Compositions comprising modified photodimerizable polymers and alkaline agents and / or aminoalkoxysilane derivatives and treatment methods implementing the same

Abstract

The present invention relates to a composition comprising: - at least one photocrosslinkable polymer comprising at least one photodimerizable side group; - one or more alkaline agents and / or aminoalkoxysilane derivatives, said alkaline agents and / or aminoalkoxysilane derivatives being present in said composition in an amount ranging from 0.01 to 10% by weight relative to the total weight of said composition, said composition having a pH greater than or equal to 7.

Description

[0001] The present invention relates to a composition, in particular a cosmetic composition, in particular a hair composition, comprising a specific content of at least one modified photocrosslinkable polymer and an alkaline agent and / or an aminoalkoxysilane derivative. Such a composition can produce a washing-resistant coating whose properties are stable over time. The use of photocrosslinkable materials, such as those from vinyl monomers and in particular (meth)acrylate monomers, is known to those skilled in the art.

[0002] Thus, US document 5,300,285 describes a method for perming hair and a composition for carrying out this method, and in particular a neutralizing composition based on silicone, comprising a silicone with vinyl functional groups, a free radical photoinitiator and a solvent. This composition acts as a substitute for neutralizing solutions based on hydrogen peroxide when applied to the hair and a photocrosslinking composition after a process of permanent deformation of the hair. This composition has the advantage of simultaneously acting as a crosslinker for keratin, while giving the hair advantages such as conditioning and a soft feel. The photocrosslinking of the composition is triggered by a photoinitiator (generally an acetophenone derivative) which releases free radicals when exposed to radiation in the UVA domain (350-385 nm).

[0003] Unfortunately, photopolymerization of siloxane with vinyl functional groups in the presence of a photoinitiator results in irreversible photocrosslinking of the siloxane with the vinyl functional groups. In other words, once it is photocrosslinked, the deposit may not be easily and readily removed from the hair.

[0004] Document EP 1572139 describes photodimerizable compositions that can form deposits on keratin materials, in particular hair. This document teaches that such deposits allow long-lasting deposits to be obtained, which provide cosmetic properties that last over time and are easy to remove. However, the deposits obtained from the crosslinkable compounds described in this document have limited persistence. In addition, these compounds are not deposited uniformly on the hair and the deposits depend greatly on the amount of hair damage. Therefore, the result is uneven between the root and the tip of the hair.

[0005] In order to obtain a uniform deposit throughout the hair, it has been proposed to use polymers with photodimerizable side groups and hydrophobic side groups, as described in particular in WO 2017108767. However, the photodimerizable polymers are slightly stable over time. The performance and safety of the composition are not necessarily guaranteed over time.

[0006] There is a need to further improve the results obtained in terms of stability.

[0007] The present invention therefore concerns the provision of a composition comprising a photocrosslinkable polymer which does not exhibit the disadvantages of the compositions of the prior art. An object of the present invention is in particular to develop a photodimerizable composition which is stable over time and which allows an effective, uniform, reproducible and durable coating of keratin materials and in particular of the hair, which coating withstands washing.

[0008] Accordingly, one of the subjects of the present invention is a composition comprising:

[0009] - at least one photocrosslinkable polymer comprising at least one photodimerizable side group:

[0010] one or more alkaline agents and / or aminoalkoxysilane derivatives, present in the composition in a content ranging from 0.01% to 10% by weight relative to the total weight of the composition, the pH of the composition being greater than or equal to 7.

[0011] Another subject of the invention is a method for treating keratin materials comprising the steps of applying said composition and irradiating the composition on the keratin material in order to crosslink the composition.

[0012] In this way a composition is obtained which is stable over time and which makes it possible to obtain a uniform coating of the hair which is stable upon washing.

[0013] For the purposes of the present invention and unless otherwise indicated:

[0014] ■ "Alkylene chain" means a non-cyclic C1-C 20 A divalent hydrocarbon chain, in particular a C1-C6 chain, more in particular a C1-C2 chain, is optionally substituted by one or more groups, which may be identical or different, selected from: i) hydroxy, ii) (C1-C2) alkoxy, iii) (poly) hydroxy (C2-C4) alkoxy (di) (C1-C2) (alkyl) amino, iv) R a -Z a -C(Z b )-Z c , and v) R a -Z a -S(O) t --Z c , where Z a and Z b may be the same or different, representing an oxygen or sulfur atom, or a group NR a ,,Z c represents a bond, an oxygen or sulfur atom, or a group NR a ; R arepresents an alkali metal, a hydrogen atom, an alkyl group, or alternatively is absent (if another part of the cation molecule and R a ' represents a hydrogen atom or an alkyl group); more particularly, the group iv) is selected from the group consisting of carboxylate -C(O)O - or -C(O)O metal (metal = alkali metal), carboxyl -C(O)-OH, guanidino H2H-C(NH2)-NH-, amidino H2H-C(NH2)-, (thio)ureido H2N-C(O)-NH- and H2N-C(S)-NH-, aminocarbonyl -C(O)-NRa'2 or aminothiocarbonyl -C(S)-NRa'2; carbamoyl Ra'-C(O)-NRa'- or thiocarbamoyl Ra'-C(S)-NRa', wherein Ra' may be identical or different and represent a hydrogen atom or a (C1-C4)alkyl group;

[0015] ■ An "aryl" or "heteroaryl" group or the aryl or heteroaryl part of a group may be substituted by at least one substituent carried by a carbon atom, the at least one substituent being selected from:

[0016] -C1-C 16 and preferably C1-C8 alkyl, optionally substituted by one or more radicals selected from the group consisting of hydroxy, C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, amido, amino substituted by two C1-C4 alkyl radicals, which may be identical or different, optionally carrying at least one hydroxyl group, or which may form with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered and preferably 5- or 6-membered heterocyclic ring, which optionally contains a further nitrogen or non-nitrogen heteroatom;

[0017] - halogen atoms;

[0018] -Hydroxyl;

[0019] -C1-C2 alkoxy;

[0020] -C2-C4 (poly)hydroxyalkoxy;

[0021] -amino group;

[0022] -5-membered or 6-membered heterocycloalkyl;

[0023] - an optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, optionally substituted by (C1-C4)alkyl, preferably methyl;

[0024] - amino substituted by one or two identical or different C1-C6-alkyl groups, optionally carrying at least:

[0025] i) a hydroxyl group,

[0026] ii) one amino group optionally substituted by one or two optionally substituted C1-C3 alkyl groups which may form with the nitrogen atom to which they are attached a saturated or unsaturated, optionally substituted 5- to 7-membered heterocyclic ring which optionally contains at least one further nitrogen or non-nitrogen heteroatom,

[0027] iii) a quaternary ammonium group -N + R′R″R″′,M - , wherein R′, R″ and R′″, which may be the same or different, represent a hydrogen atom or a C1-C4 alkyl group; and M - represents the counter ion of an organic or inorganic acid or the corresponding halide;

[0028] iv) alternatively, an optionally cationic 5- or 6-membered heteroaryl, preferably imidazolium, optionally substituted by (C1-C4)alkyl, preferably methyl;

[0029] -acylamino (-NR-C(O)-R'), wherein the R group is a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group, and the R' group is a C1-C2 alkyl group;

[0030] -carbamoyl ((R)2N-C(O)-), in which the R groups can be identical or different and represent a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group;

