PROCESS FOR TREATING KERATIN MATERIALS USING A FLAVIN DERIVATIVE, A POLYMERIZABLE MOLECULE AND LIGHT RADIATION

Abstract

The present invention relates to a process for treating keratin materials, especially human keratin fibers, comprising the application of a composition comprising i) at least one flavin derivative and ii) at least one polymerizable molecule, preferably a photopolymerizable molecule, and at least one step of exposing said materials to artificial or natural light radiation, in particular for caring for and/or repairing the keratin materials.

Claims

1-20. (canceled)

21. A method for treating keratin materials, wherein the method comprises: 1) applying to the keratin materials a composition (A) or a composition (B), wherein the composition (A) comprises i) at least one flavin derivative and ii) at least one polymerizable molecule, and the composition (B) is obtained by exposing the composition (A) to at least one artificial or natural light radiation; and 2) supplying energy to the keratin materials by exposing the keratin materials to at least one artificial or natural light radiation; wherein the at least one flavin derivative is chosen from compounds of formula (I) below: ##STR00033## organic or mineral acid or base salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof; wherein in formula (I): R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which may be identical or different, are chosen from a hydrogen atom, a halogen atom, or a group chosen from hydroxyl, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkylthio, (di)(C.sub.1-C.sub.6)(alkyl)amino, or nitro(so); R.sup.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.8)alkyl group optionally substituted with a group chosen from i) hydroxyl, ii) R.sup.6—C(Y″)—O—, wherein R.sup.6 is chosen from a hydrogen atom, a (C.sub.1-C.sub.4)alkyl group, or an aryl(C.sub.1-C.sub.4)alkyl group, and Y″ is chosen from an oxygen atom, a sulfur atom, or N(R.sup.7), wherein R.sup.7 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, iii) phosphoric (HO).sub.2P(O)—O—, iv) —O—[(HO)P(O)—O].sub.n-Suc-Het, wherein Suc is chosen from a divalent sugar group, and Het is chosen from a heteroaryl group, and n is an integer equal to 0, 1 or 2; X is chosen from a nitrogen atom or a methylene group C(R.sup.8), wherein R.sup.8 is chosen from a hydrogen atom or a (C1-C4)alkyl group; X′ is chosen from an oxygen atom or a group NR.sup.9, wherein R.sup.9 is chosen from a hydrogen atom or a (C1-C6)alkyl group; and Y and Y′, which may be identical or different, are chosen from an oxygen atom, a sulfur atom, or a group NR.sup.10, wherein R.sup.10 is chosen from a hydrogen atom or a (C1-C6)alkyl group; wherein steps 1) and 2) are performed simultaneously or step 2) is performed subsequently after step 1); and wherein the at least one polymerizable molecule comprises at least one unsaturated group.

22. The method of claim 21, wherein in formula (I), R.sup.1 and R.sup.4 are chosen from a hydrogen atom and R.sup.2 and R.sup.3 are chosen from a (C.sub.1-C.sub.4)alkyl group.

23. The method of claim 21, wherein in formula (I), R.sup.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group.

24. The method of claim 21, wherein in formula (I), R.sup.5 is chosen from a (C.sub.1-C.sub.6)alkyl group substituted with at least one group, which may be identical or different, chosen from i) hydroxyl, ii) R.sup.6—C(O)—O—, with R.sup.6 being chosen from a hydrogen atom, or a (C.sub.1-C.sub.4)alkyl group, iii) phosphoric (HO).sub.2P(O)—O—, iv) —O—[(HO)P(O)—O].sub.n-Suc-Het, wherein Suc is chosen from a monosaccharide and Het is chosen from an optionally substituted heteroaryl group, and n is an integer equal to 1 or 2.

25. The method of claim 21, wherein in formula (I), taken together or separately, X is a nitrogen atom; X′ is chosen from a group NR.sup.9 with R.sup.9 being chosen from a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group; and Y and Y′ are identical and chosen from an oxygen atom or a sulfur atom.

26. The method of claim 21, wherein at least one compound of the compounds of formula (I) is chosen from compounds 1 to 7 below: (2R,3S,4S)-5-(7,8-dimethyl-2,4-dioxo-3,4 dihydrobenzo[g]pteridin-10(2H)-yl)-2,3,4-trihydroxypentyl dihydrogen phosphate or riboflavin-5′-phosphate (compound 1); 7,8-dimethyl-10-((2R,3R,4S)-2,3,4,5-tetrahydroxypentyl)benzo[g]pteridine-2,4-(3H,10H)-dione, or vitamin B2, lactoflavin (compound 2); Flavin adenine dinucleotide (FAD) (compound 3); 7,8-dimethylbenzo[g]pteridine-2,4(3H,10H)-dione (compound 4); 7,8,10-trimethylbenzo[g]pteridine-2,4(3H,10H)-dione (compound 5); Riboflavin tetrabutyrate (compound 6); or 10-methylbenzo[g]pteridine-2,4(3H,10H)-dione (compound 7); TABLE-US-00007 Structure 1 2 3 4 5 6 7 organic or mineral acid or base salts thereof, optical isomers thereof, tautomers thereof, or solvates thereof.

