oxobutanoate, ethyl ether (CAS number: 497932-48-6);

- dextran, 3-oxobutanoate (CAS number: 882428-66-2);

- D-Glucan, 3-oxobutanoate (CAS number: 2135428-66-7);

- guar gum, 3-oxobutanoate (CAS number: 497932-49-7);

- hyaluronic acid, 3-oxobutanoate (CAS number: 2135428-62-3);

- starch, 3-oxobutanoate (CAS number: 78207-15-5);

- starch, 3-oxobutanoate, methyl ether (CAS number: 2135428-59-8);

- starch, 3-oxobutanoate, 2-carboxymethyl ether (CAS number: 2135428-60-1);

- starch, 2-hydroxypropyl ether, 3-oxobutanoate (CAS number: 2135428-61-2);

- starch, 3-oxobutanoate, 2-hydroxypropyl ether (CAS number: 2223678-15-5);

- pullulan acetoacetate (CAS number: 2762209-81-2);

- cyclodextrin, ethyl-3-oxobutanoate (CAS number: 152154-93-3);

- cyclodextrin, 3-oxobutanoate (CAS number: 2135428-63-4); And

- myristoyl pullulan acetoacetate.

According to a preferred embodiment, the polysaccharides and/or oligosaccharides having acetoacetate functions are chosen from the compounds of formula (XI) as well as their optical isomers, their acid or base salts, organic or mineral, and their solvates such as hydrates, and preferably chosen from pullulan acetoacetate (CAS no.: 2762209-81-2) and myristoyl pullulan acetoacetate.

According to an alternative embodiment, the polysaccharide(s) and/or oligosaccharide(s) having acetoacetate functions of formula (I) are obtained by (poly)condensation(s) of n equivalents of dicarbonyl reagent with a polysaccharide R ¹ (XH) _n comprising n equivalents of nucleophilic functions -XH according to the following scheme:

diagram in which:

- R ¹ , R ² , R ^a , R ^b and n are as defined in formula (I) described above;

- R³represents a hydrogen atom, a group (C₁-C₄)alkyl, in particular methyl, ethyl, isobutyl, t-butyl, or an electrofuge group such as CHal₃, or Hal₃C-SO₂- such as triflate, with Hal, identical or different, representing a halogen atom ; And

- X’ represents an oxygen or sulfur atom, preferably an oxygen atom.

Such a preparation process is notably described in patent application WO2020026143, or in the publications “Synthesis and properties of cellulose acetoacetates”, Macromolecules (1995), 28(12), 4122-8, and “A facile method of functional derivatization based on starch acetoacetate”, Carbohydrate Polymers, 2022, 289, 119468.

According to another embodiment variant, the polysaccharide(s) and/or oligosaccharide(s) having acetoacetate functions of formula (I) are obtained by enzymatic esterification, as described in patent application US6528644B1, or in patent application US20100003730, by (poly)condensation(s) of n equivalents of 2-Oxetanone, 4-methylene reagent with an oligo/polysaccharide nucleophilic reagent R ¹ (OH) _n comprising n equivalents of -OH nucleophilic functions according to the following scheme:

scheme in which R ¹ and n are as defined in formula (I) described above.

According to another variant embodiment, the polysaccharide(s) and/or oligosaccharide(s) having acetoacetate functions of formula (I) are obtained by (poly)condensation(s) of n equivalents of propylenedioxy carbonyl reagent with an oligo/polysaccharide nucleophilic reagent R ¹ (XH) _n comprising n equivalents of -XH nucleophilic functions according to the following scheme:

diagram in which:

- R ¹ , R ² , R ^a , R ^b and n are as defined in formula (I) described above;

- R³represents a hydrogen atom, a group (C₁-C₄)alkyl, in particular methyl, ethyl, isobutyl, t-butyl, or an electrofuge group such as CHal₃, or Hal₃C-SO₂- such as triflate, with Hal, identical or different, representing a halogen atom ; And

- X’ represents an oxygen or sulfur atom, preferably an oxygen atom.

Such a preparation process is notably described in the publication “Acetoacetylation with 2,2,6-trimethyl-4H-1,3-dioxin-4-one: a convenient alternative to diketene”, Journal of Organic Chemistry (1985), 50(14), 2431-5.

According to a preferred embodiment variant, the polysaccharide(s) and/or oligosaccharide(s) having acetoacetate functions of formula (I) are obtained by (poly)condensation(s) of n equivalents of propylenedioxy carbonyl reagent with an oligo/polysaccharide nucleophilic reagent R ¹ (OH)n comprising n equivalents of -OH nucleophilic functions according to the following scheme:

diagram in which:

- R ¹ , R ² , R ^a and n are as defined previously in formula (I);

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

Such a preparation process is notably described in the publications “Efficient and catalyst free synthesis of cellulose acetoacetates”, Cellulose, 2018, 25 (9), 4919-4928, “2,2,6-trimethyl-4H-1,3-dioxin-4-one: a convenient alternative to diketene”, Journal of Organic Chemistry 50(14), 2431-5, (1985), “Acetoacetylation of O-(hydroxypropyl)cellulose by 2,2,6-trimethyl-4H-1,3-dioxin-4-one”, Carbohydrate Research 156, 232-5, (1986), or in patent applications WO9740074 and WO9303063.

According to a preferred embodiment of the invention, the compounds of formula (I) are prepared by reacting a polysaccharide with n equivalents of ester R ₂ -C(O)-C(Ra)(Rb)-C(O)-O-tBu in a polar aprotic solvent such as DMSO, DMF, preferably DMSO, at a temperature of between 25 °C and 190 °C, preferably 50 °C to 130 °C, and preferably at atmospheric pressure. The preparation method is for example that described in the scientific article "A facile method of functional derivatization based on starch acetoacetate", Carbohydrate Polymers, 289, 119468 (2022).

The polysaccharide(s) and/or oligosaccharide(s) having acetoacetate functions of formula (I) as well as their optical, geometric isomers, their acid or base salts, organic or mineral, and solvates as defined above, are preferably present in a content ranging from 1% to 30% by weight, in particular from 2% to 25% by weight, more particularly from 4% to 22% by weight, relative to the total weight of the composition containing them.

Another subject of the invention is the compound myristoyl pullulan acetoacetate, its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, of formula:

formula in which:

- m is as defined previously;

- R ¹¹ , identical or different, represents a hydrogen atom or a (C ₁₀ -C ₁₆ )alkyl group, linear or branched, preferably linear, such as CH ₁₃ H ₂₇ , or (C ₁₀ -C ₁₆ )alkylcarbonyl, linear or branched, preferably linear, such as CH ₁₃ H ₂₇ -C(O)- or a group R ⁹ as defined above;

it being understood that at least one, preferably at least two, R group(s)¹¹, and that at least one group (C₁₀-C₁₆)alkyl or (C₁₀-C₁₆)alkylcarbonyl, such as CH₁₃H₂₇ Or CH₁₃H₂₇-C(O)-, are present in the myristoyl pullulan acetoacetate compound above.

Another subject of the invention is a cosmetic composition comprising at least one myristoyl pullulan acetoacetate compound as defined above.

According to a particular embodiment of the invention, the composition “C1” as defined above is an aqueous composition.

CROSSLINKING AGENT

According to a particular embodiment, the treatment method according to the invention as described above comprises the application to the keratin materials, (i) of at least one or more compounds of formula (I) as well as their optical, geometric isomers, their acid or base salts, and/or solvates, and (ii) of at least one crosslinking agent.

For the purposes of the invention, the term “crosslinking agent”, also called “R”, denotes a compound capable of establishing with at least one acetoacetate function of the compound(s) of formula (I) used in the treatment method according to the invention:

- at least one covalent bond,

- at least one donor-acceptor (dative) bond, and/or

- at least one coordination link,

and thus to crosslink this or these compound(s).

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

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

Compositions “C2”, “C3” and “C4” as defined above may 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. Composition “C2” may be an aqueous composition.

According to one aspect, the treatment method of the invention uses a so-called “C3” composition, in particular a cosmetic composition for keratin materials, in particular for the care and/or makeup of the skin, lips, eyelashes and/or eyebrows and/or for the care, styling and/or coloring of keratin fibers, preferably hair, comprising i) at least one compound of formula (I) as well as their optical, geometric isomers, their acid or base salts, and/or solvates as defined above, ii) at least one crosslinking agent, iv) at least one cosmetic active ingredient, in particular as defined above, in particular at least one coloring agent, more particularly at least one pigment, and optionally iii) water.