[0031] -alkylsulfonylamino (R'-S(O)2-N(R)-), wherein the R group represents a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group, and the R' group represents a C1-C4 alkyl group, or a phenyl group; aminosulfonyl ((R)2N-S(O)2-), wherein the R groups may be the same or different, represent a hydrogen atom or a C1-C4 alkyl group optionally carrying at least one hydroxyl group,

[0032] - carboxyl groups in the form of an acid or a salt (preferably salified with an alkali metal or substituted or unsubstituted ammonium);

[0033] - cyano;

[0034] - nitro or nitroso;

[0035] -polyhaloalkyl, preferably trifluoromethyl;

[0036] The cyclic, cycloalkyl or heterocyclic portion of the non-aromatic group may be substituted with at least one group selected from:

[0037] -Hydroxyl;

[0038] - C1-C4 alkoxy or C2-C4 (poly)hydroxyalkoxy;

[0039] -C1-C4 alkyl;

[0040] -alkylcarbonylamino (RC(O)-N(R′)-), in which the R′ group is a hydrogen atom or a C1-C4-alkyl group optionally carrying at least one hydroxyl group, and the R group is a C1-C2-alkyl group or an amino group optionally substituted by one or two identical or different C1-C4-alkyl groups optionally carrying at least one hydroxyl group, said alkyl groups possibly forming with the nitrogen atom to which they are attached a saturated or unsaturated and optionally substituted 5- to 7-membered heterocyclic ring optionally containing at least one further nitrogen or non-nitrogen heteroatom;

[0041] -alkylcarbonyloxy (RC(O)-O-), wherein the R group is C1-C4-alkyl or amino optionally substituted by one or two identical or different C1-C4-alkyl groups which themselves optionally carry at least one hydroxyl group, wherein the alkyl groups may form with the nitrogen atom to which they are attached a saturated or unsaturated and optionally substituted 5- to 7-membered heterocyclic ring which optionally contains at least one further nitrogen or non-nitrogen heteroatom;

[0042] - alkoxycarbonyl (RGC(O)-), wherein the R group is a C1-C4 alkoxy group, G is an oxygen atom or an amino group optionally substituted by a C1-C4 alkyl group optionally carrying at least one hydroxyl group, wherein the alkyl group can form, together with the nitrogen atom to which they are attached, a saturated or unsaturated, optionally substituted, 5- to 7-membered heterocyclic ring optionally containing at least one further nitrogen or non-nitrogen heteroatom;

[0043] ■ a cyclic, cycloalkyl or heterocyclic group or a non-aromatic part of an aryl or heteroaryl group, which may also be substituted by one or more oxo groups;

[0044] ■ Cycloalkyl is a monocyclic or bicyclic hydrocarbon radical containing 3 to 10 carbon atoms, preferably 4 to 7 carbon atoms, such as cyclopentyl or cyclohexyl;

[0045] ■When the hydrocarbyl chain contains one or more double bonds and / or one or more triple bonds, the chain is unsaturated;

[0046] ■ an "aryl" group means a monocyclic or fused or non-fused polycyclic carbonyl group containing from 6 to 22 carbon atoms and wherein at least one ring is aromatic; preferably, the aryl group is phenyl, biphenyl, naphthyl, indenyl, anthracenyl or tetrahydronaphthyl;

[0047] ■“Heteroaryl” means an optionally cationic 5- to 22-membered monocyclic or fused or non-fused polycyclic radical containing from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium, at least one of whose rings is aromatic; preferably, the heteroaryl is selected from acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl, benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl, benzoxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl, imidazopyridyl, imidazolyl, indolyl, isoquinolyl, naphthoimidazolyl, naphthooxazole 1-dinitro-1,1-dinitro-1,1-dinitro-2,1-dinitro-3,1-dinitro-4,1-dinitro-5,1-dinitro-6,1-dinitro-7,1-dinitro-8,1-dinitro-9,1-dinitro-10,1-dinitro-11,1-dinitro-12,1-dinitro-13,1-dinitro-14,1-dinitro-15,1-dinitro-16,1-dinitro-17,1-dinitro-18,1-dinitro-19,1-dinitro-20,1-dinitro-21,1-dinitro-22,1-dinitro-23,1-dinitro-24,1-dinitro-25,1-dinitro-26,1-dinitro-27,1-dinitro-28,1-dinitro-29,1-dinitro-30,1-dinitro-31,1-dinitro-32,1-dinitro-33,1-dinitro-34,1-dinitro-35,1-dinitro-36,1-dinitro-37,1-dinitro-38,1-dinitro-39,1-dinitro-40,1-dinitro-31,1-dinitro-31

[0048] ■ "heterocyclic group" is a 5- to 22-membered monocyclic or fused or non-fused polycyclic group which may contain one or two degrees of unsaturation but is non-aromatic and contains from 1 to 6 heteroatoms selected from nitrogen, oxygen, sulfur and selenium atoms;

[0049] ■“Heterocycloalkyl” is a heterocyclic group containing at least one saturated ring;

[0050] ■ "Cationic heteroaryl" is a heteroaryl as defined above, which contains an endo- or exo-quaternized cationic group,

[0051] o When the cationic charge is endocyclic, it is included in the electron delocalization via a mediating effect; for example, it is a pyridinium, imidazolium, or indolium group:

[0052]

[0053] wherein R and R′ are heteroaryl substituents as defined above, and in particular (hydroxy)(C1-C8)alkyl such as methyl;

[0054] o When the cationic charge is exocyclic, it is, for example, ammonium or phosphonium R + Substituents, such as trimethylammonium, which are in addition to heteroaryl groups, such as the pyridyl, indolyl, imidazolyl or naphthoimidyl groups in question:

[0055]

[0056] wherein R is a heteroaryl substituent as defined above and R + Ammonium R a R b R c N+ -、R a R b R c P + - or ammonium R a R b R c N + -(C1-C6)alkylamino, wherein R a , R b and R c may be the same or different and represent a hydrogen atom or a (C1-C8)alkyl group such as methyl;

[0057] ■ "Cationic aryl carrying an exocyclic charge" means an aryl ring whose quaternized cationic group is outside the ring; it is especially an ammonium or phosphonium R + Substituents, such as trimethylammonium, other than aromatic groups such as phenyl or naphthyl:

[0058]

[0059] ■ "Alkyl" is a straight or branched C1-C 20 and preferably a C1-C8 hydrocarbon-based group;

[0060] ■ "Alkenylene" is a divalent radical based on an unsaturated hydrocarbon as defined previously, which may contain from 1 to 4 conjugated or non-conjugated double bonds -C=C-; alkenylene contains in particular 1 or 2 degrees of unsaturation;

[0061] The term "optionally substituted" as applied to an alkyl group means that the alkyl group may be substituted by one or more groups selected from the group consisting of: i) hydroxy, ii) C1-C4 alkoxy, iii) acylamino, iv) amino optionally substituted by one or two identical or different C1-C4 alkyl groups, wherein the alkyl groups may form a 5- to 7-membered heterocyclic ring with the nitrogen atom carrying them, which optionally contains one further nitrogen or non-nitrogen heteroatom; v) or a quaternary ammonium group -N + R′R″R″′,M - R', R" and R"' (which may be the same or different) represent a hydrogen atom or a C1-C4 alkyl group, or -N + R'R"R"' forms a heteroaryl group optionally substituted with C1-C4 alkyl, such as imidazolium, and M - represents the counter ion of the corresponding organic acid, inorganic acid or halide;

