Photodimerizable polymers comprising at least one polyoxyalkylated group, composition comprising them and cosmetic processing method

Abstract

The present invention relates to specific photodimerizable polymers comprising at least one polyoxyalkylated group, as well as to a composition comprising at least one of these polymers. The present invention also relates to a cosmetic treatment method for keratinous materials, particularly preferably human keratinous fibers such as hair, comprising applying at least one of these specific photodimerizable polymers to said keratinous materials.

Description

Title of the invention: Photodimerizable polymers comprising at least one polyoxyalkylated group, composition comprising them and cosmetic processing method

[0001] The present invention relates to particular photodimerizable polymers comprising at least one polyoxyalkylene group, as well as to a composition comprising at least one of these polymers.

[0002] The present invention also relates to a cosmetic treatment method for keratinous materials, in particular preferably human keratinous fibers such as hair, comprising the application to said keratinous materials of at least one of these particular photodimerizable polymers.

[0003] Hair is generally damaged and weakened by the action of external atmospheric agents such as light and weather, and by mechanical or chemical treatments such as brushing, combing, dyeing, bleaching, perms and / or straightening.

[0004] Thus, to remedy these drawbacks, it is now common to use hair care involving the implementation of care compositions which condition the hair following these treatments in order to give it in particular shine, softness, suppleness, lightness, a natural feel as well as detangling properties.

[0005] These hair care compositions can advantageously be compositions to be applied after shampooing, and which can be in the form of gels, hair lotions or creams of varying thicknesses.

[0006] To improve the cosmetic properties of these compositions, it is known to introduce cosmetic agents called conditioning agents, primarily intended to repair or limit the harmful or undesirable effects induced by the various treatments or aggressions to which hair fibers are subjected, more or less repeatedly. These conditioning agents can, of course, also improve the cosmetic behavior of natural hair.

[0007] For this purpose, it has already been proposed to use cosmetically active organic compounds such as cationic polymers and silicones as conditioning agents in cosmetic care compositions such as conditioners to give hair satisfactory cosmetic properties, in particular shine, softness, suppleness, lightness, a natural feel and improved detangling ability.

[0008] However, the use of these compounds in cosmetic skincare compositions and / or conditioning does not provide hair with fully satisfactory and lasting cosmetic properties. Indeed, these compositions generally provide cosmetic properties, such as detangling dry and wet hair, suppleness, smoothness, shine, coating, and individualized hair character, which remain insufficient and tend to fade after washing the hair with a regular shampoo.

[0009] Thus, there is a real need to make available new compounds capable of overcoming the aforementioned drawbacks, that is to say, compounds capable of providing all types of keratinous materials with detangling and conditioning properties that are not only satisfactory from the first application, but that also last over time and resist washing. These properties must also be homogeneous across all keratinous materials, particularly keratin fibers.

[0010] These goals are achieved by the present invention which relates in particular to a photodimerizable (P) (or photocrosslinkable or photosensitive) polymer comprising at least one photodimerizable pendant group and at least one polyoxyalkylated pendant group.

[0011] The photodimerizable polymers (P) according to the invention make it possible to give good conditioning properties to keratin materials, in particular to keratin fibers, including shine, softness, flexibility, lightness, a natural feel, as well as improved detangling ability.

[0012] Furthermore, the conditioning properties provided by the photodimerizable polymer according to the invention are highly resistant to the various aggressions that hair may be subjected to, such as light, weathering, washing, and perspiration. In particular, they are resistant to shampoos.

[0013] The present invention also relates to a composition comprising one or more photodimerizable polymers (P) as defined above.

[0014] The present invention further relates to a cosmetic treatment process for keratinous materials, in particular keratinous fibers, preferably human, such as hair, comprising: (a) an application step on said keratinous materials of one or more photodimerizable polymers (P), as defined above, (b) followed by a possible drying step of said keratinous materials, (c) followed by a step of exposing said keratinous materials to natural or artificial light radiation.

[0015] Irradiation of the photodimerizable polymers (P) of the invention makes it possible, in particular, to obtain a homogeneous and durable deposit on all keratinous materials, which also has a good conditioning effect and is suitable for all types of keratinous materials. Ratinics. The materials treated in this way exhibit satisfactory, or even improved, conditioning properties that last over time and withstand washing. Hair, in particular, is easy to detangle and has a soft, smooth feel.

[0016] Other objects, features, aspects and advantages of the invention will become even clearer upon reading the description and examples that follow.

[0017] In what follows, and unless otherwise indicated:

[0018] - the boundaries of a domain of values ​​are included in that domain, in particular in the expressions "between" and "ranging from ... to ...";

[0019] - the expression "at least one" used in this description is equivalent to the expression "one or more";

[0020] - by "alkylene chain" is meant an acyclic divalent hydrocarbon chain in Ci-C2o; particularly in Ci-C6, more particularly in Ci-C2 when the chain is linear; possibly substituted by one or more groups, identical or different, chosen from i) hydroxy, ii) (Ci-C2)alkoxy, iii) (poly)hydroxy(C2-C4)alkoxy(di)(Ci-C2)(alkyl)amino, iv) Ra-Za-C(Zb)-Zc-, and v) Ra-Za-S(O)t-Zc- with Za, Zb, identical or different, representing an oxygen atom, a sulfur atom, or an NR a' group, Zc representing a bond, an oxygen atom, a sulfur atom, or an NRa group; Ra representing an alkali metal, a hydrogen atom, an alkyl group or is absent if another part of the cationic molecule and Ra' representing a hydrogen atom or an alkyl group;more specifically the groups iv) are chosen from carboxylate -C(O)O or -C(O)OMetal (Metal = alkali metal), carboxyl -C(O)-OH, guanidino H2H-C(NH2)-NH-, amidino H2H-C(NH2)-, (thio)ureo H2 NC(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'- with Ra', identical or different, representing a hydrogen atom or a (C1-C4) alkyl group; ;