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

In particular, the crosslinking agent(s) and the compound(s) of formula (I) are preferably present in a mass content ranging from 1% to 35% by weight, relative to the total weight of the composition comprising them.

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

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

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

The metal alkoxide compounds are defined below.

A) (Poly)amino compounds

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

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

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

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

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

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

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

- R' ₁ is a linear or branched, saturated or unsaturated, cyclic or acyclic C ₁ -C ₆ hydrocarbon chain substituted by a group chosen from the primary NH ₂ or secondary -N(H)R amine groups with R representing a C ₁ -C ₄ alkyl, an aryl, a benzyl substituted by an amino group or by a C ₁ -C ₄ aminoalkyl group; R' ₁ may be interrupted in its chain by a heteroatom (O, S, NH) or a carbonyl group C(O), R' ₁ being linked to the silicon atom directly via a carbon atom,

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

- z denotes an integer from 1 to 3, and

- x denotes an integer ranging from 0 to 2,

with z + x = 3.

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

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

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

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

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

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

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

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

formula (IV) in which:

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

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

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

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

• ALK[(O-ALK’)_m-NH₂]₂(V)

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

• ALK[(O-ALK') _m -NH ₂ ] ₂ (V)

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

Or

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

formulas (V) and (VI) in which:

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

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

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

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

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

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

As (poly)amino compounds which are triaminated, polyether triamines are particularly cited, and in particular 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)amine compound(s) comprise more than three primary and/or secondary amine groups, preferably primary (NH ₂ ).

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

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

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

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

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

formula (VII) in which:

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

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

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

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

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

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

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

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

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

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

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

B) (Poly)thiolated compounds

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

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

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

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

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

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

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

L(SH) _q (VIII)

formula (VIII) in which:

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

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

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

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

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

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

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

R' ₁ -Si(OR' ₂ )z(R' ₃ ) _x (VIII')

formula (VIII’) in which:

- R' ₁ is a C ₁ -C ₁₂ hydrocarbon chain, linear or branched, saturated or unsaturated, cyclic or acyclic, substituted by one or more groups chosen from thiol groups; and aryl, aryloxy, arylthio, arylamino, the aryl group being substituted by one or more thiol groups, or thiol(C ₁ -C ₆ )alkyl, preferably thiol(C ₁ -C ₆ )alkyl; and R' ₁ is optionally interrupted in its hydrocarbon chain by one or more heteroatoms such as O, S, N, a carbonyl group C(O), or their association such as ester -C(O)-O-, or amide -C(O)-N(H)-, R' ₁ being linked to the silicon atom directly via a carbon atom,

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

- z denotes an integer from 1 to 3, and

- x denotes an integer ranging from 0 to 2,

with z + x =3.

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

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

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

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

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

Preferably, z is equal to 3.

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

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

formula (IX) in which:

- p is 0 or 1;

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

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

- R ² and R ³ , identical or different, preferably identical, are chosen from a (C ₁ -C ₆ )alkyl group, in particular C ₁ -C ₄ , such as methyl, and a (C ₁ -C ₆ )alkoxy group, in particular (C ₁ -C ₄ )alkoxy, such as methoxy;

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

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

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

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

formula (IX’) in which:

- q is 0 or 1;

- X represents an oxygen or sulfur atom, preferably sulfur;

- R' ¹ denotes a (C ₁ -C ₆ )alkyl radical;

- R' ² and R' ³ , identical or different, preferably identical, are chosen from a (C ₁ -C ₆ )alkoxy group, in particular C ₁ -C ₄ , and a (C ₁ -C ₆ )alkyl radical;

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

- R ⁴ represents a hydrogen atom or a C ₁ -C ₄ alkyl group, in particular methyl;

- L ² represents a divalent hydrocarbon group, linear or branched saturated in C ₁ -C ₂₀ , optionally interrupted by a heteroatom such as -N(H)-, and/or optionally substituted by one or more hydroxy, thiol or amino groups.

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

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

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

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

Examples include polymers described in the following documents: Polymers containing groups of biological activity, CG Overberger et al, Polytechnic Institute of Brooklyn, http://pac.iupac.org/publications/pac/pdf/1962/pdf/0402x0521.pdf ; EP 1 247 515 A2 ; 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 denotes a polymeric radical, preferably carbon or silicone; POLY being optionally interrupted by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their combinations such as -O-, -OC(X)-, -N(R)-C(X)-, -Si(R _c )(R _d )-O- with R representing a hydrogen atom or a (C ₁ -C ₆ )alkyl group such as methyl; and/or POLY being optionally substituted by one or more halogen atoms, or a group chosen from R _a (R _b )N- and -(X') _a -C(X)-(X'') _b -R _a ; X, X' and X'', identical or different, represent an oxygen atom, sulfur atom, or an N(R _b ) group; a, and b being 0 or 1, preferably the sum of a + b is 1; R _a and R _b , identical or different, represent a hydrogen atom, or a (C ₁ -C ₁₀ )alkyl, or aryl(C ₁ -C ₄ )alkyl group, such as benzyl, preferably R _a and R _b represent a hydrogen atom; and R _c and R _d , identical or different, represent a (C ₁ -C ₁₀ )alkyl, aryl(C ₁ -C ₄ )alkyl or (C ₁ -C ₁₀ )alkoxy group.

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

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

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

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

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

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

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

formula (XI) in which:

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

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

- L ⁴ and L ⁵ , identical or different, preferably identical, represent a hydrocarbon chain comprising from 1 to 100 carbon atoms, saturated or unsaturated, linear or branched, optionally cyclic, optionally interrupted by one or more heteroatoms, such as oxygen, sulfur or nitrogen, in particular oxygen, in particular represent a covalent bond, a (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy, oxy-(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylenoxy or oxy(C ₁ -C ₆ )alkylene-oxy(C ₁ -C ₆ )alkylene group, preferably a (C ₁ -C ₆ )alkylene, (C ₁ -C ₆ )alkyleneoxy, oxy-( _C1 - _C6 )alkylene, or ( _C1 - _C6 )alkyleneoxy( _C1 - _C6 )alkylene.

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

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

formula (XII) in which:

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

- n is as defined in formula (XI).

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

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

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

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

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

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

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

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

C) (Poly)acrylate compounds

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

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

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

L[-YC(O)-C(R ^e )=CH ₂ ] _q (XIV)

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

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

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

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

formula (XV) in which:

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

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

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

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

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

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

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

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

D) Metal alkoxides

• M-(OR₁)_n(XIV_a)
• R-M-(OR₁)_n-1(XIV_b)
• (R₁O)_n-1-M-R’’-M’-(OR₁’)_{n ’ -1}(XIV_c)
• R-M(R’)-(OR₁)_n-2(XXIV_d)

According to a particular embodiment, the crosslinking agent R is a compound chosen from the metal alkoxides of formulae (XIV _a ), (XIV _b ), (XIV _c ) and (XIV _d ) below, 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 _a ), (XIV _b ), (XIV _c ) 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 linear or branched, saturated or unsaturated hydrocarbon group 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 linear, branched, acyclic or cyclic, saturated or unsaturated hydrocarbon group, having from 1 to 30 carbon atoms, preferably from 2 to 20 carbon atoms, 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 being optionally substituted by one or more hydroxyl 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 carbon atoms, 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 titanium or zirconium, even more preferably titanium.

Preferably, the organometallic compound(s) are chosen from alkoxides of formula (XIV _a ) as defined above. According to this preferred embodiment, the organometallic compound(s) are more particularly chosen from 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 linear or branched, saturated hydrocarbon group 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 a titanium atom; n represents the valence 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 ), titanium 2-ethylhexyloxide (Ti(OCH ₂ CH(C ₂ H ₅ )(CH ₂ ) ₃ CH ₃ ) ₄ ), and mixtures thereof, more preferably chosen from zirconium propoxide, titanium propoxide, titanium butoxide and mixtures thereof.

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.

E) (Poly)carbonyl compounds

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

In particular, the (poly)carbonyl compound is selected 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 nonionic or anionic oxidized polysaccharides such as oxidized inulins, in particular those of formula (II) as defined below. In particular, the (poly)carbonyl compounds comprise a 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 terephthalide.

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

It is understood that oxidized polysaccharides are different from compounds of formula (I) in that they do not include a group:

with R ² , R ^a , R ^b , and X as defined in formula (I).

These anionic groups are preferably carboxy or carboxylate groups.