[0062] ■ "Alkoxy" is an alkyloxy group, wherein the alkyl group is based on a straight or branched C1-C 16 and preferably a C1-C8 hydrocarbon group; when the alkoxy group is optionally substituted, this means that the alkyl group is optionally substituted as defined above;

[0063] ■ "Organic acid or inorganic acid salt" means more particularly a salt selected from the group consisting of salts derived from: i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H2SO4, iv) alkylsulfonic acids: Alk-S(O)2OH, such as methanesulfonic acid and ethanesulfonic acid; v) arylsulfonic acids: Ar-S(O)2OH, such as benzenesulfonic acid and toluenesulfonic acid; vi) citric acid; vii) succinic acid; viii) tartaric acid; ix) lactic acid; x) alkoxysulfinic acids: Alk-OS(O)OH, such as methoxysulfinic acid and ethoxysulfinic acid; xi) aryloxysulfinic acids, such as tolyloxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3PO4; xiii) acetic acid CH3C(O)OH; xiv) trifluoromethanesulfonic acid CF3SO3H; and xv) tetrafluoroboric acid HBF4;

[0064] ■ "Anionic counterion" is intended to mean an anion or anionic group derived from an organic acid or an inorganic acid salt, which anion or anionic group balances the cationic charge of the colorant; more particularly, the anionic counterion is selected from: i) a halide, such as chloride or bromide; ii) a nitrate; iii) a sulfonate, including a C1-C6 alkylsulfonate: Alk-S(O)2O - , such as methanesulfonate or methanesulfonate and ethanesulfonate; iv) arylsulfonate: Ar-S(O)2O - , such as benzenesulfonate and toluenesulfonate or tosylate; v) citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfate: Alk-OS(O)O - , such as methyl sulfate and ethyl sulfate; x) aryl sulfate: Ar-OS(O)O - , such as benzene sulfate and toluene sulfate; xi) alkoxy sulfate: Alk-OS(O)2O - , such as methoxysulfate and ethoxysulfate; xii) aryloxysulfate: Ar-OS(O)2O - , xiii) Phosphate O=P(OH)2-O - , O=P(O - )2-OH O=P(O - )3. HO-[P(O)(O - )] w -P(O)(O - )2, wherein w is an integer; xiv) acetate; xv) trifluoromethanesulfonate; and xvi) borate, such as tetrafluoroborate, xvii) disulfate (O=)2S(O - )2 or SO4 2- and monosulfate HSO4- ;

[0065] The anionic counterion derived from an organic or inorganic acid salt ensures the electroneutrality of the molecule; therefore, it is understood that when the anion contains several anionic charges, the same anion can be used for the electroneutrality of several cationic groups in the same molecule, or can be used for the electroneutrality of several molecules; for example, a polymer containing two cationic species can contain two "single-charged" anionic counterions or one "doubly-charged" anionic counterion, such as (O=)2S(O - )2 or O=P(O - )2-OH;

[0066] ■Addition salts which can moreover be used in the context of the present invention are chosen especially from addition salts with cosmetically acceptable bases, such as alkaline agents as defined below, for example alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, ammonia, amines or alkanolamines;

[0067] ■ The expression "at least one" is equivalent to "one or more"; and

[0068] ■ The expression "inclusive" for a concentration range means that the limit value of the range is included in the defined range.

[0069] For the purposes of the present invention, the term "photodimerizable group" means a chemical group that causes a photodimerization reaction under irradiation. For the purposes of the present invention, photodimerization is a chemical reaction between two double bonds (2+2 type) or two pairs of double bonds (4+4 type), and more particularly between two double bonds (2+2 type).

[0070] The reaction between two double bonds can be represented schematically in the following way:

[0071]

[0072] These photodimerization reactions are defined in the following book: Advanced Organic Chemistry, J. Marck, 4th edition, Wiley Interscience, New York 1992, p. 855.

[0073] Thus, when stimulated by light, typically when subjected to specific UV radiation, this double bond proves capable of reacting with another double bond by cyclization.

[0074] According to the invention, the double bond is said to be activated, ie it can photodimerize spontaneously, without the presence of a photoinitiator or a chemical initiator.

[0075] This double bond is usually activated by the presence of an electron-withdrawing substituent in the alpha position of this photodimerizable double bond. As electron-withdrawing substituents, mention may be made of aromatic rings, such as phenyl groups optionally substituted with one or more halogen atoms or electron-withdrawing groups, such as NO2, CN, R'-YC(Y')-, R'-C(Y')-Y-, R'-YC(Y')-Y-, R'-YS(O)2-, -S(O)2-YR', wherein R' represents a hydrogen atom or a (C1-C4)alkyl group optionally substituted with one or more halogen atoms, wherein Y and Y' may be identical or different and represent an oxygen or sulfur atom, or NR", wherein R" represents a hydrogen atom or a (C1-C6)alkyl group.

[0076] The method according to the invention comprises the step a) of applying a composition comprising a polymer comprising at least one photodimerizable side group.

[0077] Preferably, the photodimerizable side groups that can be used according to the invention are selected from monovalent groups having the following formulae (I) and (II):

[0078]

[0079] and its geometric isomers,

[0080] In the formulae (I) and (II):

[0081] - Y and Z independently represent a nitrogen atom or a group C(R), wherein R represents a hydrogen atom or a (C1-C4)alkyl group such as a methyl group;

[0082] -A represents a bond or a divalent group selected from the group consisting of (C1-C8)alkylene, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio)carbonyl, (C2-C8)alkenylene, and combinations thereof;

[0083] -B represents a monovalent group selected from the group consisting of: (C1-C8)alkyl, aryl, optionally cationic heteroaryl, cycloalkyl, optionally cationic heterocycloalkyl, (thio)carbonyl, (C2-C8)alkenyl, and combinations thereof;

[0084] -X represents a divalent group selected from the group consisting of (C2-C8)alkylene, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio)carbonyl, (C2-C8)alkenylene, and combinations thereof;

[0085] - p represents an integer from 1 to 5 and including the end values, more particularly from 1 to 3, preferably p is 1;

[0086] - represents the bond connecting the portion of the monovalent group to the rest of the molecule;

[0087] and

[0088] Each of the groups listed may be optionally substituted by one or more halogen atoms or a group selected from the following: (C1-C6) alkyl, hydroxy, amino, (di) (C1-C6) alkylamino, phenyl, carboxyl, (C1-C6) alkoxy, (C1-C6) alkoxy (thio) carbonyl, hydrogen (thio) -carbonyl, sulfonate ROS (O) 2- or RS (O) 2-O-, amide RR 'NC (O) - or RC (O) -N (R ') - or acyl RC (O) -, ammonium RR 'R "N + - group, in which R, R' and R'' may be the same or different and represent a hydrogen atom or a (C1-C4)alkyl group.

[0089] Dimerizable side groups according to the invention are in particular those listed in US Pat. No. 2,811,510, EP 0 313 220, EP 0 313 221, EP 092 901, GB 2 030 575, and GB 2 076 826, and in the articles “Chemical Review 83, 51983, p. 507”, “Polym, Paint Colour Journal 1988, 178, p. 209” and “Current Trends in Polymer Photochemistry, Ellis Morwood Editions, New York, 1995”.