[0021] - by "(hetero)aryl" we mean the aryl and heteroaryl groups; The "aryl" or "heteroaryl" radicals, or the aryl or heteroaryl part of a radical, can be substituted by at least one substituent attached to a carbon atom, chosen from: - an alkyl radical in CrCi6, preferably in CrC8, possibly substituted by one or more radicals chosen from among the hydroxy, alkoxy radicals in CrC2, (poly)-hydroxyalkoxy in C2-C4, acylamino, amino substituted by two alkyl radicals, identical or different, in CrC4, possibly bearing at least one hydroxy group or, the two radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising 5 to 7 links, preferably 5 or 6 links, saturated or unsaturated possibly substituted possibly comprising another heteroatom identical or different from the nitrogen; - a halogen atom such as chlorine; - a hydroxy group; - an alkoxy radical in Ci-C2; - a C2-C4 (poly)-hydroxyalkoxy radical; - an amino radical; - a heterocycloalkyl radical with 5 or 6 links; - a heteroaryl radical with 5 or 6 links possibly cationic, preferably imidazolium, and possibly substituted by an alkyl (CrC4) radical, preferably methyl; - an amino radical substituted by one or two alkyl radicals, identical or different, in the Ci-C6 configuration, possibly bearing at least: i) a hydroxyl group, ii) an amino group possibly substituted by one or two Ci-C3 alkyl radicals possibly substituted, said alkyl radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising 5 to 7 links, saturated or unsaturated possibly substituted possibly comprising at least one other heteroatom different or not from nitrogen, iii) a quaternary ammonium group -N+R'R”R”', M for which R', R”, R'”, identical or different represent a hydrogen atom or a Ci-C4 alkyl group; and M represents a counterion of the corresponding organic acid, mineral or halide, (iv) or a 5- or 6-membered heteroaryl radical possibly cationic, preferably imidazolium, and possibly substituted by an alkyl (CrC4) radical, preferably methyl; - an acylamino radical (-N(R)-C(O)-R') in which the radical R is a hydrogen atom, an alkyl radical in Ci-C4 possibly bearing at least one hydroxy group and the radical R' is an alkyl radical in CrC2; - a carbamoyl radical ((R)2N-C(O)-) in which the R radicals, identical or not, represent a hydrogen atom, an alkyl radical in CrC4 possibly bearing at least one hydroxy group; - an alkylsulfonylamino radical (R'-S(O)2-N(R)-) in which the radical R represents a hydrogen atom, an alkyl radical in Ci-C4 possibly bearing at least one hydroxy group and the radical R' represents an alkyl radical in CrC4, a phenyl radical; - an aminosulfonyl radical ((R)2N-S(O)2-) in which the R radicals, identical or not, represent a hydrogen atom, an alkyl radical in Ci-C4 possibly bearing at least one hydroxy group, - a carboxylic radical in acidic or salt form (preferably with a metal) alkaline or an ammonium, substituted or not); - a cyano group; - a nitro or nitroso group; - a polyhaloalkyl group, preferably trifluoromethyl; The cyclic, cycloalkyl or heterocyclic part of a non-aromatic radical can be substituted by at least one substituent chosen from the following groups: - hydroxy; - C1-C4 alkoxy, (poly)hydroxyalkoxy C2-C4; - alkyl in CrC4; - alkylearbonylamino (RC(O)-N(R')-) in which the radical R' is a hydrogen atom, an alkyl radical in CrC4 possibly bearing at least one hydroxy group and the radical R is an alkyl radical in Ci-C2, amino possibly substituted by one or two identical or different alkyl groups in CrC4 themselves possibly bearing at least one hydroxy group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising 5 to 7 links, saturated or unsaturated possibly substituted possibly comprising at least one other heteroatom different or not from nitrogen; - alkylearbonyloxy (RC(O)-O-) in which the radical R is a Ci-C4 alkyl radical, amino group possibly substituted by one or two identical or different Ci-C4 alkyl groups themselves possibly bearing at least one hydroxy group, said alkyl radicals being able to form with the nitrogen atom to which they are attached, a heterocycle comprising 5 to 7 links, saturated or unsaturated possibly substituted possibly comprising at least one other heteroatom different or not from nitrogen; - alkoxycarbonyl (RGC(O)-) in which the radical R is an alkoxy radical in CrC4, G is an oxygen atom, or an amino group possibly substituted by an alkyl group in CrC4 itself possibly bearing at least one hydroxy group, said alkyl radical being able to form with the nitrogen atom to which they are attached, a heterocycle comprising 5 to 7 links, saturated or unsaturated possibly substituted possibly comprising at least one other heteroatom different or not from nitrogen;

[0022] - a cyclic, cycloalkyl, heterocyclic radical, or a non-aromatic part of a radical aryl or heteroaryl, can also be substituted by one or more oxo groups;

[0023] - a cycloalkyl radical is a mono- or bicyclic, hydrocarbon radical, comprising 3 to 10 carbon atoms, preferably 4 to 7 carbon atoms such as cyclopentyl, or cyclohexyl;

[0024] - a hydrocarbon chain is unsaturated when it comprises one or more double bonds and / or one or more triple bonds;

[0025] - an "aryl" radical represents a mono- or polycyclic carbon group, condensed or not, comprising from 6 to 22 carbon atoms, and of which at least one ring is aromatic; preferably the aryl radical is a phenyl, biphenyl, naphthyl, indenyl, anthracenyl, or tetrahydronaphthyl;

[0026] - a "heteroaryl radical" represents a mono- or polycyclic group, condensed or not, comprising 5 to 22 links, 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms, and of which at least one ring 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, phenoxazolyl, pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl, pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl, thiadiazolyl, thiazolyl, thiazolopyridinyl, thiazoylimidazolyl, thiopyrylyl, triazolyl, xanthylyl and its ammonium salt;

[0027] - a "heterocyclic radical" is a radical that can contain one or two insa turations but non-aromatic, mono- or polycyclic, condensed or non-condensed, containing 5 to 22 links, comprising 1 to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and selenium atoms;

[0028] - a "heterocycloalkyl radical" is a heterocyclic radical comprising at a saturated cycle;

[0029] - a "cationic heteroaryl radical" is a heteroaryl group as defined previously which includes an endocyclic or exocyclic cationic group; - when the charge is endocyclic, it is taken up in the electron delocalization by mesomeric effect, for example it is a pyridinium, imidazolium or indolinium group: with R and R' being a heteroaryl substituent as defined previously and particularly a (hydroxy)(Ci-C8)alkyl group such as methyl; - When the charge is exocyclic, it is not involved in electron delocalization by mesomeric effect; for example, this applies to R+ ammonium or phosphonium substituents such as trimethylammonium, located outside the heteroaryl group. that pyridinyl, indolyl, imidazolyl, or naphthalimidyl in question: with R a heteroaryl substituent as defined below and R+ an ammonium RaRbRcN+-, phosphonium RaRbRcP+- or ammonium RaRbRcN+-(Ci-C6 )alkylamino, RaRbRcN+-(Ci-C6)alkyl or RaRbRcN+-(Ci-C6)alkoxy group where Ra, Rb and Rc are identical or different represent a (CrC8)alkyl group such as methyl;

[0030] - a "cationic aryl ring with exocyclic charge" means an aryl ring whose quaternized cationic group is located outside said ring, this includes R+ ammonium or phosphonium substituents such as trimethylammonium, located outside the aryl group such as phenyl or naphthyl:

[0031] - an "alkyl radical" is a hydrocarbon radical in the form of C1 to C2O, linear or branched, of preference in Ci to Ci0, more preferentially in Ci to C8>better in Ci to C6>and better still in Ci to C4;

[0032] - an "alkenylene radical" is an unsaturated divalent hydrocarbon radical such as defined previously which can contain from 1 to 4 double bonds -C=C-, conjugated or not; particularly the alkenylene group contains 1 or 2 unsaturation(s);

[0033] - the expression "possibly substituted" attributed to the alkyl radical implies that said alkyl radical may be substituted by one or more radicals chosen from among the following radicals: i) hydroxy, ii) alkoxy in Ci-C4, iii) RZC(X)-Y- with X, Y and Z representing an oxygen, sulfur or N(R') atom, or else X and / or Z represent(s) a bond, R and R', identical or different, represent a hydrogen atom or a (Ci-C6)alkyl group, preferably X representing an oxygen atom, iv) amino possibly substituted by one or two alkyl radicals, identical or different, in CrC4, said alkyl radicals being able to form with the nitrogen atom bearing them a heterocycle comprising 5 to 7 links, possibly including another heteroatom different or not from nitrogen;(v) or a quaternary ammonium group N+R'R”R'”, M for which R', R”, R'”, identical or different represent an alkyl group in CrC4, or -N+R'R”R”' forms a heteroaryl such as imidazolium possibly substituted by an alkyl CrC4 group, and M represents the anionic counter-ion, (vi) carboxy C(O)OH, (vii) carboxylate C(O)O, M+ with M+ representing a; against cationic ion such as alkali or alkaline earth metal, viii) sulfonic -SO3H, ix) sulfonate -SO3, M+ with M+ as defined previously, x) cyano and xi) phenyl;