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

P–(CHO) _m (COOQ) _n (XX)

formula (XX) in which:

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

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

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

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

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

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

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

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

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

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

Another oxidation process is described in the article “Water soluble oxidized starches by peroxide reaction extrusion” Industril Crops and Products 7, R. E. Wing, J. L. Willet 45-52 (1997).

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

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

In particular, said (poly)amine 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 chain end), c) polyether triamines, such as Polyetheramine (or jeffamine), d) aminoalkoxysilanes, such as APTES, e) spermidine and f) polydialkylsiloxanes comprising primary amine groups at the chain end or on side chains, particularly polydimethylsiloxanes comprising primary amine groups, such as poly(dimethoxysiloxane) terminated with bis(3-aminopropyl) (PDMS-diNH ₂ ) and amodimethicones comprising amine groups on side chains such as bis-cetearyl amodimethicone, notably that marketed by Momentive Performance Materials.

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

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

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

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

A) (poly)amino compounds chosen from:

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

ib) polyether diamines, in particular polyethylene glycol α, ω-diamine, with amine function at the end of the chain,

(ic) polyether triamines, in particular polyetheramine (or jeffamine),

(id) aminoalkoxysilanes, in particular APTES,

ie) spermidine, and

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

B) (poly)thiolated compounds chosen from:

(iia) polydialkylsiloxanes with thiol functions, and

(iib) alkoxysilanes with thiol functions,

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

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

formula (XIII) in which:

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

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

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

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

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

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

L[-YC(O)-C(R ^e )=CH ₂ ] _q (XIV)

formula (XIV) in which:

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

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

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

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

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

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

COSMETIC ACTIVE INGREDIENTS iv)

According to a particular embodiment, the method of the invention further comprises the application of iv) at least one cosmetic active ingredient, to said keratin materials.

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

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

(a) colouring matters (or colouring agents), in particular chosen from pigments, direct dyes and their mixtures,

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

c) UV filters, and

d) their mixtures.

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

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

COLOURING MATERIALS

According to a particular embodiment, the method 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 at a rate of at least 0.01% by weight, relative to the total weight of the composition considered.

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

Preferably, at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5” comprises at least one coloring material chosen from pigments, direct dyes and their mixtures, more preferably pigments.

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

PIGMENTS

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

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

These pigments can be synthetic or natural.

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

They can be coated or uncoated.

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

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

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

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

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

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

By "organic pigment" is meant any pigment that meets the definition of the Ullmann encyclopedia in the organic pigment chapter. Among the organic pigments useful in the present invention, mention may be made of nitroso, nitro, azo, xanthene, pyrene, quinoline, quinoline, anthraquinone, triphenylmethane, fluorane, phthalocyanine, metal complex type, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, indigo, thioindigo, dioxazine, triphenylmethane and quinophthalone. In particular, the white or colored organic pigments may be chosen from carmine, carbon black, aniline black, azo yellow, quinacridone, phthalocyanine blue, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the orange pigments codified in the Color Index under the references CI 11725, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 26100, 45380, 45410, 58000, 73360, 73915, 75470, the pigments obtained by oxidative polymerization of indole, phenolic derivatives as described in patent FR 2 679 771.

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

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

The organic pigment can also be a lake.

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

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

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

The pigment can also be a special effects pigment.

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

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

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

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

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

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

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

DIRECT DYES

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

By "direct dye" we mean natural and/or synthetic dyes, different from oxidation dyes. These are dyes that 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. Mention may be made of cationic hydrazono dyes of formulas (A) and (B) below and cationic azo dyes of formulas (C) and (D) below:

Hét ⁺ -C(Ra)=NN(Rb)-Ar, Q ^- (A)

Het ⁺ -N(Ra)-N=C(Rb)-Ar, Q ^- (B)

Het ⁺ -N=N-Ar, Q ^- (C)

Ar ⁺ -N=N-Ar'', Q ^- (D)

formulas (A) to (D) in which:

- Het ⁺ represents a cationic heteroaryl radical, preferably with an endocyclic cationic charge such as imidazolium, indolium, or pyridinium, optionally substituted preferably by at least one (C ₁ -C ₈ )alkyl group such as methyl;

- Ar ⁺ represents an aryl radical, such as phenyl or naphthyl, with an exocyclic cationic charge, preferably ammonium, particularly tri(C ₁ -C ₈ )alkyl-ammonium such as trimethylammonium;

- Ar represents an aryl group, in particular phenyl, optionally substituted, preferably by one or more electron-donating groups such as (C ₁ -C ₈ )alkyl optionally substituted, (C ₁ -C ₈ )alkoxy optionally substituted, (di)(C ₁ -C ₈ )(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxy group, aryl(C ₁ -C ₈ )alkylamino, and N-(C ₁ -C ₈ )alkyl-N-aryl(C ₁ -C ₈ )alkylamino optionally substituted or Ar represents a julolidine group;

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

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

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

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

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

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

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

(E)

(F)

formula (E) or (F) in which:

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

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

- R ⁴ represents a hydrogen atom or an electron-donating group such as (C ₁ -C ₈ )alkyl optionally substituted, (C ₁ -C ₈ )alkoxy optionally substituted, (di)(C ₁ -C ₈ )(alkyl)amino optionally substituted on the alkyl group(s) by a hydroxy group; particularly R ⁴ is a hydrogen atom;

- Z represents a CH group or a nitrogen atom, preferably CH;

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

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

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

Anionic direct dyes may be selected from acid nitrate direct dyes, acid azo dyes, acid azine dyes, acid triarylmethane dyes, acid indoamine dyes, acid anthraquinone dyes, indigoids and acid natural dyes.

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

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

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

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

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

CARE ACTIVE INGREDIENTS

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

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

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

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

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

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

UV FILTERS

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

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

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

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

They can be lipophilic, hydrophilic or insoluble organic.

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

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

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

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

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

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

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

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

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

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

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

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

Preferably, the method for treating keratin materials, in particular keratin fibers, and the compositions “C1”, “C2”, “C3”, “C4” or “C5” use or comprise 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, in particular red, such as D&C RED 7.

FATTY PHASE – FATTY SUBSTANCES

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(xii) their mixtures;

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

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

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

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

In particular, the amount of oil(s) in at least one of the compositions “C1”, “C2”, “C3”, “C4” or “C5” used in the process according to the invention ranges from 1% to 50% by weight, relative to the total weight of the composition, more particularly from 2% to 30% by weight, preferentially from 3% to 20%, better still from 5% to 15% by weight, relative to the total weight of the composition.

COMPOSITIONS

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

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

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

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

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

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

More particularly, the compositions “C1”, “C2”, “C3”, “C4” and/or “C5”, preferably “C1”, “C2” and/or “C3” are aqueous.

According to a particular embodiment, the compositions “C1”, “C2”, “C3”, “C4” and/or “C5” are hydroalcoholic. In particular, they comprise an ethanol/water mixture, in particular in a volume ratio of between 1/99 to 99/1, more particularly between 10/90 to 90/10, even more particularly between 20/80 and 80/20, preferably 40/60 to 60/40, such as 50/50.

According to a particular embodiment, the compositions “C1”, “C2”, “C3”, “C4” and/or “C5” comprise an isododecane/ethanol mixture, in particular in a volume ratio of between 1/99 to 99/1, more particularly between 10/90 to 90/10, even more particularly between 20/80 and 80/20, preferably 40/60 to 60/40, such as 50/50.

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

According to a particular embodiment, the composition “C1” is anhydrous. In particular, the composition “C1” is anhydrous, and it comprises at least one oil, in particular volatile, preferably isododecane.

According to a particular embodiment, the composition “C2” is anhydrous. In particular, the composition “C2” is anhydrous, and it comprises at least one oil, in particular volatile, preferably isododecane.

According to a particular embodiment, the composition “C3” is anhydrous. In particular, the composition “C3” is anhydrous, and it comprises at least one oil, in particular volatile, preferably isododecane.

According to another particular embodiment of the invention, the composition “C4” is anhydrous. According to another variant, the composition “C5” is anhydrous.

The compositions “C1” to “C5” used in the process of the invention may further comprise one or more organic solvents, distinct from the water-soluble solvent(s) with which the compound(s) of formula (I) may be used.

An "organic solvent" means an organic substance capable of dissolving another substance without chemically modifying it.

As organic solvent, mention may be made, for example, of 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, notably chosen from polyols notably having from 2 to 10 carbon atoms, preferably having from 2 to 6 carbon atoms, preferably glycerin.