[0090] As examples, one may more particularly cite photodimerizable side groups selected from monovalent groups from the following compounds:

[0091] -Stilbene,

[0092] -Styrylpyridinium (stilbenazolium) and its geometric isomers having the following formula:

[0093]

[0094] in:

[0095] ●R 1 and R 3 may be the same or different and represent a halogen atom or a (C1-C6) alkyl group; or two adjacent R 1 or R 3 The group together with the carbon atom that carries it forms a benzo group;

[0096] ●R 2represents a hydrogen atom, a (C1-C6)alkyl group optionally substituted by one or more halogen atoms such as chlorine or hydroxyl, preferably R 2 represents (C1-C6) alkyl such as methyl, ethyl, propyl;

[0097] q and r represent integers from 0 to 4, inclusive; and

[0098] Q - represents an anionic counterion preferably selected from halides such as chloride, bromide, iodide, perchlorate, tetrafluoroborate, methylsulfate, phosphate, sulfate, methanesulfonate, p-toluenesulfonate;

[0099] ● represents the bond connecting the monovalent group to the rest of the molecule, it being understood that the side group A2 may be connected via R 2 connected to the rest of the molecule;

[0100] Preferably, the The bond is present on A1 on the phenyl group in the para position relative to the styryl group or on A2 via R 2 connected to the rest of the molecule; preferably, the styryl groups of A1 and A2 are present in the para position to the pyridinium group;

[0101] -Styrylazoles and their geometric isomers having the formula:

[0102]

[0103] in:

[0104] ●A represents a sulfur atom, an oxygen atom or NR 2 or C(R 2 )2 group; and

[0105] ● Q - , r, q, R 1 , R 2 , and R 3 is as defined previously,

[0106] Preferably, The bond is present on the phenyl group in the para position relative to the styryl group,

[0107] -Styrylpyrazine,

[0108] - Chalcone,

[0109] - (thio)cinnamate and (thio)cinnamate,

[0110] -maleimide,

[0111] -(Thio)coumarin,

[0112] -thymine,

[0113] - uracil,

[0114] -Butadiene

[0115] - anthracene,

[0116] -pyridone,

[0117] -Pyrrolizinone,

[0118] - acridizinium salts,

[0119] -Furanone,

[0120] -phenylbenzoxazole, and

[0121] - their derivatives.

[0122] According to a specific embodiment, the photodimerizable side groups of the present invention are selected from:

[0123] a) a photodimerizable group carrying a stilbazolium functional group having the following formula (Ia) or (Ib), and geometric isomers thereof:

[0124]

[0125] in:

[0126] -R represents a hydrogen atom, or a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group,

[0127] -R' represents a hydrogen atom or a C1-C4 alkyl group, and

[0128] -X - indicates an anionic counterion selected from halides such as chloride, bromide, iodide, perchlorate, tetrafluoroborate, methylsulfate, phosphate, sulfate, methanesulfonate, p-toluenesulfonate; preferably, the styrene group is present in the para position and / or Key alignment;

[0129]

[0130] in

[0131] -R" indicates a divalent alkylene group having 2 to 8 carbon atoms,

[0132] -R' represents a hydrogen atom or a C1-C4 alkyl group, and

[0133] -X - has the same meaning as described for the aforementioned formula (Ia);

[0134] -in has the same meaning as before;

[0135] Preferably, the styryl group is present in the para position to the pyridinium group;

[0136] or

[0137] b) a photodimerizable group carrying a styrylazole functional group of the following formula (IIa):

[0138]

[0139] in:

[0140] -R1 indicates a hydrogen atom or a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group;

[0141] -A indicates a sulfur atom, an oxygen atom or an NR′ or C(R′)2 group, R′; wherein R′ represents a hydrogen atom or a C1-C4 alkyl group, and R′ preferably represents a hydrogen atom; and

[0142] -X - has the same meaning as described for the aforementioned formula (Ia);

[0143] -in has the same meaning as before;

[0144] Preferably, the styryl group is present in the phenyl In the counterpoint.

[0145] Such chemical groups carry activated double bonds and therefore photodimerization of these double bonds starts spontaneously in the UVA range without the need for photoinitiators.

[0146] Photoinitiators within the meaning of the present invention are understood to be compounds which initiate a photodimerization reaction and release free radicals upon irradiation, in particular in the UV range.

[0147] According to one particular embodiment, the composition of the present invention does not contain a photoinitiator.

[0148] According to particular embodiments of the present invention, the polymer may comprise one or more hydrophobic side groups.

[0149] As hydrophobic side groups, mention may be made of:

[0150] -Saturated or unsaturated (C1-C 30 ) alkyl, which is optionally substituted and / or interrupted by one or more heteroatoms,

[0151] -alkenyl,

[0152] - aryl, such as phenyl, pyridyl, furyl, indolyl, benzofuranyl, thienyl, imidazolyl, oxazolyl, thiazolyl, pyrazinyl, pyrimidinyl;

[0153] - fluorinated groups, such as fluorocarbon groups, such as -CF3, -CHF2, -OCF3, -SCF3, CF3C(O)-,

[0154] -Silicone groups, such as -SiR a R b R c , such as -Si(CH3)3, polydimethylsiloxane-PDMS, -Si(OR)3, α,ω-diaminopropyl PDMS, α,ω-dihydroxyalkyl PDMS, α,ω-dicarboxyalkyl PDMS, wherein R a , R b and R c are the same or different and represent (C1-C8)alkyl optionally interrupted and / or terminated by one or more non-adjacent heteroatoms such as O or S; and R represents (C1-C6)alkyl.

[0155] Preferably, the hydrophobic side groups are selected from (C2-C 22 ) alkyl, more preferably (C3-C 16 ) alkyl and especially propyl.

[0156] The polymer backbone may have altered properties. This polymer backbone may be natural or synthetic. As natural polymer backbones, polysaccharides may be mentioned.

[0157] As polysaccharides, mention may be made of xanthan gum, carrageenan, chitosan, cellulose and its derivatives, alginates, starch, dextran, pullulan, galactomannans and their biologically acceptable salts, and derivatives thereof. As synthetic backbones, mention may be made of poly(vinyl) polymers and polydiorganosiloxanes.

[0158] Among the poly(vinyl) polymers, mention may be made of partially or completely hydrolyzed polyvinyl acetate and polyvinyl alcohol (PVA).

[0159] As regards the polymers containing photodimerizable groups bearing stilbazolium functions, they are obtained by reacting the polymer in question with a chemical species comprising a group having formula (Ia) or (Ib).

[0160] Preferably, the chemical substance comprising group (Ia) carries a reactive group W of the aldehyde or acetal type.

[0161] As chemical species that can be used to graft styrylpyridinium groups, mention may be made especially of quaternary ammonium salts of 2-(4-formylstyryl)-pyridinium, 4-(4-formylstyryl)-pyridinium, 2-(3-formylstyryl)-pyridinium, N-methyl-2-(4-formylstyryl)-pyridinium, N-methyl-3-(4-formylstyryl)-pyridinium, N-methyl-2-(3-formylstyryl)-pyridinium, yl)-pyridinium, N-methyl-2-(2-formylstyryl)-pyridinium, N-ethyl-2-(4-formylstyryl)-pyridinium, N-(2-hydroxyethyl)-2-(4-formylstyryl)-pyridinium, N-(2-hydroxyethyl)-4-(4-formylstyryl)-pyridinium, N-methyl-4-(4-formylstyryl)-pyridinium, N-methyl-4-(3-formylstyryl)-pyridinium.