27. The method of claim 21, wherein the at least one polymerizable molecule has a molecular weight of less than or equal to 500 g/mol.

28. The method of claim 21, wherein the at least one polymerizable molecule comprises a photopolymerizable molecule.

29. The method of claim 21, wherein the at least one polymerizable molecule is chosen from compounds of formula (II) below: ##STR00041## organic or mineral acid or base salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof; wherein in formula (II): R.sub.1 and R.sub.2, which may be identical or different, are chosen from a hydrogen atom, a (C.sub.1-C.sub.8)alkyl group, or a (C.sub.2-C.sub.8)alkenyl group, wherein the (C.sub.1-C.sub.8)alkyl and the (C.sub.2-C.sub.8)alkenyl groups are: optionally interrupted with at least one heteroatom chosen from O, S, or N(R.sub.5), wherein R.sub.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, and/or optionally substituted with at least one radical chosen from the following radicals: hydroxyl, (di)(C.sub.1-C.sub.4)(alkyl)amino, (C.sub.1-C.sub.4)alkoxy, or C(Y′.sub.1)—Y′.sub.2—R′.sub.4; R.sub.3 is chosen from a hydrogen atom, a (C.sub.1-C.sub.8)alkyl group, a (C.sub.2-C.sub.8)alkenyl group, or a group of —C(Y′.sub.1)—Y′.sub.2—R′.sub.4; Y.sub.1, Y.sub.2, Y′.sub.1 and Y′.sub.2, which may be identical or different, are chosen from an oxygen atom, a sulfur atom, or N(R.sub.5), wherein R.sub.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; and R.sub.4 and R′.sub.4, which may be identical or different, are chosen from a hydrogen atom or a (C.sub.1-C.sub.16)alkyl group optionally substituted with at least one radical, which may be identical or different, chosen from the following radicals: a) amino (NH.sub.2), or mono- or di(C.sub.1-C.sub.4)alkylamino, b) hydroxyl (OH), c) SO.sub.3H, d) carboxyl (CO.sub.2H), e) cyano, f) (poly)(halo)(C.sub.1-C.sub.4)alkyl, g) (C.sub.1-C.sub.4)alkoxycarbonyl; wherein the alkyl radical is optionally interrupted with at least one heteroatom; Z is a radical R.sub.4 or a radical (Z′) of formula: ##STR00042## wherein in formula (Z′): Y.sub.1a, Y.sub.2a, R.sub.1a, R.sub.2a and R.sub.3a have, respectively and independently, the same meanings as that of Y.sub.1, Y.sub.2, R.sub.1, R.sub.2 and R.sub.3; alk is a divalent (C.sub.1-C.sub.16)alkylene radical optionally interrupted with an oxygen atom or a sulfur atom, or with an NH group, the divalent (C.sub.1-C.sub.16)alkylene radical being optionally substituted with at least one radical chosen from hydroxyl or a radical of formula (Z″): ##STR00043## wherein in formula (Z″): Y.sub.1b, Y.sub.2b, Y.sub.2c, R.sub.1b, R.sub.2b and R.sub.3b have, respectively and independently, the same meanings as that of Y.sub.1, Y.sub.2, R.sub.1, R.sub.2 and R.sub.3; ALK is a (C.sub.1-C.sub.6)alkylene radical (divalent radical); and p is equal to 0 or 1; ##STR00044## in formula (Z′), the symbol represents the point of attachment between alk and Y.sub.2; and ##STR00045## in formula (Z″), the symbol represents the point of attachment between (Y.sub.2)p and ALK.

30. The method of claim 29, wherein R.sub.1 is chosen from a hydrogen atom, a (C.sub.1-C.sub.4)alkyl group, or a (C.sub.1-C.sub.4)alkyl group substituted with a radical chosen from hydroxyl or a —C(Y′.sub.1)—Y′.sub.2—R′.sub.4 group.