The compositions “C1”, “C2”, “C3”, “C4” or “C5” used in the process of the invention may further comprise one or more adjuvants commonly used in cosmetics, in particular chosen from thickeners, film-forming agents other than the compounds of formula (I), gelling agents, trace elements, softeners, sequestering agents, perfumes, alkalizing or acidifying agents, dispersing agents, preservatives, fillers, surfactants, anti-hair loss agents, anti-dandruff agents, anti-free radical agents, propellants, polar additives, polymers, or mixtures thereof.

Another subject of the invention is a composition “C3”, preferably aqueous, comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, as defined above, ii) at least one crosslinking agent, in particular as defined above, iv) at least one cosmetic active ingredient, in particular as defined above, and optionally iii) water.

Another object of the invention is the cosmetic use of the composition “C3” as defined above, for the treatment of keratin materials, in particular for the care, styling and/or coloring of keratin fibers, preferably hair.

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

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

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

• soit d’un produit coloré pour les lèvres ;
• soit d’un produit de soin de la peau, éventuellement coloré, en particulier une crème ou un fluide présentant des propriétés hydratantes et/ou de comblement et/ou à effet tenseur ; ou
• soit d’un produit capillaire, en particulier d’un produit de coloration capillaire ou encore d’un produit de coiffage notamment dénué de matière colorante, comme une laque, ou un produit dit de « styling » de type mousse ou gel.

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

• either a colored lip product;
• either a skin care product, possibly colored, in particular a cream or fluid with moisturizing and/or filling and/or tightening properties; or
• either a hair product, in particular a hair coloring product or a styling product, in particular one without coloring matter, such as a hairspray, or a so-called “styling” product such as mousse or gel.

KIT

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

- at least one compartment containing at least i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, as defined above, optionally iii) water, and optionally iv) at least one cosmetic active ingredient, in particular as defined above, in particular comprising the composition “C1” as defined above;

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

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

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

METHODS AND MEASURES

SKIN APPLICATION

a) 1-step protocol

The compounds of formula (I) with acetoacetate functions, and optionally the crosslinking agents, are mixed together before application. The system remains fluid long enough to allow application to the substrate.

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

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

b) 2-step protocol

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

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

The deposit is left to dry for 24 hours.

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

RESISTANCE TO OLIVE OIL/SEBUM/WATER

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

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

Resistance is assessed according to the following scale:

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

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

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

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

EVALUATION OF MATTENESS

The formulas are applied using an applicator (wet thickness 100 µm) on a contrast card (reference: byko-charts Opacity chart #2810).

Using a gloss meter, the gloss is measured at 20° (angle of incidence) from the card, then the gloss/mattness of the deposit 24 hours after application.

PROTOCOL REMANENCE OF BRILLIANCE

The compositions, comprising a compound of formula (I), a matting agent (Stearalkonium hectorite, marketed under the reference Bentone 27 V CG, by the company Elementis), and/or a crosslinker and a solvent, are applied using an applicator (wet thickness 100 µm) on a contrast card (reference: byko-charts Opacity chart #2810).

Using a gloss meter, the gloss at 20° (angle of incidence) of the card is measured, then the gloss/mattness of the deposit 24 hours after application.

Once dry, 0.5 ml of water, olive oil and sebum are deposited and left for 5 minutes.

The drops of aggressors are then rubbed using a cotton pad (15 passes) and the shine/matteness measurement is carried out on the attacked area (average of 5 measurements).

HAIR COLORING APPLICATION

The hair coloring evaluation protocol is detailed below:

The assessments are conducted according to two different protocols: in 1 or 2 steps, each on strands of 90% white natural hair.

a) 1-step protocol

The compounds of formula (I) with acetoacetate functions, and optionally the crosslinking agents, are mixed together before application. The system remains fluid long enough to allow application to the substrate.

The composition is applied to strands of 90% white natural dry hair, at a rate of 1 g of composition per gram of strand.

The hair strands are left for 5 minutes at room temperature.

The hair strands are then combed and blow-dried for 3 minutes.

The hair strands are left at room temperature for 18 hours at 80% relative humidity. The hair is colored evenly and intensely.

The locks of hair thus colored are then subjected to a test of several repeated shampoos in order to evaluate the tenacity (the persistence) of the coloring obtained from the shampoos, according to the shampoo protocol described below.

b) 2-step protocol

A first composition, called a "base coat", is applied to strands of 90% white natural dry hair, at a rate of 0.5 g of composition per gram of strand. The strands are then combed. This deposit is applied to the keratin materials, then it is left to set for between 10 seconds and 24 hours, particularly between 1 minute and 1 hour, such as 30 minutes, at room temperature (25°C). This drying step can be accelerated by subjecting the keratin material to heating after application, for example using a hair dryer.

After this first step, a second composition, called “top coat”, is applied to the lock of hair, at a rate of 0.5 g per gram of lock.

After application, the hair strands are then combed and dried with a hair dryer.

The hair strands are left at room temperature for 24 hours under a hood. The hair is colored evenly and intensely.

The locks of hair thus colored are then subjected to a test of several repeated shampoos in order to evaluate the tenacity (the persistence) of the coloring obtained from the shampoos, according to the shampoo protocol described below.

SHAMPOO PROTOCOL

The colored hair strands are combed, moistened under water at 35 °C before being passed between the fingers 5 times for 5 seconds. The hair strands are then wrung out between two fingers.

A standard shampoo (Garnier Ultra Doux) is applied evenly to the colored strands at a rate of 0.4 g of standard shampoo per gram of strands, gently kneading the strands of hair lengthwise (6 passes) for 15 seconds, from root to tip.

The hair strands are then placed in a watch glass and left for 1 minute.

Then, the hair strands are rinsed with water by passing the strand between the fingers (15 passes). The hair strands are then wrung out between two fingers before the next shampoo.

Once the several shampoo tests are done, the hair strands are combed and dried with a hair dryer.

REMANENCE PROTOCOL

The color persistence of the strands was evaluated in the CIE L*a*b* system, using a Minolta Spectrophotometer CM3600A colorimeter (illuminant D65, angle 10°, specular component included).

In this L*a*b* system, L* represents the color intensity, a* indicates the green/red color axis and b* the blue/yellow color axis.

The persistence of the colour is assessed by the colour difference ΔE between the coloured strands before shampooing, then after undergoing 1 and 3 shampoos according to the protocol described above. The lower the value of ΔE, the more the colour persists after shampooing.

The value of ΔE is calculated according to the following equation:

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

STYLING APPLICATION: STYLING EVALUATION PROTOCOL

The styling assessment protocol is detailed below:

1) Application without crosslinker

2 g of a solution containing the formulas described below are applied to a strand (90% Natural White BN hair, length 20.5 cm) spread on aluminum foil, then the strand is wrapped around a brush (approximate diameter of 2 cm by a length of 3 cm) and is held by a hair clip for 24 hours, then the strand is released from the support (brush + clip).

The length of the wick is measured immediately and 24 hours later, after storage at room temperature at 25°C.

To check the water resistance after the 24-hour measurements, the strands are immersed in a water bath for 20 min then dried hanging at room temperature for 24 h and measured.

A comparison of the retention of the loop is carried out between the compositions according to the invention and the comparative compositions.

2) Application with crosslinker

2 g of a solution containing the formulas described below (“Base coat”) are applied to a strand (90% Natural White BN hair, length 20.5 cm) spread on aluminum foil and then, directly afterwards, 2 g of solution comprising at least one crosslinker is applied (“Top Coat”). The strand is wrapped around a brush (approximate diameter of 2 cm by a length of 3 cm) and is held by a hair clip for 24 hours, then the strand is released from the support (brush + clip).

The length of the wick is measured immediately and 24 hours later, after storage at room temperature at 25°C.

To check the water resistance after the 24-hour measurements, the strands are immersed in a water bath for 20 min then dried hanging at room temperature for 24 h and measured.

A comparison of the retention of the loop is carried out between the compositions according to the invention and the comparative compositions.

EXAMPLE 1: Synthesis of Pullulan with acetoacetate function (polysaccharide 1)

Polysaccharide 1 was prepared according to the following scientific article “Enzyme-Responsive Biopolymeric Nanogel Fibers by Extrusion: Engineering of High-Surface-Area Hydrogels and Application in Bacterial Enzyme Detection”, ACS Applied Materials and Interfaces, 13(11), pp. 12928-12940 (2021).