[0034] - an "alkoxy radical" is an alkyl-oxy radical for which the alkyl radical is a hydrocarbon radical, linear or branched, in CrCi6 preferably in CrC8; when the alkoxy group is possibly substituted, this implies that the alkyl group is possibly substituted as defined above;

[0035] - by "organic or mineral acid salt" we mean more particularly salts chosen from a salt derived from i) hydrochloric acid HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H2SO4, iv) alkylsulfonic acids: Alk-S(O)2OH such as methylsulfonic acid and ethylsulfonic 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 tolueneoxysulfinic acid and phenoxysulfinic acid; xii) phosphoric acid H3PO4; xiii) acetic acid CH3C(O)-OH; xiv) triflic acid CF3SO3H and xv) tetrafluoro-roboric acid HBF4;

[0036] By "anionic counter-ion" is meant an anion or anionic group derived from an organic or mineral acid that counterbalances the cationic charge of the compound; more particularly, the anionic counter-ion is chosen from i) halides such as chloride, bromide; ii) nitrates; iii) sulfonates, including Ci-C6 alkylsulfonates: 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) carboxylates Alk-C(O)-OH with Alk representing a (Ci-C6)alkyl group optionally substituted by one or more hydroxy or carboxylate groups such as citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl sulfates: Alk-OS(O)O such as methysulfate and ethylsulfate; x) aryl sulfates: Ar-OS(O)O such as benzenesulfate and toluenesulfate;xi) alkoxy sulfates: Alk-OS(O)2O such as methoxy sulfate and ethoxysulfate; xii) aryloxy sulfates: Ar-OS(O)2O; xiii) phosphates: O=P(OH)2-O, O=P(O)2-OH, O=P(O)3, HO-[P(O)(O)]WP(O)(O)2, with w being an integer; xiv) acetate; xv) triflate; and xvi) borates such as tetrafluoroborate; and xvii) sulfate (O=)2S(O)2 or SO42 and hydrogen sulfate HSO4; The anionic counterion, derived from the salt of an organic or mineral acid, ensures the electroneutrality of the molecule: thus, it is understood that when the anion contains several anionic charges, the same anion can serve for the electroneutrality of several cationic groups in the same molecule, or can serve for the electroneutrality of several molecules; for example, a dye that contains two cationic groups may contain either two "single-charged" anionic counter-ions or one "double-charged" anionic counter-ion such as (O=)2S(O )2 or O=P(O )2 -OH;

[0037] - moreover, the addition salts usable within the framework of the invention are in particular chosen from among the addition salts with a cosmetically acceptable base such as alkalizing agents as defined below as alkali metal hydroxides such as soda, potash, ammonia, amines or alka-nolamines.

[0038] For the purposes of this invention, a "photodimerizable" group is defined as a chemical group that undergoes photodimerization reactions under irradiation, that is, after exposure to natural or artificial light. In the context of this invention, photodimerization is a chemical reaction between two double bonds (of the 2+2 type) or two pairs of double bonds (of the 4+4 type), and more particularly between two double bonds (of the 2+2 type).

[0039] The case of a reaction between two double bonds can be schematically represented as follows:

[0040] These photodimerization reactions are defined in the document "Advanced Organic Chemistry, J Marck, 4th edition, Wley Interscience, NY 1992, p 855".

[0041] Thus, the double bond, when photo-stimulated, generally when subjected to UV radiation, is capable of reacting with another double bond by cyclization. According to the present invention, the double bond is said to be activated, that is to say, it is spontaneously photodimerizable without requiring the presence of a photoinitiator or a chemical initiator.

[0042] The activation of this double bond is generally induced by the presence of an electron-withdrawing substituent in the alpha position of this photodimerizable double bond. Examples of electron-withdrawing substituents include aromatic rings, such as the phenyl group possibly substituted by 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-Y-R', with R' representing a hydrogen atom or a (Ci-C4)alkyl group possibly substituted by one or more halogen atoms, Y, and Y', identical or different, representing an oxygen, sulfur, or NR atom, with R" representing a hydrogen atom or a (Ci-C6)alkyl group. Photodimerizable polymers (P)

[0043] The present invention relates to a photodimerizable polymer (P) comprising at least one photodimerizable pendant group and at least one polyoxyalkylated pendant group.

[0044] The terms photodimerizable, photocurable and photosensitive are equivalent for the purposes of the present invention.

[0045] Preferably, the photodimerizable pendant groups usable according to the invention are chosen from the following monovalent radicals of formulas (I) and (II): as well as their geometric isomers, formulas (I) and (II) in which: - Y and Z independently designate a nitrogen atom or a C(R) group with R representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl; - A represents a bond or a divalent group chosen from the radicals (CrC8)alkylene, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio)carbonyl, (C2-C8)alkenylenes and their combinations; - B represents a monovalent group chosen from among (CrC8)alkyl radicals, aryl radicals, possibly cationic heteroaryl radicals, cycloalkyl radicals, possibly cationic heterocycloalkyl radicals, (thio)carbonyl radicals, (C2-C8)alkenyl radicals and their combinations; - X represents a divalent group chosen from the radicals (C2-C8)alkylenes, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio)carbonyls, (C2-C8)alkenylenes and their combinations; - p represents an integer between 1 and 5 inclusively, in particular between 1 and 3, preferably p equals 1; - rcPæscntc 'a ^a^son clu' re^e 'a part of the monovalent radical to the rest of the molecule; and Each of the aforementioned groups may optionally be substituted by one or more halogen atoms or groups chosen from among the (Ci-C6)alkyl, hydroxy, amino, (di)(Ci-C6)alkylamino, phenyl, carboxy, (Ci-C6)alkoxy, (Ci-C6)alkoxy(thio)carbonyl, hydrogeno(thio)-carbonyl, sulfonato ROS(O)2- or RS(O) groups 2-O-, amide RR'NC(O)- or RC(O)-N(R')- or acyl RC(O)-, ammonium R'R”N+- with R, R' and R”, identical or different, representing a hydrogen atom or a (Ci-C4)alkyl group.

[0046] The dimerizable pendant groups according to the invention are in particular those cited in US patents 2,811,510, EP 0 313 220, EP 0 313 221, EP 092 901, GB 2 030 575 and GB 2 076 826, as well as in the articles "Chemical review Vol 83,5 1983, p 507" "Polym, Paint colour Journal 1988, 178, p 209" and "Current Trends in Polymer Photochemistry, Ellis Morwood edition, NY, 1995".