[0162] The quaternary pyridinium ammonium salt may be a chloride, bromide, iodide, perchlorate, tetrafluoroborate, methylsulfate, phosphate, sulfate, methanesulfonate or p-toluenesulfonate salt. Such chemical species are described in GB-A-2030575.

[0163] Examples of species that may be mentioned include 4-(4-formylphenylvinyl)-1-methylpyridinium methylsulfate, 1-(3-ethoxycarbonylmethyl)-4-[2-(4-formylphenyl)vinyl]pyridinium bromide and 1-(methoxycarbonylpropyl)-4-[2-(4-formylphenyl)vinyl]pyridinium bromide. Such species are described in US 2007 / 0 112 094.

[0164] Preference is given to using n-methyl-4-(4-formylstyryl)pyridinium methylsulfate (RN=74401-04-0), sold in particular by the company Wako.

[0165] As described below, these polymers functionalized with photodimerizable groups, such as those containing styryl groups and hydrophobic groups, can be synthesized based on the protocol of T. Uhlich et al. (Reactive & Functional Polymers, 28, 55-40 (1995)).

[0166]

[0167] Compounds of formula (III) to (VIII'), wherein

[0168] R may be the same or different and represent a hydrogen atom or a (C1-C 10)alkyl, preferably R represents a hydrogen atom or a (C1-C4)alkyl group, such as methyl, ethyl or propyl, more preferably R represents a hydrogen atom;

[0169] R 1 represents a hydrogen atom or (C1-C 10 ) alkyl, preferably R 1 represents a hydrogen atom or a (C1-C4) alkyl group;

[0170] R 2 represents a saturated or unsaturated (C1-C 30 ) alkyl, alkenyl, aryl such as phenyl, pyridyl, furyl, indolyl, benzofuranyl, thienyl, imidazolyl, oxazolyl, thiazolyl, pyrazinyl, pyrimidinyl; fluorinated groups such as fluorocarbon groups such as -CF3, -CHF2, -OCF3, -SCF3, CF3C(O)-, silicone groups such as -SiR a R b R c , such as -Si(CH3)3, polydimethylsiloxane-PDMS, -Si(OR)3, α,ω-diaminopropyl PDMS, α,ω-dihydroxyalkyl PDMS, α,ω-dicarboxyalkyl PDMS, wherein R a , R b and R c may be the same or different, represents a (C1-C8)alkyl group optionally interrupted and / or terminated by one or more non-adjacent heteroatoms such as O or S; and wherein R represents a (C1-C6)alkyl group; preferably R 2 It means (C2-C 22 ) alkyl, more preferably (C3-C 16 )alkyl;

[0171] A represents a group derived from a photodimerizable compound, preferably a styrylpyridinium, such as (I), (II), (A1), (A2), (Ia), (Ib) or (IIa) as defined previously, more particularly selected from (A1) or (Ia) as defined previously;

[0172] X represents oxygen or sulfur, preferably an oxygen atom;

[0173] X' and X" represent oxygen or sulfur atoms or N(R 3 ) group, wherein R 3 indicates a hydrogen atom or a (C1-C4) alkyl group; preferably, X′ and X′′ represent an oxygen atom;

[0174] Mainly, the product obtained is of formula (VI).

[0175] Advantageously, these chemical species react with polyvinyl alcohol or polyvinyl acetal type polymers as described in the previously cited documents and with polymer (III) such as described in the above scheme, for which polymer (III) X, X′ and X″ represent oxygen atoms and R and R1 are as previously described.

[0176] For example, a grafted polyvinyl alcohol polymer comprising the following structural units is obtained, wherein A represents a group (I), (A1) or (Ia):

[0177]

[0178] Polyvinyl alcohol polymers grafted with styrylpyridinium groups are described, inter alia, in the publication Ichimura K. et al., Preparation and characteristics of photo-crosslinkable poly(vinyl alcohol), Journal of Polymer Science, Polymer Chemistry Edition, Vol. 20, 1419-1432 (1982).

[0179] The polymers are obtainable by reacting polyvinyl alcohol or partially hydrolyzed polyvinyl acetate with a styrylpyridinium salt carrying a formyl or acetal group, as described in GB-A-2 030 575, WO 96 / 29312, US Pat. No. 5 061 603, GB-A-2 076 826 and EP-A-092 901.

[0180] Cellulosic polymers grafted with styrylpyridinium groups are described, inter alia, in US 2007 / 0 112 094.

[0181] Preferably, the chemical species comprising group (A1) or (Ia) carries a reactive group which is a halogen atom, such as chlorine.

[0182] In this variant, the chemical species corresponds, for example, to the following formula:

[0183]

[0184] Advantageously, the photocrosslinkable polymer comprising groups (Ib) is obtained, for example, by reacting the above species with a polysaccharide chosen from those previously defined.

[0185] As regards the polymers containing photodimerizable groups bearing styrylazole functional groups, they are obtained by reacting the polymers with chemical species comprising groups having formula (IIa).

[0186] Preferably, the chemical species comprising group (IIa) carries a reactive group W of the aldehyde or acetal type.

[0187] As chemical species that can be used for grafting styrylazole groups of the type mentioned, mention may be made of those described in EP-A-313 220.

[0188] Advantageously, these chemical species react with polymers of the polyvinyl alcohol or polyvinyl acetate type, as described in the documents previously cited.

[0189] A grafted polyvinyl alcohol polymer comprising the following structural units is obtained,

[0190]

[0191] where B corresponds to the following group

[0192]

[0193] or (IIa) as previously defined.

[0194] Polyvinyl alcohol polymers grafted with styrylazolium groups are described, inter alia, in EP-A-313 220. In said document, these polymers are obtainable by reacting polyvinyl alcohol or partially hydrolyzed polyvinyl acetate with styrylazolium salts bearing aldehyde or acetal groups.

[0195] According to one embodiment, the polymer carrying photodimerizable groups is in the form of particles, in particular dispersed particles. Thus, in the latter case, the polymer particles are very preferably polyvinyl alcohol particles.

[0196] According to a preferred embodiment, the polymers carrying photodimerizable groups according to the invention are soluble in the cosmetic medium.

[0197] Thus, according to one embodiment variant, the polymer is a polyvinyl alcohol (PVA) polymer partially functionalized with one or more hydroxyl functional groups and one or more functional groups having formula (IX):

[0198]

[0199] The degree of polymerisation of the PVA may be between 100 and 5000 and the level of substitution in % of functional groups of formula (I) as defined above may be between 0.1 and 25.

[0200] The following scheme represents a variant in which the polymer is a polymer (III) as previously defined carrying functional groups grafted with styryl azolium species, such as those of formula (A1) as previously defined, which polymer can be crosslinked under the action of light, as explained below.

[0201]

[0202] These materials respond to radiation, which may include both UV and visible light, particularly low dose UV.

[0203] Preferably, the following scheme represents a polymer of PVA-SbQ (polymer of polyvinyl acetate carrying several hydrolyzed functional groups and several functional groups grafted with stilbazolium species) which can be crosslinked under the action of light, as explained below.

[0204]

[0205] These materials are particularly attractive because they do not require a photoinitiator and react in the presence of radiation including both UV and visible light (particularly low dose UV).

[0206] Preference is given to side groups that are reactive in both UV and visible light.

[0207] According to another embodiment variant, the photocrosslinkable polymer is characterized by a natural polymer functionalized with photodimerizable groups.