In a three-necked flask (1 liter) topped with a Dean-Stark and a condenser, 350 g of DMSO are introduced. The reaction medium is heated to 90 °C and stirred using a magnetic bar. 42.5 g of pullulan is then added in successive additions, ensuring the good solubility of each of the fractions introduced (addition over approximately 24 h). 23 g of tert-butyl acetoacetate is added dropwise via a dropping funnel and the mixture is then maintained at 120 °C for 2 h. After 2 h, the mixture is brought back to 60 °C.

The mixture is then introduced drop by drop into cold isopropanol (ice bath) – fractional addition in 5 x 600 ml. A paste is obtained and filtered on a Buchner funnel, dried (rotavapor 45 °C), then redissolved at 90 °C in DMSO. After cooling to room temperature, the mixture is introduced fractionally into cold acetone (4 x 600 ml), in an ice bath.

A white solid is obtained, the latter then being filtered on Buchner.

The product is then dried at 45°C under reduced pressure (rotavapor), then under high vacuum (Schlenck line 50°C, 8 h).

EXAMPLE 2: Synthesis of myristoyl Pullulan with acetoacetate function (polysaccharide 2)

The synthesis is represented by the following preparation scheme:

• m est tel que défini précédemment ;
• R¹¹est tel que défini précédemment ;

• R^{1 2}, identiques ou différents, représentent un atome d’hydrogène ou un groupe n-CH₁₃H₂₇-C(O)-, étant entendu que le myristoyl pullulan possède au moins un groupe CH₁₃H₂₇-C(O)-.

diagram in which:

• m is as defined previously;
• R ¹¹ is as defined above;

• R ^{1 2} , identical or different, represent a hydrogen atom or a n-CH ₁₃ H ₂₇ -C(O)- group, it being understood that myristoyl pullulan has at least one CH ₁₃ H ₂₇ -C(O)- group.

In a three-necked flask (250 mL) equipped with mechanical stirring and a distillation column, 20 g of Pullulan Myristoyl and 100 g of tert-butyl acetoacetate are introduced. The reaction medium is heated using an oil bath (oil bath temperature 150 °C-160 °C) for 10 h. The reaction medium is then purified in a rotavapor at 150 °C under continuous vacuum, then 100 g of isododecane are introduced. The extract is rectified to 25% active material in isododecane. The polymer is obtained in the form of a solution in isododecane.

EXAMPLE 3: Preparation of compositions A and B – Without crosslinker

Composition A comprising a polysaccharide compound of formula (I), and composition B, devoid of compound of formula (I), are prepared from the contents indicated in the table below. The contents are expressed as a percentage by weight, relative to the total weight of the composition.

Compositions A and B are prepared by simply mixing the ingredients detailed in Table 1 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

EXAMPLE 4: 1-step skin application of compositions A and B (without crosslinker)

Simplex formula evaluations were conducted to show performance for skin application.

Compositions A and B are applied according to the 1-step skin application protocol described above.

The deposits are then evaluated according to the olive oil and sebum resistance protocols of the formulations on Bioskin.

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

It appears that the application of composition A according to the method of the invention makes it possible to obtain a persistence to sebum and olive oil, improved compared to the application of composition B.

We therefore obtain, thanks to the application of composition A according to the process of the invention, deposits resistant to daily chemical attacks (sebum/olive oil).

EXAMPLE 5: Preparation of compositions C and D – With crosslinker

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

The “Base Coat” compositions are prepared by simply mixing the ingredients detailed in Table 3 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

The “Top Coat” compositions are prepared by simply mixing the ingredients detailed in Table 3 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

EXAMPLE 6: 2-step skin application of compositions C and D (with crosslinker)

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

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

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

It appears that the application of composition C according to the process of the invention makes it possible to obtain a persistence to water and olive oil, improved compared to the application of composition D. The application of composition C according to the invention leads in particular to a water-resistant deposit.

We therefore obtain, thanks to the application of composition C according to the process of the invention, deposits resistant to daily chemical attacks (water/olive oil).

EXAMPLE 7: Preparation of compositions E and F – With crosslinker

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

The “Base Coat” compositions are prepared by simply mixing the ingredients detailed in Table 5 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

The “Top Coat” compositions are prepared by simply mixing the ingredients detailed in Table 5 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

EXAMPLE 8: 2-step skin application of compositions E and F (with crosslinker)

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

The deposits are then evaluated according to the water, olive oil and sebum resistance protocols of the formulations on Bioskin.

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

It appears that the application of composition E according to the process of the invention makes it possible to obtain a persistence to water, sebum and olive oil, improved compared to the application of composition F.

We therefore obtain, thanks to the application of composition E according to the process of the invention, deposits resistant to daily chemical attacks (water/sebum/olive oil).

EXAMPLE 9: Preparation of compositions G and H – With crosslinker

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

The “Base Coat” compositions are prepared by simply mixing the ingredients detailed in Table 7 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

The “Top Coat” compositions are prepared by simply mixing the ingredients detailed in Table 7 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

EXAMPLE 10: 2-step skin application of compositions G and H (with crosslinker)

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

The deposits are then evaluated according to the water, olive oil and sebum resistance protocols of the formulations on Bioskin.

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

It appears that the application of composition G according to the process of the invention makes it possible to obtain a persistence to water, sebum and olive oil, improved compared to the application of composition H.

We therefore obtain, thanks to the application of composition G according to the process of the invention, deposits resistant to daily chemical attacks (water/sebum/olive oil).

EXAMPLE 11: Preparation of compositions I and J – With crosslinker

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

The “Base Coat” compositions are prepared by simply mixing the ingredients detailed in Table 9 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

The “Top Coat” compositions are prepared by simply mixing the ingredients detailed in Table 9 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at temperature.

EXAMPLE 12: 2-step skin application of compositions I and J – Evaluation of mattness

Compositions I and J are applied according to the matteness evaluation protocol described above.

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

It appears that the application of composition I according to the process of the invention makes it possible to obtain a more matte crosslinked film compared to that obtained by the application of composition J.

EXAMPLE 13: Preparation of composition K – With crosslinker

Composition K is prepared from the contents indicated in the table below. The contents are expressed as a percentage by weight, relative to the total weight of the composition considered.

The composition of “Base Coat” is prepared by simply mixing the ingredients detailed in Table 11 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

The composition of “Top Coat” is prepared by simply mixing the ingredients detailed in Table 11 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

EXAMPLE 14: 2-step skin application of composition K – Evaluation of shine/matteness persistence

Composition K is applied according to the gloss/matte persistence protocol described above.

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

It appears that the application of composition K according to the method of the invention makes it possible to obtain a matte crosslinked film. In addition, it appears that the application of composition K according to the method of the invention makes it possible to significantly improve the persistence of the matte finish, after aggression with water, olive oil and sebum.

EXAMPLE 15: Preparation of composition L – With crosslinker

Composition L is prepared from the contents indicated in the table below. The contents are expressed as a percentage by weight, relative to the total weight of the composition considered.

The composition of “Base Coat” is prepared by simply mixing the ingredients detailed in Table 13 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

The composition of “Top Coat” is prepared by simply mixing the ingredients detailed in Table 13 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

EXAMPLE 16: 2-step hair coloring application of composition L (with crosslinker)

Composition L is applied according to the 2-step hair coloring application protocol described above.

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

The locks of hair colored according to the invention have a ΔE value of less than 1. It therefore appears that the application of composition L according to the process of the invention makes it possible to obtain very good color persistence.

EXAMPLE 17: Preparation of compositions M to P – Without crosslinker

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

Compositions M to P are prepared by simply mixing the ingredients detailed in Table 15 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

EXAMPLE 18: Application of styling without crosslinker of compositions M to P (without crosslinker) – Evaluation of the loop

Compositions M to P are applied according to the styling protocol without crosslinker described previously.

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

It appears that the application of composition O according to the process of the invention makes it possible to significantly improve the water resistance of non-crosslinked locks, compared to the application of compositions M, N and P.

EXAMPLE 19: Preparation of compositions Q and R – With crosslinker

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

The “Base Coat” compositions are prepared by simply mixing the ingredients detailed in Table 17 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

The “Top Coat” compositions are prepared by simply mixing the ingredients detailed in Table 17 using a Speed Mixer (a mixing device that uses centrifugal force) for 2 minutes, at 3500 rpm and at room temperature.

EXAMPLE 20: 2-step styling application with crosslinking of compositions Q and R – Evaluation of the curl

Compositions Q and R are applied according to the styling protocol with crosslinker described above.