[0047] More preferably, the photodimerizable pendant group(s) are chosen from among the monovalent radicals of the following compounds: - stilbene, - styrylpyridinium (stilbazolium) with the following formulas (Al) and (A2), and their geometric isomers: Al A2 in which: - R1 and R3, identical or different, represent a halogen atom or a (Ci-C6)alkyl group; or two contiguous R1 or R3 groups together with the carbon atoms that bear it form a benzo group; - R2 represents the hydrogen atom, a (Ci-C6)alkyl group possibly substituted by one or more halogen atoms such as chlorine or hydroxy, preferably R2 represents a (Ci-C6)alkyl group such as methyl, ethyl, propyl; - q and r represent an integer between 0 and 4 inclusive; and - Q represents an anionic counter ion preferably chosen from halide ions such as chlorides, bromides, iodides, perchlorates, tetrafluoroborates, methyl sulfate, phosphates, sulfates, methanesulfonates, p-toluenesulfonate; and represents the bond that connects the monovalent radical part to the rest of the molecule being understood that the pendant group A2 can be linked to the rest of the molecule via R2; preferably the bond is located on the phenyl in the para position of the styryl group on Al or linked to the rest of the molecule via R2 on A2; preferably the styryl group of Al and A2 is located para to the pyridinium group; - styrylazolium with the following formulas (B1 and B2) and their geometric isomers: in which: - A represents a sulfur atom, an oxygen atom, or an NR2 or C(R2)2 group; and 'Q'r'R*'R2'ctR3 being such as defined previously, preferably the α bond is located on the phenyl group in the para position of the I

[0048]

[0049] Stryryle group, - styrylpyrazine, - chalcone, - (thio)cinnamate and (thio)cinnamamide, - Malimides, - (thio)coumarin, - thymine, - uracil, - butadiene, - anthracene, - pyridone, - pyrrolizinone, - acridizinium salts, - furanone, - phenylbenzoxazole, and - their derivatives. According to a particular embodiment, the photodimerizable pendant group(s) are chosen from: a) the photodimerizable group(s) bearing a stylbazolium function of formula (la) or (Ib) and their geometric isomers: R' X (the) in which: - R represents a hydrogen atom, a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group; - R' represents a hydrogen atom or an alkyl group in C1-C4, and - X designates an anionic counter ion preferably chosen from halide ions such as chlorides, bromides, iodides, perchlorates, tetrafluoroborates, methyl sulfate, phosphates, sulfates, methanesulfonates, p-toluenesulfonate; preferably the styryl group is located para to the pyridinium group and / or para to the α bond; A (JD)

[0050]

[0051] in which: - R' ' denotes a divalent alkylene radical having from 2 to 8 carbon atoms, - R' represents a hydrogen atom or an alkyl group in C1-C4, and - X having the same meaning as that described for the previous formula (la), g having the same meaning as before; preferably the styryl group is located para to the pyridinium group; Or b) photodimerizable groups bearing a styrylazolium function of formula (lia): (lia) in which: - Ri designates the hydrogen atom, a C1-C4 alkyl group or a C1-C4 hydroxyalkyl group; - A designates a sulfur atom, an oxygen atom, or an NR' or C(R') group 2, R'; with R' representing the hydrogen atom or an alkyl group in CrC4, R' preferably representing the hydrogen atom; and - X having the same meaning as that described for the previous formula (the); having the same meaning as before; Preferably, the styryl group is located on the phenyl group in the para position of the bond

[0052] Such photodimerizable pendant groups have activated double bonds, so that the photodimerization of these double bonds is triggered spontaneously in the UVA range, without requiring a photoinitiator.

[0053] By "photoinitiator", for the purposes of the present invention, we mean a compound which initiates the photodimerization reaction and releases a radical under irradiation, particularly in the UV range.

[0054] The photodimerizable polymer(s) (P) according to the present invention further comprise one or more polyoxyalkylated pendant groups.

[0055] Preferably, the polyoxyalkylated pendant group(s) comprise one or several polyoxyalkylated groups chosen from the groups with the following formula: -[OX]n-OR in which, X represents an alkylene group having 2 to 3 carbon atoms, preferably 2 carbon atoms, n denotes an integer from 10 to 1000, preferably from 20 to 200, and more preferably from 25 to 150 and R represents an alkyl chain, linear or branched, having 1 to 6 carbon atoms.

[0056] According to a first embodiment, the polyoxyalkylated pendant group(s) of the photodimerizable polymer(s) (P) comprise one or more polyoxyethylenated groups, corresponding to the formula -[O-CH2-CH2]n-OR, where n is an integer from 20 to 500, preferably from 30 to 150, and R represents a linear or branched alkyl chain having from 1 to 6 carbon atoms. In other words, according to this embodiment, the photodimerizable polymer(s) (P) comprise one or more PEG (polyethylene glycol) groups. In particular, we will use photodimerizable polymers (P) comprising one or more polyoxyethylenated groups, corresponding to the formula -[O-CH2-CH2]n-OR, with n denoting an integer from 40 to 50 or from 120 to 150, and R representing an alkyl chain, linear or branched, having from 1 to 6 carbon atoms.

[0057] According to another embodiment, the polyoxyalkylated pendant group(s) of the photodimerizable polymers (P) comprise one or more poly- Linear or branched oxypropylene polymers, preferably conforming to the formula -[O-CH2-CH2-CH2]n-OR, where n is an integer from 10 to 500, preferably from 30 to 200, and R represents a linear or branched alkyl chain having from 1 to 6 carbon atoms. In other words, according to this embodiment, the photodimerizable polymer(s) (P) comprise one or more PPG (polypropylene glycol) groups.

[0058] The photodimerizable polymer(s) (P) comprise one or more polyoxyalkylated pendant groups preferably comprising 30 to 150 polyoxyethylened groups.

[0059] The skeleton of the photodimerizable polymer(s) (P) according to the invention can be of various kinds. This polymer skeleton can be natural or synthetic. Polysaccharides are examples of natural polymer skeletons.

[0060] Examples of polysaccharides include xanthan gum, carrageenan, chitosan, cellulose and its derivatives, alginate, starch, dextran, pullulan, galactomannan and their biologically acceptable salts, as well as their derivatives.

[0061] Examples of synthetic skeletons include polyvinyl alcohols, poly(vinyl) polymers and polydiorganosiloxanes.

[0062] Among poly(vinyl) polymers, we can mention poly(vinyl acetate), by partially or totally hydrolyzed and polyvinyl alcohol (PVA).

[0063] The photodimerizable polymer(s) (P) of the invention have a natural or synthetic skeleton preferably chosen from polysaccharides, poly(vinyl) polymers and polydiorganosiloxanes, and more preferably from polyvinyl alcohols and poly(vinyl acetate), preferably partially hydrolyzed.

[0064] As regards photodimerizable polymers (P) having photodimerizable pendant groups bearing a stylbazolium function, they are obtained by reaction of the polymer in question with a chemical entity comprising a group of formula (la) or (Ib).

[0065] Preferably, the chemical entity comprising a group (la) carries a reactive group W of the aldehyde or acetal type.

[0066] Examples of chemical entities that can be used to graft styrylpyridinium-type groups include quaternary salts of 2-(4-formylstyryl)-pyridinium, 4-(4-formyl-styryl)-pyridinium, 2-(3-formylstyryl)-pyridinium, N-methyl-2-(4-formylstyryl)pyridinium, N-methyl-3-(4-formylstyryl)-pyridinium, N-methyl-2-(3-formylstyryl)-pyridinium, N-methyl-2-(2-formylstyryl)pyridinium, N-ethyl-2-(4-formyl-styryl)-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.