[0208] The polymer may in particular be a polysaccharide which may in particular be chosen from chondroitin sulfate, keratan, keratan sulfate, heparin, heparan sulfate, xanthan gum, carrageenan, hyaluronic acid, chitosan, cellulose and its derivatives, alginates, starches, dextran, pullulan, galactomannans and biologically acceptable salts thereof.

[0209] The functionality is of course adjusted to provide the desired degree of crosslinking during activation.

[0210] According to the invention, the functionality with photodimerizable units is at least 0.1%, or even at least 0.5%, or even at least 2%.

[0211] Preferably, in the composition according to the invention, the photodimerizable groups are carried by polyvinyl acetate or a polysaccharide polymer.

[0212] The cross-linkable polymers can be delivered in aqueous media.

[0213] The composition may contain a single polymer with photodimerizable side groups, which groups may or may not be of different nature.

[0214] It is also possible to use mixtures of polymers having different functional groups.

[0215] Thus, the reaction may occur between two photodimerizable groups which may or may not be of the same chemical nature.

[0216] The activated double bond can react with another double bond of the same chemical nature or can react with another double bond of a different chemical nature.

[0217] As an example of a polymer that can be used in the present invention, mention may be made of a polymer PVA comprising side groups referred to below as PVA-SbQ-propional, wherein, preferably, the amount of SbQ units is from 0.5 to 5 mol%, preferably from 2 to 4 mol%, for example about 2 mol%, the amount of propional groups is from 2 to 20 mol%, preferably from 5 to 15 mol%, for example about 10 mol%, and the amount of hydroxyl groups is from 50 to 97.5 mol%, preferably from 60 to 97.5 mol%, for example about 86 mol%:

[0218]

[0219] Where Q - is as defined previously, preferably mesylate CH3OSO3 - .

[0220] According to a particular embodiment, the molecular weight Mw of the PVA is from 10 000 to 100 000 g / mol and preferably from 25 000 to 80 000 g / mol.

[0221] According to a particular embodiment, the molecular weight Mw is about 27 000 g / mol.

[0222] The polymer comprising at least one photodimerizable group preferably represents from 0.01% to 25%, better still from 0.1% to 20% and even better still from 1% to 15% relative to the total weight of the composition.

[0223] The composition according to the invention may also comprise an effective amount of at least one photosensitizer.

[0224] In the meaning of the present invention, a photosensitizer is understood to mean a component which changes the wavelength of the irradiation and thus triggers the photodimerization reaction.

[0225] For example, photodimerization of dimethylmaleimide groups is triggered by irradiation centered in the wavelength range from 270 to 300 nm. In the presence of a photosensitizer such as thioxanthone, photodimerization becomes effective in the presence of irradiation centered in the wavelength domain ranging from 360 to 430 nm.

[0226] Among the photosensitizers that can be used according to the invention, mention may especially be made of thioxanthone, rose bengal, phloxanthone, eosin, erythrosine, fluorescein, acriflavin, thionine, riboflavin, proflavin, chlorophyll, hematoporphyrin, methylene blue and mixtures thereof.

[0227] In practice, the photosensitizer that may be used according to the invention may comprise from 0.00001% to 5% by weight of the total composition.

[0228] The composition according to the invention also comprises one or more alkaline agents and / or one or more aminoalkoxysilane derivatives.

[0229] The alkaline agent may be selected from:

[0230] - mineral alkaline agents soluble in water, such as

[0231] - an alkali metal or alkaline earth metal hydroxide, preferably a hydroxide of lithium, magnesium, calcium, sodium or potassium, buffered with one or more amino acids such as glycine,

[0232] - carbonates, bicarbonates or bicarbonates, carbonates buffered with bicarbonate to obtain a pH < 12.0,

[0233] - phosphates of alkali metals or alkaline earth metals such as lithium, calcium, sodium or potassium,

[0234] -ammonia,

[0235] - alkanolamines, such as mono-, di- and triethanolamine, mono-, di- and tris(hydroxymethyl)aminomethane and also derivatives thereof,

[0236] - basic amino acids,

[0237] - basic poly(amino)acids or basic poly(amino)acids, such as polylysine and polyarginine,

[0238] - polyamines, such as polyethyleneimine (PEI), polyvinylamine, and compounds of the following formula (A):

[0239]

[0240] In the formula (A), W is a (C1-C6) alkylene group such as a propylene group which is optionally substituted by a hydroxyl group, an amino group or a C1-C4 alkyl group; R x , R y , R z and R t The groups may be the same or different and represent a hydrogen atom or a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group.

[0241] Examples of amines of formula (A) that may be mentioned include 1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

[0242] The term "alkanolamine" means an organic amine comprising a primary, secondary or tertiary amine functional group, and one or more linear or branched C1-C8 alkyl groups bearing one or more hydroxyl groups.

[0243] Organic amines selected from alkanolamines containing 1 to 3 identical or different C1-C4 hydroxyalkyl groups, such as monoalkanolamines, dialkanolamines or trialkanolamines, are particularly suitable for carrying out the present invention.

[0244] Among compounds of this type, mention may be made of monoethanolamine (MEA), diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, N,N-dimethylethanolamine, aminopropanol, 1-aminopropanol, 2-amino-2-methyl-1-propanol, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, tris(hydroxymethylamino)methane, aminobutanol, aminopentanol and aminohexanol, preferably 2-amino-2-methyl-1-propanol.

[0245] More particularly, the amino acids that may be used are of natural or synthetic origin, in their L, D or racemic form and contain at least one acid function more particularly chosen from: carboxylic acid, sulfonic acid, phosphonic acid or phosphoric acid functions.

[0246] As amino acids that can be used in the present invention, mention may especially be made of basic amino acids comprising an additional amine function, optionally contained in a ring or ureido function.

[0247] Such basic amino acids are preferably selected from those corresponding to the following formula (B) and also salts thereof

[0248] R-CH2-CH(NH2)-C(O)-OH(B)

[0249] In the formula (B), R represents a group selected from the following: imidazolyl, preferably 5-imidazolyl; -(CH2)3-NH2; -(CH2)2-NH2; -(CH2)2N(H)-C(O)-NH2; and -(CH2)2-N(H)-C(NH)-NH2.

[0250] The compounds corresponding to formula (B) are histidine, lysine, arginine, ornithine and citrulline.

[0251] The organic amine may also be chosen from organic amines of the heterocyclic type. In addition to histidine already mentioned among the amino acids, mention may in particular be made of pyridine, piperidine, imidazole, triazole, tetrazole and benzimidazole.

[0252] The term "poly"amine or "poly"amino acid means a basic reagent comprising at least two amino acids or amino acid groups attached to the same molecule; they are in particular polymers whose backbone comprises or is substituted with one or more amine groups or amino acid groups.

[0253] The organic amine may also be selected from amino acid dipeptides. As amino acid dipeptides that can be used in the present invention, mention may be made especially of carnosine, anserine and whale.

[0254] The organic amine can also be chosen from compounds containing a guanidine functional group. In addition to arginine, which has already been mentioned as an amino acid, amines of this type that can be used in the present invention include creatine, creatinine, 1,1-dimethylguanidine, 1,1-diethylguanidine, guanidinoacetic acid, metformin, agmatine, N-amidinoalanine, 3-guanidinopropionic acid, 4-guanidinobutyric acid, and 2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.

[0255] As hybrid compounds, mention may be made of the salts of the previously mentioned amines with acids such as carbonic acid or hydrochloric acid.