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

It appears that the strand treated with formula R, according to the process of the invention, makes it possible to significantly improve the shape of the curls which appear sharper and closer together unlike the strand treated with the comparative formula Q.

Furthermore, even after 20 minutes in a water bath and then 24 hours at room temperature, the lock treated with formula R, according to the process of the invention, has a much better curl retention than the lock treated with the comparative formula Q.

Claims (22)

Process for treating keratin materials, comprising the application to said keratin materials, in one or more successive steps, of at least:
(i) one or more compounds of formula (I) and their optical or geometric isomers, their acid or base salts, and/or solvates, such as hydrates, or a composition containing it or them:

(I)
formula (I) in which:
- R ¹ represents a multivalent, linear or cyclic polysaccharide radical, preferably linear, consisting of at least 3 monosaccharide units, each comprising at least 5 carbon atoms, particularly between 7 and 9 carbon atoms, preferably at least 6 carbon atoms, more particularly between 6 and 8 carbon atoms, and more preferentially 6 carbon atoms, and of which one or more of the hydroxy (-OH), carbonyl (-C(O)), carboxy (-C(O)-OH) or amino -NH ₂ groups, of all or part of at least one of the monosaccharide units, are optionally substituted by one or more R ³ groups;
- 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, more preferably methyl;
- R ³ , identical or different, represents a group chosen from:
1) sulfonate -SO ₃ ^- , Cat ⁺ ,
2) (C ₁ -C ₂₂ )alkyl, linear or branched, and
3) (C ₁ -C ₂₂ )alkylcarbonyl, linear or branched,
the (C ₁ -C ₂₂ )alkyl group being optionally interrupted by one or more heteroatoms or groups X as defined below; and/or
the (C ₁ -C ₂₂ )alkyl group being optionally substituted by one or more groups chosen from: a) hydroxy (-OH); b) sulfonate -SO ₃ ^- , Cat ⁺ ; c) sulfate -O-SO ₃ ^- , Cat ⁺ ; d) -(CH ₂ -CH ₂ -O) _p -R ⁴ ; e) –O-(CH ₂ -CH ₂ -O) _p -R ⁴ ; f) -C(O)-R ⁴ ; g) -C(O)-OR ⁴ ; h) -OC(O)-R ⁴ ; i) -C(O)-N(R')-R ⁴ ; j) -N(R')-C(O)-R ⁴ ; k) ammonium -N ⁺ R''₃; An ^- and l) mixtures thereof;
- R ⁴ represents a hydrogen atom, a linear or branched (C ₁ -C ₈ )alkyl group _, preferably R ⁴ represents a hydrogen atom or a linear or branched (C ₁ -C ₆ )alkyl group, more preferably a linear or branched (C ₁ -C ₄ )alkyl group, in particular methyl;
- R ^a and R ^b , identical or different, represent a hydrogen atom or a (C ₁ -C ₄ )alkyl group, preferably a hydrogen atom;
- X is a heteroatom or group selected from -O-, -S-, -N(R')-, and combinations thereof such as -C(O)-O-, -OC(O)-, -C(O)-N(R')-, -N(R')-C(O)-, -N(R')-C(O)-O-, -N(R')-C(O)-N(R')-, preferably X represents -O-;
- R', identical or different, represents a hydrogen atom, a (C ₁ -C ₆ )alkyl group, linear or branched, optionally substituted by at least one hydroxyl group (OH), preferably R' represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, in particular methyl, more preferably R' represents a hydrogen atom;
- R'', identical or different, represents a hydrogen atom or a linear or branched (C ₁ -C ₆ )alkyl group, preferably a (C ₁ -C ₄ )alkyl group, in particular methyl;
- n denotes an integer ranging from 2 to 3000, in particular from 5 to 2500, more particularly from 10 to 2300, preferably from 15 to 1000, preferentially from 20 to 500, and more preferentially from 25 to 200;
- p denotes an integer ranging from 0 to 3;
- An ^- represents an anionic counterion;
- Cat ⁺ represents a cationic counterion;
ii) optionally at least one crosslinking agent; and
iii) optionally water, preferably water, or optionally water mixed with a polar organic solvent, preferably chosen from (C ₂ -C ₆ )alkanol, more preferably ethanol. Treatment method according to the preceding claim, in which the compound(s) of formula (I) is (are) such that the polysaccharide chain, represented by R ¹ , is chosen from polysaccharide radicals derived from agarose, starch and its derivatives, cationic starch, alginate and its derivatives, hyaluronic acid, cellulose and its derivatives, in particular chosen from methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxypropylmethylcellulose and hydroxybutylcellulose, carrageenan, curdlan, dextran, glucan, guar gum, gellan, konjac, inulin, pectin, pullulan, scleroglucan, xanthan and their derivatives, preferably chosen from starch and its derivatives, cellulose and its derivatives and alginate and its derivatives, and more preferentially chosen from pullulan and its derivatives. derivatives, such as myristoyl pullulan. Treatment method according to any one of the preceding claims, in which the compound(s) of formula (I) is (are) chosen from:
(a) cellulose, starch, amylose and their derivatives, of formula (II) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(II)
(b) alginate, pectin and their derivatives, of formula (III) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(III)
(c) hyaluronic acid and its derivatives, of formula (IV) and their isomers and solvates:

(IV)
(d) dextran and its derivatives, of formula (V) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(V)
(e) inulin and its derivatives, of formula (VI) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(VI)
(f) guar gum and its derivatives, of formula (VII) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(VII)
(g) glucan and its derivatives, of formula (VIII) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(VIII)
(h) carrageenan and its derivatives, in particular of formula (IX), as well as their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(IX)
in particular chosen from the derivatives γ-carrageenan, δ-carrageenan, μ-carrageenan, ν-carrageenan, λ-carrageenan, and their respective basic forms β-carrageenan, α-carragenene, κ-carrageenan, ι-carrageenan, θ-carrageenan, it being understood that the carragenans comprise at least one group of formula (XII), preferably at least two groups of formula (XII);
(i) cyclodextrin and its derivatives, of formula (X):

(X)
(j) pullulan and its derivatives, of formula (XI) and their optical isomers, their organic or mineral acid or base salts, and solvates, such as hydrates:

(XI)
formulas (II) to (XI) in which:
- R ⁶ , identical or different, represents -CH ₂ -OR ⁷ or -C(O)-OR ⁷ ,
- R ⁷ , identical or different, represent a hydrogen atom or a group R ³ as defined in formula (I), preferably a (C ₁ -C ₂₂ )alkyl group, optionally substituted by at least one hydroxy group (-OH) or a -C(O)-R ⁸ group, with R ⁸ representing a (C ₁ -C ₂₂ )alkyl group, or a -CH ₂ -CH(OH)-CH ₂ -N ⁺ (CH ₃ ) ₃ An ^{- group} , or a group R ⁹ of formula (XII), R ^7' represents a radical R ⁷ or a -SO ₃ ^- group, Cat ⁺ , Cat ⁺ being as defined above:

(XII)
formula (XII) in which R ^a , R ^b , and R ² are as defined above for the compounds of formula (I), preferably R ² denotes a methyl radical and R ^a and R ^b denote a hydrogen atom;
- R ¹⁰ , identical or different, represent a hydrogen atom, a (C ₁ -C ₄ )alkyl group, such as -CH ₃ or an R ⁹ group as defined above;
- m denotes an integer ranging from 2 to 3000, in particular from 5 to 2500, more particularly from 10 to 2300, preferably from 15 to 1000, preferentially from 20 to 500, and more preferentially from 25 to 200;
- An ^- being as defined above;
it being understood that formulas (II) to (XI) have at least one R ⁹ unit, and preferably at least two R ⁹ units, in their structure. Treatment method according to any one of the preceding claims, in which the compound(s) of formula (I) is (are) chosen from:
- alginic acid 3-oxobutanoate (CAS no.: 2135428-65-6);
- amylose 3-oxobutanoate (CAS no.: 106254-13-1);
- cellulose, 3-oxobutanoate, 2-hydroxyethyl ether (CAS number: 104708-71-6);
- cellulose, 3-oxobutanoate, carboxymethyl ether (CAS number: 105953-68-2);
- cellulose, 3-oxobutanoate, 2-hydroxypropyl ether (CAS number: 105953-69-3);
- cellulose, 3-oxobutanoate, methyl ether (CAS number: 105953-70-6);
- cellulose, tris(3-oxobutanoate) (CAS number: 119466-02-3);
- cellulose, 3-oxobutanoate (CAS number: 80619-14-3);
- cellulose, acetate 3-oxobutanoate (CAS number: 168608-38-6);
- cellulose, hexanoate 3-oxobutanoate (CAS number: 1696417-96-5);
- cellulose, 3-oxobutanoate propanoate (CAS number: 163381-45-1);
- cellulose, butanoate 3-oxobutanoate (CAS number: 163438-87-7);
- cellulose, 4-methoxy-3-oxobutanoate (CAS number: 2410687-10-2);
- cellulose, 3-oxobutanoate, 2-hydroxypropyl methyl ether (CAS number: 2223678-14-4);
- cellulose, acetate butanoate 3-ethoxypropanoate 3-oxobutanoate (CAS number: 334475-56-8);
- cellulose, 2-hydroxypropyl ether, 3-oxobutanoate (CAS number: 497932-47-5);
- cellulose, 3-oxobutanoate, ethyl ether (CAS number: 497932-48-6);
- dextran, 3-oxobutanoate (CAS number: 882428-66-2);
- D-Glucan, 3-oxobutanoate (CAS number: 2135428-66-7);
- guar gum, 3-oxobutanoate (CAS number: 497932-49-7);
- hyaluronic acid, 3-oxobutanoate (CAS number: 2135428-62-3);
- starch, 3-oxobutanoate (CAS number: 78207-15-5);
- starch, 3-oxobutanoate, methyl ether (CAS number: 2135428-59-8);
- starch, 3-oxobutanoate, 2-carboxymethyl ether (CAS number: 2135428-60-1);
- starch, 2-hydroxypropyl ether, 3-oxobutanoate (CAS number: 2135428-61-2);
- starch, 3-oxobutanoate, 2-hydroxypropyl ether (CAS number: 2223678-15-5);
- pullulan acetoacetate (CAS number: 2762209-81-2);
- cyclodextrin, ethyl-3-oxobutanoate (CAS number: 152154-93-3);
- cyclodextrin, 3-oxobutanoate (CAS number: 2135428-63-4); And
- myristoyl pullulan acetoacetate. Treatment method according to any one of the preceding claims, in which the compound(s) of formula (I) is (are) chosen from pullulan acetoacetate and myristoyl pullulan acetoacetate. Treatment method according to any one of the preceding claims, comprising the application to said keratin materials of at least iii) water. Treatment method according to any one of the preceding claims, comprising the application to said keratin materials of at least ii) a crosslinking agent. Treatment method according to any one of the preceding claims, comprising the application to said keratin materials of at least ii) a crosslinking agent chosen from (poly)amine, (poly)thiolated, (poly)carbonyl, (poly)acrylate, metal alkoxide compounds, and their mixtures, preferably chosen from (poly)amine, (poly)thiolated, (poly)acrylate compounds and their mixtures, and more preferably chosen from (poly)amine, (poly)thiolated compounds and their mixtures. Treatment method according to any one of the preceding claims, comprising the application to said keratin materials of at least ii) one crosslinking agent chosen from:
A) (poly)amino compounds chosen from:
ia) chitosans such as poly(D-Glucosamine),
ib) polyether diamines, in particular polyethylene glycol α, ω-diamine, with amine function at the end of the chain,
(ic) polyether triamines, in particular polyetheramine (or jeffamine),
(id) aminoalkoxysilanes, in particular APTES,
ie) spermidine, and
(if) polydialkylsiloxanes comprising primary amine groups at the chain end or on side chains, in particular polydimethylsiloxanes comprising primary amine groups, more particularly poly(dimethoxysiloxane) terminated with bis(3-aminopropyl) (PDMS-diNH ₂ ) and amodimethicones comprising amine groups on side chains, more particularly bis-cetearyl amodimethicone;
B) (poly)thiolated compounds chosen from:
(iia) polydialkylsiloxanes with thiol functions, and
(iib) alkoxysilanes with thiol functions,
and in particular chosen from compounds iia) polydialkylsiloxanes with thiol functions, preferably from polydimethylsiloxanes comprising thiol groups on the side chain, in particular mercaptopropyl, and more particularly chosen from compounds of formula (XIII):
R ^a -Si(R ^b )(R ^d )-O-[Si(R ^a )(R ^b )-O] _m -[Si(R ^b )(ALK ₁ -SH)-O] _n -Si(R ^b )(R ^d )-R ^a (XIII)
formula (XIII) in which:
- R ^a and R ^b , identical or different, preferably identical, represent a (C ₁ -C ₄ )alkyl group, in particular methyl, a (C ₁ -C ₄ )alkoxy group, in particular methoxy, an aryl group, in particular phenyl, an aryloxy group, in particular phenoxy, an aryl(C ₁ -C ₄ )alkyl group, in particular benzyl, or an aryl(C ₁ -C ₄ )alkoxy group, in particular benzoxy, and preferably a (C ₁ -C ₄ )alkyl group, more preferably methyl,
- R ^d represents a (C ₁ -C ₄ )alkyl group, in particular methyl, a (C ₁ -C ₄ )alkoxy group, in particular methoxy, an aryl group, in particular phenyl, an aryloxy group, in particular phenoxy, an aryl(C ₁ -C ₄ )alkyl group, in particular benzyl, an aryl(C ₁ -C ₄ )alkoxy group, in particular benzoxy, or a (C ₁ -C ₆ )alkyl group substituted by a (C ₁ -C ₄ )alkylamino, amino, or thiol group, and preferably a (C ₁ -C ₄ )alkyl group, more preferably methyl,
and preferably R ^a , R ^b , and R ^d , are identical and represent a (C ₁ -C ₆ )alkyl group, more preferably methyl,
- ALK ₁ represents a divalent hydrocarbon chain comprising from 1 to 100 carbon atoms, saturated or unsaturated, linear or branched, optionally cyclic, optionally interrupted by one or more heteroatoms, such as oxygen, sulfur or nitrogen, in particular oxygen, a (thio)carbonyl group C(X) with X representing O or S, or their associations, in particular -O-, -OC(O)- or -C(O)-O-, preferably ALK ₁ represents a (C ₁ -C ₆ )alkylene group, more preferably (C ₁ -C ₄ )alkylene, even more preferably propylene,
- n and m, identical or different, represent an integer greater than 2, and in particular the values of m and n are such that the weight-average molecular weight of said polyorganosiloxane is between 1000 and 55000 g.mol ^-1 ; and
C) (poly)acrylate compounds of formula (XIV):
L[-YC(O)-C(R ^e )=CH ₂ ] _q (XIV)
formula (XIV) in which:
- q represents an integer greater than or equal to 2, in particular n is inclusively between 2 and 10, and preferably between 2 and 5,
- L denotes an at least divalent multivalent group, in particular comprising between 1 and 500 carbon and/or silicon atoms, more particularly between 2 and 40 carbon and/or silicon atoms, even more particularly between 3 and 30 carbon and/or silicon atoms, preferably between 6 and 20 carbon atoms, linear or branched, saturated or unsaturated, or (hetero)cyclic, saturated or unsaturated; L being optionally interrupted and/or terminated by one or more heteroatoms or groups chosen from O, S, N, Si, C(X), and their combinations, in particular -O-, -OC(X)-, -N(R)-C(X)-, -Si(R _c )(R _d )-O- with R representing a hydrogen atom or a (C ₁ -C ₆ )alkyl group, in particular methyl; and/or L being optionally substituted by one or more groups chosen from: -N(R _a )R _b , and -(X') _a -C(X)-(X'') _b -R _a , with X, X' and X'', identical or different, representing an oxygen atom, sulfur atom, or an N(R _b ) group, a and b being 0 or 1, preferably the sum of a and b being 1, R _a and R _b , identical or different, representing a hydrogen atom, a (C ₁ -C ₆ )alkyl group, or an aryl(C ₁ -C ₄ )alkyl group, in particular benzyl, preferably R _a and R _b represent a hydrogen atom, and R _c and R _d , identical or different, represent a (C ₁ -C ₆ )alkyl, aryl(C ₁ -C ₄ )alkyl or (C ₁ -C ₆ )alkoxy group,
- R ^e represents a hydrogen atom or a (C ₁ -C ₄ )alkyl group, in particular methyl, preferably R ^e represents a hydrogen atom, and
- Y represents an oxygen atom or an amino group -N(H)-, preferably an oxygen atom,
preferably Y is an oxygen atom and R ^e is a hydrogen atom, preferably L represents a di or trivalent, preferably trivalent, hydrocarbon chain comprising from 1 to 8 carbon atoms, q is 2 or 3, preferably 3, and
more preferably the compounds of formula (XIV) are trimethylolpropane triacrylate. Treatment method according to any one of the preceding claims, in which iv) at least one cosmetic active ingredient is additionally applied to said keratin materials. Treatment method according to the preceding claim, in which the cosmetic agent(s) iv) are chosen from:
(a) colouring matters, in particular chosen from pigments, direct dyes and their mixtures,
b) active ingredients for the care of keratin materials, preferably skin,
c) UV filters, and
(d) their mixtures;
preferably the cosmetic agent(s) iv) are chosen from a) coloring materials, preferably chosen from pigments, direct dyes and their mixtures, more preferably the pigment(s) are chosen from carbon black, iron oxides, in particular yellow, red and black and micas coated with iron oxide, triarylmethane pigments, in particular blue and violet, in particular BLUE 1 LAKE, azo pigments, in particular red, more particularly D&C RED 7, the alkali metal salt of lithol red, in particular the calcium salt of lithol red B, and
even more preferentially among red iron oxides, yellow iron oxides and azo pigments, in particular red ones, more particularly D&C RED 7. Treatment method according to any one of the preceding claims, in which v) at least one fatty substance, in particular at least one oil, preferably at least one volatile oil, is additionally used. Treatment method according to the preceding claim, in which v) at least one fatty substance chosen from volatile oils chosen from:
- hydrocarbon oils having from 8 to 16 carbon atoms, in particular branched C ₈ -C ₁₆ alkanes, in particular isoalkanes, more particularly isoalkanes (also called isoparaffins), preferably C ₁₃ -C ₁₆ Isoparaffin, isododecane, isodecane, isohexadecane, for example oils sold under the trade names Isopars or Permetyls, alone or in mixtures, preferably isododecane (also called 2,2,4,4,6-pentamethylheptane), linear alkanes, in particular C ₁₁ -C ₁₆ , alone or in mixtures, in particular hexane, decane, undecane, tridecane, isoparaffins in particular n-dodecane (C ₁₂ ) and n-tetradecane (C ₁₄ ), the undecane-tridecane mixture, mixtures of n-undecane (C ₁₁ ) and n-tridecane (C ₁₃ ), and mixtures thereof as well as mixtures of n-undecane (C ₁₁ ) and n-tridecane (C ₁₃ ), and volatile non-aromatic cyclic C ₅ -C ₁₂ alkanes;
- short-chain esters having 3 to 8 carbon atoms in total, in particular ethyl acetate, methyl acetate, propyl acetate, n-butyl acetate;
- carbonate hydrocarbon oils of structure R' ₁ -OC(O)-O-R' ₂ in which R' ₁ and R' ₂ independently denote a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably a C ₄ -C ₈ alkyl group, advantageously, more preferentially chosen from dibutylcarbonate or dipentylcarbonate;
- ether oils of formula R ₁ -OR ₂ , in which R ₁ and R ₂ denote, independently of one another, a linear, branched or cyclic C ₄ -C ₈ alkyl group, preferably a C ₄ -C ₈ alkyl group;
- silicone oils, in particular comprising from 2 to 7 silicon atoms, and optionally comprising alkyl or alkoxy groups having from 1 to 10 carbon atoms, in particular dimethicones with a viscosity of 5 and 6 cSt, cyclopentadimethylsiloxane, dodecamethylpentasiloxane, cyclohexadimethylsiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane, heptamethyl hexyltrisiloxane, heptamethyloctyl trisiloxane, hexamethyl disiloxane, octamethyl trisiloxane, decamethyl tetrasiloxane, dodecamethyl pentasiloxane, and mixtures thereof;
more preferably the volatile oil(s) v) are chosen from C ₈ -C ₁₆ alkanes, in particular branched, preferably isododecane. Process for the treatment, in particular cosmetic, of keratin materials according to any one of the preceding claims, in particular for the care and/or make-up of the skin, lips, eyelashes and/or eyebrows and/or for the care, styling and/or coloring of keratin fibers, preferably hair, comprising the application to said keratin materials of at least:
- a composition, called "C1", comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, according to any one of claims 1 to 5, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular according to any one of claims 10 or 11;
- a composition, called "C2", comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, according to any one of claims 1 to 5, optionally ii) at least one crosslinking agent, in particular according to any one of claims 8 or 9, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular according to any one of claims 10 or 11;
- a composition, called "C3", comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, according to any one of claims 1 to 5, ii) at least one crosslinking agent, in particular according to any one of claims 8 or 9, iv) at least one cosmetic active agent, in particular according to any one of claims 10 or 11, and optionally iii) water;
- a composition, called "C4", comprising ii) at least one crosslinking agent, in particular according to any one of claims 8 or 9, optionally iv) at least one cosmetic active ingredient, in particular according to any one of claims 10 or 11, and optionally iii) water; and/or
- a composition, called “C5”, comprising iv) at least one cosmetic active ingredient, in particular according to any one of claims 10 or 11, and optionally iii) water;
it being understood that the compositions “C1”, “C2”, “C3”, “C4” and “C5” may be anhydrous, aqueous, and/or comprise one or more fatty substances v), in particular according to any one of claims 12 or 13. Treatment method according to the preceding claim, characterized in that it comprises a single step of applying the composition “C1” or the composition “C2” or the composition “C3” to said keratin materials. Treatment method according to claim 14, characterized in that it comprises two successive steps of application to said keratin materials of two different compositions, preferably composition “C1” then composition “C4”. Cosmetic treatment process for the care, styling and/or coloring of keratin fibers, preferably hair, comprising the successive application of at least:
- a composition, called "C1", comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, according to any one of claims 1 to 5, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular according to any one of claims 10 or 11; then
- a composition, called “C4”, comprising ii) at least one crosslinking agent, in particular according to any one of claims 8 or 9, optionally iv) at least one cosmetic active ingredient, in particular according to any one of claims 10 or 11, and optionally iii) water;
at least one of the compositions “C1” and/or “C4” containing at least one coloring matter, in particular according to claim 11, preferably at least one pigment, and more preferably the composition “C1” comprises at least one pigment. Composition “C3”, preferably aqueous, comprising i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, according to any one of claims 1 to 5, ii) at least one crosslinking agent, in particular according to any one of claims 8 or 9, iv) at least one cosmetic active ingredient, in particular according to any one of claims 10 or 11, and optionally iii) water. Cosmetic use of the composition “C3” according to claim 18, for the treatment of keratin materials, in particular for the care, styling and/or coloring of keratin fibers, preferably hair. Kit, particularly cosmetic, with several compartments comprising:
- at least one compartment containing at least i) at least one compound of formula (I) as well as its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, according to any one of claims 1 to 5, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular according to any one of claims 10 or 11, in particular comprising the composition “C1” according to any one of claims 14 or 17;
- at least one compartment distinct from that which contains i) and containing ii) at least one crosslinking agent, in particular according to any one of claims 8 or 9, optionally iii) water, and optionally iv) at least one cosmetic active agent, in particular according to any one of claims 10 or 11, in particular comprising the composition “C4” according to any one of claims 14 or 17; and
- optionally, at least one compartment distinct from those which contain i) and ii), and containing iv) at least one cosmetic active ingredient, in particular according to any one of claims 10 or 11, identical or different from that/those possibly contained in the compartments comprising i) and ii). Compound myristoyl pullulan acetoacetate its optical, geometric isomers, its salts of organic or mineral acid or base, and/or solvates, such as hydrates, of formula:

formula in which:
- m is as defined in claim 3;
- R¹¹, identical or different, represents a hydrogen atom or a group (C₁₀-C₁₆)alkyl, linear or branched, preferably linear, such as CH₁₃H₂₇, or (C₁₀-C₁₆)alkylcarbonyl, linear or branched, preferably linear, such as CH₁₃H₂₇-C(O)- or a group R⁹as previously defined;
it being understood that at least one, preferably at least two, R group(s)¹¹, and that at least one group (C₁₀-C₁₆)alkyl or (C₁₀-C₁₆)alkylcarbonyl, such as CH₁₃H₂₇Or CH₁₃H₂₇-C(O)-, are present in the myristoyl pullulan acetoacetate compound above. Cosmetic composition comprising at least one myristoyl pullulan acetoacetate compound as defined according to claim 21.