[0067]

[0068]

[0069]

[0070] The quaternary salts of pyridinium can be chloride, bromide, iodide, perchlorate, tetrafluoroborate, methosulfate, phosphate, sulfate, methanesulfonate, or p-toluenesulfonate salts. Such chemical entities are described in GB-A-2030575. Examples of such entities include 4-(4-formylphenylethenyl)l-methylpyridinium methosulfate, l-(3-ethoxycarbonylmethyl)-4-[2-(4-formylphenyl)ethenyl]pyridinium bromide, and l-(methoxycarbonylpropyl)-4-[2-(4-formylphenyl)ethenyl]pyridinium bromide. Such entities are described in US 2007 / 0112094. Preferably, n-methyl-4-(4-formylstyryl)pyridinium methylsulfate (RN= 74401-04-0) is used, notably marketed by the company WAKO. The synthesis, described below, of these polymers functionalized by photodimerizable groups such as those comprising a styryl group and polyoxyalkylated groups is feasible by following the protocol of T. Uhlich et al. (Reactive & Functional Polymers, 28, 55-40 (1995)). (yi'j {VH'J (VSt') compounds of formula (III) to (VIII') in which, - R, identical or different, represents a hydrogen atom, or a (Ci-C4)alkyl group, possibly substituted and / or interrupted by one or more heteroatoms, preferably R represents a hydrogen atom or a (Ci-C4)alkyl group such as methyl, ethyl, or propyl, more preferably R represents a hydrogen atom; - R1 represents a hydrogen atom, or a (Ci-Cio)alkyl group, possibly substituted and / or interrupted by one or more heteroatoms, preferably R1 represents a hydrogen atom or a (Ci-C4)alkyl group; - R2 represents a polyoxyalkylene group, of the following formula: -[OX]n-OR in which, X represents an alkylene group having from 2 to 3 carbon atoms, preferably 2 carbon atoms, n designates an integer from 10 to 1000, preferably from 20 to 200, and more preferably from 25 to 150, and R represents an alkyl chain, linear or branched, having from 1 to 6 carbon atoms; - A represents a group derived from a photodimerizable compound, preferably styrylpy-ridinium such as (I), (II), (Al), (A2), (la), (Ib) or (lia) as defined above, more particularly chosen from (Al) or (la) as defined above; - X represents an oxygen atom or a sulfur atom, preferably oxygen; - X' and X”, represent an oxygen atom, sulfur or an N(R3) group with R3 representing a hydrogen atom or a (Ci-C4)alkyl group, preferably X' and X” represent an oxygen atom.

[0071] The majority of the products obtained are of formula (VII').

[0072] Advantageously, these chemical entities react with a polyvinyl alcohol or polyvinyl acetal type polymer as described in the documents cited above and also such as polymer (III) described in the diagram above for which X, X' and X” represent an oxygen atom, R and R1 being as described above.

[0073] For example, a polyvinyl alcohol grafted polymer having the following structural motifs is thus obtained, A representing a group (I), (Al) or (la):

[0074] Polyvinyl alcohol polymers grafted with stryrylpyridinium groups are described in particular in the publication Ichimura K et al, Preparation and Characteristics of photocross-linkable poly(vinyl alcohol), Journal of polymer science, polymer chemistry edition, Vol 20, 1419-1432 (1982).

[0075] The polymers can be obtained by reaction of partially hydrolyzed polyvinyl alcohol or polyvinyl acetate with formyl or acetal group styrylpyridinium salts as described in GB-A-2030575, WO 96 / 29312, US 5061603, GB-A-2076826, EP-A-092901.

[0076] Cellulose polymers grafted with styrylpyridinium groups are described in particular in US 2007 / 0112094.

[0077] Preferably, the chemical entity comprising an (Al) group or (the) carries a reactive group which is a halogen atom such as chlorine.

[0078] In this variant, the chemical entity corresponds, for example, to the formula

[0079] Advantageously, the photodimerizable polymer comprising the (Ib) groups is obtained for example by reaction of the above entity with the polysaccharide chosen from those defined previously.

[0080] For their part, photodimerizable polymers having photodimerizable groups bearing a styrylazolium function are obtained by reaction of the polymer with a chemical entity comprising a group of formula (lia).

[0081] Preferably, the chemical entity comprising a (lia) group carries a reactive W group of the aldehyde or acetal type.

[0082] Examples of chemical entities that can be used to graft styrylazolium-type groups include those described in EP-A-313220.

[0083] Advantageously, these chemical entities react with a polyvinyl alcohol or polyvinyl acetal type polymer as described in the documents cited above.

[0084] A polyvinyl alcohol grafted polymer having the following structural motifs is thus obtained, with B corresponding to the group or (lia) as defined previously:

[0085]

[0086]

[0087]

[0088] Polyvinyl alcohol polymers grafted with styrylazolium groups are described in particular in EP-A-313220. In this document, these polymers can be obtained by reaction of partially hydrolyzed polyvinyl alcohol or polyvinyl acetate with styrylazolium salts with aldehyde or acetal groups. According to one embodiment, the photodimerizable polymer (P) of the invention is in the form of particles, in particular dispersed particles. Thus, in the latter case, the polymer particles are more particularly polyvinyl alcohol particles. According to a preferred embodiment, the photodimerizable polymer (P) of the invention is soluble in the cosmetic medium. Thus, according to one embodiment, the photodimerizable polymer (P) is a polyvinyl acetate (PVA) type polymer partially functionalized by one or more polyoxyalkylene group(s) and one or more group(s) of formula (IX): (IX)

[0089]

[0090] with Q being as defined previously. The degree of polymerization of PVA can be between 100 and 5000 and the rate of substitution, in % of functions of formula (I) as defined above, can be between 0.1 and 25%, preferably between 0.5 and 5%. The following diagram represents a variant where the photodimerizable polymer (P) is the polymer (III) as defined previously, bearing functions grafted by stylbazolium entities such as those of formula (Al) as defined above, which are capable of crosslinking under the effect of light, as illustrated below.

[0091] These materials react to radiation which may include both a UV light component and a visible light component, in particular a low dose of UV.

[0092] Preferably, the following diagram represents the mPEG-PVA-SbQ polymer (PVAcetate type polymer bearing polyoxyethylenated functions and functions grafted by stylbazolium entities), which is capable of crosslinking under the effect of light, as illustrated below. PVA-SbQ

[0093] These materials are particularly appreciated because they do not require a photoinitiator and react to radiation that can include both a UV light component and visible light, in particular a low dose of UV.

[0094] Pendant groups having reactivity in both UV and visible light are preferred.

[0095] According to another embodiment, the photodimerizable polymer (P) is represented by a natural polymer that is functionalized by photodimerizable groups and polyoxyalkylene groups.

[0096] This may include a polysaccharide which may be selected from chondroitin sulfate, keratan, keratan sulfate, heparin, heparin sulfate, xanthan gum, carrageenan, hyaluronic acid, chitosan, cellulose and its derivatives, alginate, starch, dextran, pullulan, galactomannan and their biologically acceptable salts.

[0097] The degree of functionalization is of course adjusted to be able to confer the degree of crosslinking required during activation.

[0098] According to the invention, the degree of functionalization in photodimerizable pattern is at least 0.1%, or even at least 0.5%, or even at least 1%.

[0099] The total quantity of the photodimerizable pendant group(s) present in the photodimerizable polymer (P) according to the invention is preferably from 0.5 to 6 mol%, and more preferably from 1 to 5 mol%, relative to the total molar weight of the polymer.

[0100] The total quantity of the polyoxyalkylene pendant group(s) present in the photodimerizable polymer (P) according to the invention is preferably from 0.1 to 5 mol%, and more preferably from 0.5 to 3 mol%, relative to the total molar weight of the polymer.

[0101] The photodimerizable polymer (P) according to the invention preferably has a number average molecular weight ranging from 2000 to 200000, more preferably from 5000 to 100,000, and even better from 20000 to 80000.