[0256] In particular, guanidine carbonate or monoethanolamine hydrochloride may be used.

[0257] Preferably, the alkaline agent is selected from water-soluble mineral alkaline agents, alkanolamines, basic amino acids and organic amines, preferably organic amines.

[0258] Preferably, the alkaline agent is selected from: hydroxides of alkali metals or alkaline earth metals, preferably hydroxides of lithium, magnesium, calcium, sodium or potassium, which are buffered with one or more amino acids such as glycine; carbonates, bicarbonates or hydrogen carbonates, carbonates buffered with bicarbonate to obtain a pH < 12.0; phosphates of alkali metals or alkaline earth metals such as lithium, calcium, sodium or potassium; monoethanolamine (MEA); aminopropanol; 1-aminopropanol; 2-amino-2-methyl-1-propanol; 2-amino-2-methyl-1,3-propanediol; aminobutanol; aminopentanol; aminohexanol; arginine and guanidine.

[0259] The aminoalkoxysilane derivative may be selected from compounds corresponding to the following formula (C) and / or oligomers thereof and / or hydrolyzates thereof:

[0260] R1Si(OR2) z (R3) x (OH) y (C)

[0261] In the formula (II):

[0262] ●R1 is a linear or branched, saturated or unsaturated, cyclic or acyclic C1-C6 hydrocarbon chain substituted by a group selected from the following groups:

[0263] -amine NH2 or NHR (R = C1-C 20 and especially C1-C6 alkyl-optionally substituted by groups including silicon atoms, C3-C 40 Cycloalkyl or C6-C 30 Aromatic),

[0264] - an aryl or aryloxy group substituted and / or interrupted by at least one amino group or at least one C1-C4 aminoalkyl group,

[0265] R1 may be interrupted by a heteroatom (O, S or NH) or a carbonyl group (CO),

[0266] ● R2 and R3 may be the same or different and represent a straight or branched alkyl group containing 1 to 6 carbon atoms,

[0267] y indicates an integer ranging from 0 to 3, and

[0268] z indicates an integer ranging from 0 to 3, and

[0269] ●x indicates an integer ranging from 0 to 2,

[0270] Where z+x+y=3.

[0271] The term "oligomer" means the product of polymerization of a compound of formula (C) comprising 2 to 10 silicon atoms.

[0272] Preferably, R2 represents an alkyl group containing from 1 to 4 carbon atoms, better still a linear alkyl group containing from 1 to 4 carbon atoms, and preferably an ethyl group.

[0273] Preferably, R3 represents an alkyl group containing from 1 to 4 carbon atoms, better still a linear alkyl group containing from 1 to 4 carbon atoms, and preferably a methyl or ethyl group.

[0274] Preferably, R1 is a non-cyclic chain.

[0275] Preferably, the compound of formula (C) comprises only one silicon atom in its structure.

[0276] Preferably, R1 represents an alkyl group containing 1 to 6 carbon atoms and even more preferably a straight chain alkyl group or a C1-C6 aminoalkyl group.

[0277] Preferably, z ranges from 1 to 3. Even more preferably, z is equal to 3.

[0278] Preferably, R1 is a linear or branched, saturated or unsaturated C1-C6 hydrocarbon chain (R = C1-C6) substituted by an amine group NH2 or NHR. 20 And especially C1-C6 alkyl, C3-C 40 Cycloalkyl or C6-C 30 aromatic).

[0279] Preferably, the first composition comprises at least one compound of formula (C) selected from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-(m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane and N-(2-aminoethylaminomethyl)phenethyltrimethoxysilane, and better still selected from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane and N-(2-aminoethyl)-3-aminopropyltriethoxysilane, or oligomers and / or hydrolyzates thereof.

[0280] According to a particularly preferred embodiment, the composition comprises 3-aminopropyltriethoxysilane (APTES) or an oligomer thereof and / or a hydrolyzate thereof.

[0281] According to the invention, the alkaline agent and / or aminoalkoxysilane derivative used is present in the composition in a content ranging from 0.01 to 10% by weight, preferably from 0.02 to 5% by weight, relative to the total weight of the composition.

[0282] The pH of the composition according to the invention is greater than or equal to 7.

[0283] Preferably, the composition of the invention has a pH ranging from 7.0 to 12.0, preferably from 7.5 to 11, better still from 8 to 10, and even more preferably from 8 to 9.

[0284] Preferably, the pH of the composition is stable, ie it remains alkaline over time, that is to say greater than or equal to 7. Preferably, the pH of the composition remains alkaline for a storage time of at least 4 weeks or even 8 weeks.

[0285] The composition may comprise a cosmetically acceptable medium. The cosmetically acceptable medium that may be used in the composition of the present invention may comprise a solvent selected from water, an organic solvent and mixtures thereof.

[0286] The organic solvent may be selected from alcohols, polyols, polyol ethers and mixtures thereof, the alcohols being preferably selected from lower C1-C6 alkanols, and preferably selected from ethanol, propanol and isopropanol, the polyols being preferably selected from propylene glycol, hexylene glycol, glycerol and pentylene glycol.

[0287] Preferably, the one or more solvents comprise from 0.1% to 99% by weight of the total composition.

[0288] The composition is preferably aqueous.

[0289] According to this variant, the amount of water may range from 5% to 98% by weight, better still from 15% to 95% by weight, better still from 25% to 90% by weight and even more preferably from 30% to 90% by weight relative to the total weight of the composition.

[0290] The compositions according to the invention may also contain additives commonly used in cosmetics, such as anionic, cationic, amphoteric or nonionic surfactants, thickeners, fatty substances, fixing or conditioning polymers, preservatives, fragrances, colorants, pigments, oxidizing agents, antidandruff agents, agents for preventing hair loss, agents for breaking disulfide bonds and also most of the usual cosmetic agents.

[0291] These additives may be present in the composition according to the invention in an amount ranging from 0 to 20% by weight relative to the total weight of the composition.

[0292] Those skilled in the art will carefully select these optional additives and their amounts so that they do not compromise the properties of the compositions of the present invention.

[0293] The method of the invention comprises, after step a) of applying the composition, a step b) of irradiating the composition on the keratin material in order to crosslink the polymers.

[0294] This irradiation may consist of illumination of the composition applied to the keratin materials with ambient light or with an artificial light source.

[0295] The ambient light or artificial light may emit radiation in the visible and / or UV range. Preferably, it emits at least a certain proportion of radiation in the UV range, for example a UV proportion of at least 2% of the total illumination energy of the ambient light.

[0296] According to a particular embodiment, the exposing comprises or even consists of illuminating the surface of said coating with ambient light, in particular for a period of at least 1 minute.

[0297] The exposure time to ambient light may more particularly range from 10 to 30 seconds and especially from 2 to 15 minutes.

[0298] According to another particular embodiment, the exposing comprises or even consists of illuminating the surface of said coating with an artificial light source.

[0299] The exposure time to the artificial light may range from 1 second to 20 minutes and in particular from 1 second to 1 minute.

[0300] Cross-linking may occur in the presence of natural light or artificial light, for example with illumination using a lamp, a flash, a laser or an LED (for example in the form of an LED array).

[0301] The artificial light source may emit radiation in the visible range and / or radiation in the UV range.

[0302] The emitted light may or may not be monochromatic.The wavelength of the emitted light is preferably centered around 365 nm, in particular between 100 nm and 500 nm and better still between 200 nm and 420 nm.