[0102] By way of example of photodimerizable polymers (P) according to the present invention, the following mPEG-PVA-SbQ polymers with the following formulas may be mentioned in particular. The molar percentages of each unit (or pendant group) may be varied:

[0103] The photodimerizable polymer(s) (P) according to the present invention may optionally further comprise one or more hydrophobic pendant groups.

[0104] Examples of hydrophobic pendant groups that can be used according to the present invention include: - (Ci-C30)alkyl groups, saturated or unsaturated, possibly substituted and / or interrupted by one or more heteroatoms, - the alkenyl groups, - aryl groups such as phenyl, pyridyl, furyl, indoyl, benzofuryl, thiophenyl, imizadoyl, oxazoyl, thiazoyl, pyrazinyl, pyrimidinyl; - fluorinated groups such as fluorocarbon groups, such as -CF3, -CHF2, -OCF3, -SCF3, CF3C(O)-, - silicone groups such as -SiRaRbRc such as -Si(CH3)3, polydimethylsiloxane-PDMS, -Si(OR)3, PDMS a,w diaminopropyl, PDMS a,w dihydroxyalkyl, PDMS a,w dicarboxyalkyl, with Ra, Rb and Rc, identical or different, representing a (Ci-C8)alkyl group possibly interrupted and / or terminated by one or more non-contiguous heteroatoms such as O or S; and R representing a (Ci-C6)alkyl group.

[0105] Preferably, when present, the hydrophobic pendant group(s) represent a (C2-C22)alkyl group, more preferably a (C3-Ci6)alkyl group and even better a methyl, octyl or phenyl group. Composition

[0106] The present invention also relates to a composition comprising one or more photodimerizable polymers (P) as defined above.

[0107] According to a first variant of the invention, the composition comprises a single photodimerizable polymer (P) comprising several photodimerizable pendant groups of different or non-different natures.

[0108] According to another embodiment of the invention, the composition comprises a mixture of photodimerizable polymers (P) comprising one or more photodimerizable pendant groups of a different nature.

[0109] Consequently, the reactions can take place between two photodimerizable groups of the same or different chemical natures. The activated double bonds can react with another double bond of the same chemical nature or with another double bond of a different chemical nature.

[0110] The total content of the photodimerizable polymer(s) (P), present in the composition according to the invention, preferably ranges from 0.01 to 50% by weight, more preferably from 0.1 to 25% by weight and even better from 1 to 20% by weight, relative to the total weight of the composition.

[0111] The composition according to the present invention may optionally further comprise one or more photosensitizers.

[0112] For the purposes of this invention, photosensitizer means an ingredient which modifies the wavelength of the irradiation, thereby triggering the photodimerization reaction.

[0113] For example, the photodimerization of dimethylmaleimide groups is triggered by irradiation centered on the wavelength range from 270 to 300 nm. In the presence of a photosensitizer such as thioxanthone, photodimerization becomes effective with irradiation centered on the wavelength range from 360 to 430 nm.

[0114] Among the photosensitizers that can be used according to the invention, the following may be mentioned in particular: thioxanthone, rose of Bengal, phloxine, eosin, erythrosine, fluorescein, acriflavin, thionine, riboflavin, proflavin, chlorophylls, hematoporphyrin, methylene blue and mixtures thereof.

[0115] The total content of the photosensitizer(s), when present in the composition of the invention, preferably ranges from 0.00001% to 5% by weight, relative to the total weight of the composition.

[0116] According to another embodiment, the composition according to the present invention is preferably aqueous.

[0117] By "aqueous composition" according to the present invention, we mean a composition in which the total water content is greater than or equal to 20% by weight, relative to the weight of the composition. Preferably, the total water content is greater than or equal to 30% by weight, more preferably greater than or equal to 40% by weight of water, and even better greater than or equal to 50% by weight, relative to the total weight of the composition. Advantageously, the total water content ranges from 40 to 99% by weight, and preferably from 50 to 95% by weight, relative to the total weight of the composition.

[0118] In addition to water, the composition according to this embodiment may optionally include one or more organic solvents.

[0119] Preferably, the organic solvent(s) are chosen from linear or branched monoalcohols having 1 to 8 atoms, and more preferably 1 to 4 carbon atoms, polyols, polyethylene glycols, aromatic alcohols and mixtures thereof.

[0120] Examples of usable organic solvents according to the invention include ethanol, propanol, butanol, isopropanol, isobutanol, propylene glycol, dipropylene glycol, isoprene glycol, butylene glycol, pentylene glycol, hexylene glycol, glycerol, sorbitol, benzyl alcohol, phenoxyethanol and mixtures thereof.

[0121] The organic solvent(s) usable according to the invention can be chosen from linear or branched monoalcohols having 1 to 4 carbon atoms, and mixtures thereof, preferably from ethanol, propanol, butanol, isopropanol, isobutanol, and mixtures thereof.

[0122] The pH of the composition according to the present invention varies preferably from 3 to 9, and more preferably from 4 to 8.

[0123] The composition according to the present invention may optionally further comprise one or more additional compounds, different from the ingredients of the invention and among which may be mentioned fats, cationic, anionic, non-ionic, amphoteric or zwitterionic surfactants, cationic, anionic, non-ionic, amphoteric polymers or mixtures thereof, anti-dandruff agents, anti-seborrheic agents, anti-hair loss and / or hair regrowth agents, vitamins and provitamins including panthenol, sunscreens, sequestering agents, plasticizers, solubilizing agents, acidifying agents, thickening agents mineral or organic, including polymeric thickening agents, antioxidants, hydroxy acids, perfumes, preservatives, ceramides and mixtures thereof.

[0124] Of course, a person skilled in the art will take care to choose this or these possible additional compounds in such a way that the advantageous properties intrinsically attached to the composition according to the invention are not, or substantially not, altered by the envisaged addition(s).

[0125] The above additional compounds may generally be present in quantities of each of them between 0 and 20% by weight, relative to the total weight of the composition.

[0126] The composition according to the invention is advantageously a cosmetic composition, and preferably a hair composition, such as a shampoo, conditioner, mask or any other conventional galenic product in the hair care field.

[0127] The composition may be in liquid form, thickened or not, cream, paste or in solid form such as a powder or film. Cosmetic treatment process

[0128] The present invention also relates to a cosmetic treatment process for keratinous materials, in particular keratinous fibers, preferably human, such as hair, comprising: (a) an application step on said keratinous materials of one or more photodimerizable polymers (P), as defined above, (b) followed by a possible drying step of said keratinous materials, for example by means of a hairdryer, (c) followed by a step of exposing said keratinous materials to natural or artificial light radiation, preferably artificial.

[0129] Preferably, the photodimerizable polymer(s) (P) used in the process of the invention are incorporated into a composition as defined above. According to this embodiment, the process of the invention comprises: (a) an application step on said keratinous materials of a composition comprising one or more photodimerizable polymers (P), as defined above, (b) followed by a possible drying step of said keratinous materials, for example by means of a hairdryer, followed by (c) followed by a step of exposing said keratinous materials to natural or artificial light radiation, preferably artificial.

[0130] Preferably, the process of the invention includes a drying step (b) between step (a) of application of the photodimerizable polymer(s) and step (c) of exposure to light radiation.

[0131] The photodimerizable polymer(s) (P) or the composition implemented in the process of the invention can be applied to dry or wet keratin materials, preferably wet.

[0132] Preferably, the composition implemented in the process of the invention is applied to the keratinous materials in an amount ranging from 0.01 to 10 grams, more preferably from 0.1 to 5 grams, and even better from 0.3 and 3 grams of composition per gram of keratinous materials.

[0133] After application, the photodimer(s) (P) or the composition may optionally be left to pause on the keratin materials. In other words, after application of the photodimer(s) polymer(s) (P) or the composition, a pause time may or may not be observed before the possible drying step (b).

[0134] The application of the photodimerizable polymer(s) (P) or composition is preferably directly followed by step (b) of drying, itself followed by step (c) of exposing the keratin materials to natural or artificial light radiation, without intermediate pause time.

[0135] According to one embodiment of the invention, the light radiation is natural.

[0136] For the purposes of this invention, "natural light radiation" means light radiation from natural daylight (generated by the sun). The duration of exposure to ambient light can range more specifically from 10 seconds to 30 minutes, in particular from 2 to 15 minutes.

[0137] According to a preferred embodiment of the invention, the light radiation is artificial, and can be continuous or non-continuous.

[0138] For the purposes of this invention, "artificial light radiation" means light radiation from an artificial source, different from natural daylight (generated by the sun). The duration of exposure to said artificial light can range from 1 second to 20 minutes, in particular from 1 second to 1 minute.

[0139] Preferably, the artificial light radiation is generated using a device selected from arc lamps such as xenon and mercury lamps, fluorescent lamps, incandescent lamps such as halogens, light-emitting diodes (LEDs), organic light-emitting diodes (LEDo), lasers.

[0140] By way of example, we can cite the goLITE BLU from Philips, the Energylight HF 3319 / 01 lamp from Philips, the Dayvia White and Messa lamps from Solvital, the Lumino Plus lamp from Lanaform, the medibeam lamp from Medibeam, the M-LED 01 lamp from Meimed, the Lifemax light pod lamp from Lifemax, the Lite-Pad lamp from Reicorp, the Omnilux Clear-U and New-U lamps from Omnilux, the 1000W Xenon Arc lamp from Lot-Oriel and the Camag Box 3 (4x8W) lamp from Camag.

[0141] The artificial light source may emit radiation in the visible range and / or radiation in the UV range. The emitted artificial light may or may not be monochromatic.

[0142] Artificial light radiation is preferably carried out at a wavelength between 280 nm and 700 nm and more preferably between 300 nm and 500 nm.

[0143] Advantageously, crosslinking is initiated by simple illumination without requiring a photoinitiator.

[0144] Preferably, the source of artificial radiation emits an energy of between 1 and 50W / cm2 of keratinous materials, the exposure times being adapted accordingly.

[0145] Crosslinking can occur with reduced light intensity; the lighting system can produce this light intensity, for example, between 500 mJ / cm2 and 10 J / cm2 of keratinous material.

[0146] The dual characteristic of the absence of a photoinitiator and of relatively low light intensity is particularly advantageous because it makes it possible to limit the harmful effects of aggressive initiators or prolonged exposure to intense light, particularly in the UV wavelengths.

[0147] A person skilled in the art will be able to adapt the characteristics of the illumination, in particular in terms of exposure time and wavelengths of radiation, with regard to the nature of the photodimerizable polymer(s) (P) used.

[0148] At the end of the process of the invention, the keratin materials can optionally be washed with shampoo or rinsed with water. They can also be dried, for example with a hairdryer, or left to dry.

[0149] For the purposes of this invention, "keratinous materials" preferably refers to human keratinous materials such as skin, nails, lips, eyelashes, eyebrows, and hair. More specifically, keratinous materials are keratinous fibers, preferably human, and even better, hair.

[0150] The following examples serve to illustrate the invention without, however, being limiting in nature. Examples

[0151] Example I: Synthesis of a photocurable mPEG-PVA-SbO polymer according to the invention A photocrosslinkable mPEG-PVA-SbQ polymer according to the invention (formula below) was synthesized according to the following protocol: synthesis of the PVA-SbQ polymer followed by a step of grafting the PEG groups.

[0152] 1st-step: synthesis of the PVA-SbQ polymer according to the publication: Synthesis of hydro-phobised and photo crosslinkable pre polymer based on poly-vinyl-alcohol in Reactive & functional polymer, 1995, 28, 55-60.

[0153] The PVA-SbQ polymer was synthesized according to the following synthesis reaction

[0154] The quantities of the reaction compounds used in this synthesis are expressed (in grams) in the table below: [Tables2] Solutions Compounds Quantity (g) PVA solution PVA, Mowiol 4-98 115.42 H3PO4, 85% 23.26 h2o 2242 SbQ-4 solution SbQ-4 29.20 h2o 115.50

[0155] 115.42g of polyvinyl alcohol (PVA, Mowiol 4-98) were dissolved in 2242 g of water were stirred at 90°C (80 rpm). The reaction mixture was then cooled to 20°C and left to stir overnight. 23.26 g of 85% phosphoric acid were then slowly added to the mixture. Finally, a light shield (aluminum foil) was placed around the reactor.

[0156] In parallel, 29.20 g of SbQ-4 were dissolved in 115.5 g of water protected from light, before being added to the reaction medium (i.e., the solution of PVA above). The medium was then left under agitation (100rpm) for 5 days, protected from light.

[0157] After 3 days, a sample (15 g) of the reaction medium was taken and precipitated in 120 g of acetone. The resulting yellow solid was then washed 4 times with acetone before being dried under vacuum. NMR analysis confirmed that the product obtained corresponded to the desired PVA-SbQ polymer.

[0158] The remainder of the reaction medium was used for the 2nd step below, without prior purification.

[0159] 2nd step: grafting of PEG groups

[0160] The mPEG-PVA-SbQ polymer was synthesized according to the following synthesis reaction

[0161] The quantities of the reaction compounds used in this synthesis are expressed (in grams) in the table below: [Tables3] Quantity (g) PVA-SbQ polymer synthesized in the first step 1499.72 mPEG5K propionaldehyde 120.93 H3PO4, 85% 5.20 h2o 514.30

[0162] 120.93g of mPEG5K propionaldehyde were dissolved in water and acid phosphoric, protected from light. The solution was heated to 50°C for 1 hour before being cooled to room temperature and degassed.

[0163] The previously obtained PVA-SbQ was then added to the mixture, under stirring (300 rpm) and protected from light. After 7 days, 10 mL of the reaction medium was precipitated in 50 mL of an 80 / 20 MEK / acetone mixture. The resulting solid was then dissolved in 15 mL of methanol before being precipitated again in 32 mL of the 80 / 20 MEK / acetone mixture.

[0164] The solid product thus obtained was dried under vacuum at room temperature to obtain the desired mPEG-PVA-SbQ polymer.

[0165] Example II: Evaluation of detangling properties

[0166] a. Preparation of formulas Formula A according to the present invention and comparative formulas B1 and B2 were prepared from ingredients mentioned in the table below, expressed as a percentage of active material. [Tables 4] A (invention) B1 (comparative) B2 (comparative) mPEG-PVA-SbQ (obtained in Example I) 6% - - PVA-SbQ - 6% - Propyl-PVA-SbQ - - 6% Distilled water qsp 100% qsp 100% qsp 100%

[0167] b. Protocol The resulting formulas A, B1, and B2 were applied to 2.5g and 27cm long strands of sensitized (SA20) and damp hair at a rate of 0.5g of formula per gram of hair. Each strand was then blow-dried using a 30cm diameter round brush and a hairdryer.