[0303] Advantageously, crosslinking is initiated by simple illumination without the need for a photoinitiator.

[0304] Preferably, the illumination will be emitting 0.5 to 5 W / cm 2 The exposure time is therefore adjusted to suit the energy of the artificial light source.

[0305] Crosslinking can occur at reduced light intensities; the luminescent system can generate, for example, 500 mJ / cm 2 Up to 10J / cm 2 of this light intensity.

[0306] The dual features of the absence of photoinitiators and relatively low light intensity are particularly advantageous, as this can limit the deleterious effects of aggressive initiators or long-term exposure to intense light, particularly UV wavelengths.

[0307] For the photocrosslinkable polymer (A) used, a person skilled in the art will be able to adjust the lighting characteristics, in particular with regard to exposure time and radiation wavelength.

[0308] According to a preferred embodiment, the composition is applied to keratin fibers, such as the hair.

[0309] According to this embodiment, the composition can be applied to wet or dry, cleaned or uncleaned keratin fibers. Preferably, the keratin fibers are dry after applying the composition and before irradiation.

[0310] In the method, before or after the irradiation step b), the method may further include a pause at room temperature, or at elevated temperature, or under red light.

[0311] However, the following examples illustrate the invention without limiting its scope. Unless otherwise indicated, the amounts are given in weight percent.

[0312] Examples

[0313] The following compositions were prepared from the ingredients in the amounts indicated in the table below (% based on g of active material).

[0314] [Table 1]

[0315]

[0316]

[0317] * Partially saponified polymers of the polyvinyl acetate type carrying stilbazolium groups, adsorbed on polyvinyl acetate particles

[0318] **PVA-SbQ-propionaldehyde obtained according to previously described method

[0319] Obtaining a composition with a stable pH over time provides polymer stability.

[0320] Get an even and long-lasting coat on hair.

[0321] The same type of results were obtained for PVA-SbQ carrying phenyl groups.

Claims

1. A method for treating hair, the method comprising applying a composition comprising: - at least one photocrosslinkable polymer comprising a natural or synthetic backbone selected from poly(vinyl) polymers, at least one photodimerizable side group selected from the monovalent radicals of the following compounds: -Styrylpyridinium (stilbenazolium) and its geometric isomers having the following formula: in: -R 1 and R 3 are the same or different, represent a halogen atom or a (C1-C6) alkyl group; or then two adjacent R 1 or R 3 The group together with the carbon atom carrying it forms a benzo group; -R 2 represents a hydrogen atom, a (C1-C6)alkyl group optionally substituted by one or more halogen atoms or a hydroxyl group; -q and r represent integers from 0 to 4, inclusive; and -Q - represents an anionic counterion selected from the group consisting of halide, perchlorate, tetrafluoroborate, methylsulfate, phosphate, sulfate, methanesulfonate, and p-toluenesulfonate; - represents a bond connecting the monovalent group to the rest of the molecule, it being understood that the side group A2 may be connected via R 2 connected to the rest of the molecule; -Styrylazoles and their geometric isomers having the formula: in: -A represents a sulfur atom, an oxygen atom or NR 2 or C(R 2 )2 group; and Q - , r, q, R 1 , R 2 , and R 3 is as defined previously, -Styrylpyrazine, - Chalcone, - (thio)cinnamate and (thio)cinnamate, -maleimide, -(Thio)coumarin, -thymine, - uracil, -Butadiene - anthracene, -pyridone, -Pyrrolizinone, - acridinium salts, -Furanone, -phenylbenzoxazole, and - their derivatives; - one or more alkaline agents and / or aminoalkoxysilane derivatives, present in the composition in a content ranging from 0.01% to 10% by weight relative to the total weight of the composition, The pH of the composition is 8-12; The photocrosslinkable polymer comprises at least one hydrophobic side group selected from: -saturated or unsaturated (C2-C 22 ) alkyl, which is optionally substituted and / or interrupted by one or more heteroatoms, -alkenyl, - aryl, - fluorinated groups, - silicone groups, and The composition on the hair is irradiated to crosslink the polymers.

2. The method according to claim 1, characterized in that The photo-crosslinkable polymer has a natural or synthetic backbone selected from poly(vinyl acetate).

3. The method according to any one of claims 1 to 2, characterized in that: The polymer comprising at least one photodimerizable group is a polymer that is soluble or dispersible in the composition.

4. The method according to any one of claims 1 to 2, characterized in that: The polymer comprising at least one photo-dimerizable group is in the form of particles.

5. The method according to claim 4, characterized in that The particles are polyvinyl alcohol particles.

6. The method according to any one of claims 1 to 2, characterized in that The hydrophobic group is selected from (C3-C16) alkyl groups.

7. The method according to any one of claims 1 to 2, characterized in that: The polymer comprising at least one photodimerizable group represents 0.01% to 25% relative to the total weight of the composition.

8. The method according to any one of claims 1 to 2, characterized in that The alkaline agent is selected from ammonia water; a water-soluble mineral alkaline agent; an alkanolamine; a basic amino acid; a basic polyamino acid; a polyamine; a compound of the following formula (A): In the formula (A), W is a (C1-C6) alkylene group optionally substituted by a hydroxyl group, an amino group or a C1-C4 alkyl group; R x , R y , R z and R t The groups may be the same or different and represent a hydrogen atom or a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group.

9. The method according to any one of claims 1 to 2, characterized in that: The alkaline agent is selected from water-soluble mineral alkaline agents, alkanolamines, alkaline amino acids and organic amines.

10. The method according to any one of claims 1 to 2, characterized in that: The alkaline agent is selected from: hydroxides of alkali metals or alkaline earth metals, which are buffered with one or more amino acids; carbonates, bicarbonates or bicarbonates, carbonates buffered with bicarbonates to obtain a pH <12.0; phosphates of alkali metals or alkaline earth metals; monoethanolamine (MEA); aminopropanol; 1-aminopropanol; 2-amino-2-methyl-1-propanol; 2-amino-2-methyl-1,3-propanediol; aminobutanol; aminopentanol; aminohexanol; arginine and guanidine.

11. The method according to any one of claims 1 to 2, characterized in that: The composition comprises at least one compound selected from 3-aminopropyltriethoxysilane (APTES), 3-aminoethyltriethoxysilane (AETES), 3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-(m-aminophenoxy)propyltrimethoxysilane, p-aminophenyltrimethoxysilane and N-(2-aminoethylaminomethyl)phenethyltrimethoxysilane, or oligomers thereof and / or hydrolyzates thereof.

12. The method according to any one of claims 1 to 2, characterized in that: The composition comprises at least one compound selected from 3-aminopropyltriethoxysilane and oligomers thereof and / or hydrolyzates thereof.

13. The method according to any one of claims 1 to 2, characterized in that: The alkaline agent and / or the aminoalkoxysilane derivative is present in the composition in an amount ranging from 0.01 wt % to 10 wt % relative to the total weight of the composition.

14. The method according to any one of claims 1 to 2, characterized in that: The pH range is 8 to 9.

15. The method according to claim 14, characterized in that The method includes drying the hair prior to the irradiating step and after the applying step.

16. The method according to any one of claims 1 to 2, characterized in that: The method comprises a pause before or after the irradiating step at room temperature or at elevated temperature or under red light.

17. The method according to any one of claims 1 to 2, characterized in that: The irradiation is irradiation with radiation in the UVA or visible light domain.

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