[0168] During the blow-drying, the tangential force at the passage of the brush was measured for each of the strands using a Lloyd machine (measuring machine from AMETEK LSI) for 30 seconds.

[0169] c. Results The sums of the tensile forces measured over 30 seconds for each of the wicks are expressed in the table below. [Tables 5] Force (N) measured at t0 Force (N) measured after 5 shampoos A (invention) 479 633 B1 (comparative) 1453 1266 B2 (comparative) 1208 1094 Control - sensitized but untreated strand 2015 -

[0170] The results obtained above show that hair treated with the formula of the invention, comprising a photodimerizable polymer (P) comprising at least one polyoxyalkylated pendant group (mPEG-PVA-SbQ), exhibits better detangling properties are superior to those of hair treated with comparative formulas lacking the specific polymer (P). Indeed, the resistance to brushing measured after application of formula A is significantly lower than that measured for the comparative formulas, making blow-drying much easier. Example III: Compositions according to the invention

[0171] The compositions Al and A2 according to the present invention were prepared from ingredients mentioned in the table below, expressed as a percentage by weight of active material. [Tableauxô] Al A2 f 5 6 6 Xanthan gum 1.5 2 Amino silicone blend (Wacker Belsil ADM LOG1) - 0.074 Water qsp 100% qsp 100%

[0172] The Al and A2 compositions thus obtained confer improved conditioning properties to the hair.

Claims

Demands

1. A photodimerizable polymer (P) comprising at least one photodimerizable pendant group and at least one polyoxy-alkylated pendant group; and wherein the photodimerizable pendant group(s) are selected from the following monovalent radicals of formulas (I) and (II): as well as their geometric isomers, formulas (I) and (II) in which: - Y and Z independently designate a nitrogen atom or a C(R) group with R representing a hydrogen atom or a (Ci-C4)alkyl group such as methyl; - A represents a bond or a divalent group chosen from the radicals (Ci-C8)alkylene, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio)carbonyl, (C2-C8)alkenylenes and their combinations; - B represents a monovalent group chosen from the radicals (CrC8 )alkyls, the aryl radicals, possibly cationic heteroaryl, cycloalkyl, possibly cationic heterocycloalkyl, (thio)carbonyls, (C2-C8)alkenyls and their combinations; - X represents a divalent group chosen from the radicals (C2-C8)alkylenes, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio)carbonyls, (C2-C8)alkenylenes and their combinations; - p represents an integer between 1 and 5 inclusively, in particular between 1 and 3, preferably p equals 1; represents the bond that connects the part of the radical mo novalent to the rest of the molecule; and Each of the aforementioned groups may optionally be substituted by one or more halogen atoms or groups chosen from among the (Ci-C6)alkyl, hydroxy, amino, (di)(Ci-C6)alkylamino groups, phenyl, carboxy, (Ci-C6)alkoxy, (Ci-C6)alkoxy(thio)carbonyls, hydrogeno(thio)-carbonyls, sulfonato ROS(O)2- or RS(O)2-O-, amide RR'NC(O)- or RC(O)-N(R')- or acyl RC(O)-, ammonium R'R”N+- with R, R' and R”, identical or different, representing a hydrogen atom or a (Ci-C4)alkyl group.

2. Polymer according to the preceding claim, characterized in that the photodimerizable pendant group(s) are selected from the monovalent radicals of the following compounds: - stilbene, - styrylpyridinium (stilbazolium) with the following formulas (Al) and (A2), and their geometric isomers: Al in which: - R1 and R3, identical or different, represent a halogen atom or a (Ci-C6)alkyl group; or two contiguous R1 or R3 groups together with the carbon atoms that bear it form a benzo group; - R2 represents the hydrogen atom, a (Ci-C6)alkyl group possibly substituted by one or more halogen atoms such as chlorine or hydroxy, preferably R2 represents a (Ci-C6)alkyl group such as methyl, ethyl, propyl; - q and r represent an integer between 0 and 4 inclusive; and - Q represents an anionic counter ion preferably chosen from halide ions such as chlorides, bromides, iodides, perchlorates, tetrafluoroborates, methyl sulfate, phosphates, sulfates, methanesulfonates, p-toluenesulfonate; and represents the bond that connects the part of the radical mo novalent to the rest of the molecule, it being understood that the pendant group A2 can be linked to the rest of the molecule via R2; preferably the α bond is located on the phenyl in position para of the styryl group on Al or linked to the rest of the molecule via R2 on A2; preferably the styryl group of Al and A2 is located para of the pyridinium group; - styrylazolium with the following formulas (B1 and B2) and their geometric isomers: in which: -A represents a sulfur atom, an oxygen atom, or a group NR2 or C(R2)2; and Q, r, q, R1, R2, and R3 being as defined previously, preferably the connection is located on the phenyl group in position

3. para from the group Stryryle, - styrylpyrazine, - chalcone, - (thio)cinnamate and (thio)cinnamamide, - Malimides, - (thio)coumarin, - thymine, - uracil, - butadiene, - anthracene, - pyridone, - pyrrolizinone, - acridizinium salts, - furanone, - phenylbenzoxazole, and - their derivatives. A polymer according to any one of the preceding claims, characterized in that the polyoxyalkylated pendant group(s) comprise one or more polyoxyalkylated groups selected from the groups of the following formula: -[OX]n-OR in which, X represents an alkylene group having from 2 to 3 carbon atoms, preferably 2 carbon atoms, n denotes an integer from 10 to 1000, preferably from 20 to 200, and more preferably from 25 to 150 and R represents an alkyl chain, linear or branched, having from 1 to 6 carbon atoms.

4. Polymer according to any one of the preceding claims, characterized in that it has a natural or synthetic skeleton selected from polysaccharides, poly(vinyl) polymers and polydiorgano-siloxanes, preferably from polyvinyl alcohols and poly(vinyl acetate), preferably partially hydrolyzed.

5. Polymer according to any one of the preceding claims, characterized in that the total amount of the photodimerizable pendant group(s) ranges from 0.5 to 6 mol%, and preferably from 1 to 5 mol%, relative to the total molar weight of the polymer.

6. Polymer according to any one of the preceding claims, characterized in that the total amount of the polyoxyalkylated pendant group(s) ranges from 0.1 to 5 mol%, and preferably from 0.5 to 3 mol%, relative to the total molar weight of the polymer.

7. Composition comprising one or more photodimerizable polymers (P) as defined according to any one of the preceding claims.

8. Composition according to the preceding claim, characterized in that the total quantity of the photodimerizable polymer(s) (P) ranges from 0.01 to 50% by weight, preferably from 0.1 to 25% by weight and even better from 1 to 20% by weight, relative to the total weight of the composition.

9. Composition according to claim 7 or 8 characterized in that it further comprises water, preferably in a total content greater than or equal to 30% by weight, more preferably greater than or equal to 40% by weight, and even better greater than or equal to 50% by weight, relative to the total weight of the composition.

10. A cosmetic treatment process for keratinous materials, in particular keratinous fibers, preferably human, such as hair, comprising: (a) a step of applying one or more photodimerizable polymers (P) to said keratinous materials, as defined according to any one of claims 1 to 6, (b) followed by a possible drying step, (c) followed by a step of exposing said keratinous materials to natural or artificial light radiation.

11. A method according to claim 10, characterized in that the light radiation is artificial, preferably the artificial light radiation is carried out at a wavelength between 280 nm and 700 nm and more preferably between 300 nm and 500 nm.