31. The method of claim 21, wherein the at least one polymerizable molecule is chosen from compounds of formula (IIa) below: ##STR00046## organic or mineral acid or base salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or the solvates thereof; wherein in formula (IIa): R.sub.1 is chosen from a hydrogen atom, a (C.sub.1-C.sub.8)alkyl group, or a (C.sub.2-C.sub.8)alkenyl group, wherein the (C.sub.1-C.sub.8)alkyl and the (C.sub.2-C.sub.8)alkenyl groups are: optionally interrupted with a heteroatom chosen from O, S, or N(R.sub.5), wherein R.sub.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; and/or optionally substituted with a radical chosen from the following radicals: hydroxyl, (di)(C.sub.1-C.sub.4)(alkyl)amino, (C.sub.1-C.sub.4)alkoxy, or —C(Y′.sub.1)—Y′.sub.2—R′.sub.4; R.sub.3 is chosen from a hydrogen atom, a (C.sub.1-C.sub.8)alkyl group, a (C.sub.2-C.sub.8)alkenyl group, or a —C(Y′.sub.1)—Y′.sub.2-1=1′4 group; Y′.sub.1 and Y′.sub.2, which may be identical or different, are chosen from an oxygen atom, a sulfur atom, or N(R.sub.5), wherein R.sub.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; and R.sub.4 and R′.sub.4, which may be identical or different, are chosen from a hydrogen atom or a (C.sub.1-C.sub.16)alkyl group optionally substituted with at least one radical, which may be identical or different, chosen from the following radicals: a) amino (NH.sub.2), or mono- or di(C.sub.1-C.sub.4)alkylamino, b) hydroxyl (OH), c) SO.sub.3H, d) carboxyl (CO.sub.2H), e) cyano, f) (poly)(halo)(C.sub.1-C.sub.4)alkyl, or g) (C.sub.1-C.sub.4)alkoxycarbonyl; wherein the alkyl radical is optionally interrupted with at least one heteroatom.

32. The method of claim 21, wherein the at least one polymerizable molecule is chosen from compounds of formula (IIb) below: ##STR00047## organic or mineral acid or base salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof; wherein in formula (IIb), R.sub.1 and R.sub.2, which may be identical or different, are chosen from hydrogen or (C.sub.1-C.sub.4)alkyl.

33. The method of claim 21, wherein the at least one polymerizable molecule is chosen from compounds of formula (IIc) below: ##STR00048## organic or mineral acid or base salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof; wherein in formula (IIc), R.sub.1, R.sub.2, R.sub.3, Y.sub.1, Y.sub.2, alk, Y.sub.2a, Y.sub.1a, R.sub.1a, R.sub.2a, and R.sub.3a are as defined for formula (II), such that R.sub.1═R.sub.1a, R.sub.2═R.sub.2a, R.sub.3═R.sub.3a, Y.sub.1═Y.sub.1a, and Y.sub.2═Y.sub.2a, wherein: R.sub.1 and R.sub.2 are chosen from a hydrogen atom, a (C.sub.1-C.sub.8)alkyl group, or a (C.sub.2-C.sub.8)alkenyl group, wherein the (C.sub.1-C.sub.8)alkyl group or the (C.sub.2-C.sub.8)alkenyl group is: optionally interrupted with at least one heteroatom chosen from O, S, or N(R.sub.5), wherein R.sub.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, and/or optionally substituted with at least one radical chosen from the following radicals: hydroxyl, (di)(C.sub.1-C.sub.4)(alkyl)amino, (C.sub.1-C.sub.4)alkoxy or —C(Y′.sub.1)—Y′.sub.2—R′.sub.4, R.sub.3 and Ria are chosen from a hydrogen atom, a (C.sub.1-C.sub.8)alkyl group, a (C.sub.2-C.sub.8)alkenyl group, or a —C(Y′.sub.1)—Y′.sub.2—R′.sub.4 group; Y.sub.1, Y.sub.2, Y′.sub.1 and Y′.sub.2 are chosen from an oxygen atom, a sulfur atom, or N(R.sub.5), wherein R.sub.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; and alk is a divalent (C.sub.1-C.sub.16)alkylene radical optionally interrupted with at least one oxygen atom, a sulfur atom, or an NH group, wherein the divalent (C.sub.1-C.sub.16)alkylene radical is optionally substituted with at least one radical chosen from hydroxyl or a radical of formula (Z″): and ##STR00049## wherein in formula (Z″): Y.sub.1b, Y.sub.2b, Y.sub.2c, R.sub.1b, R.sub.2b and R.sub.3b have, respectively and independently, the same meanings as that of Y.sub.1, Y.sub.2, R.sub.1, R.sub.2 and R.sub.3; ALK is a (C.sub.1-C.sub.6)alkylene radical (divalent radical); and p is equal to 0 or 1.

34. The method of claim 21, wherein the at least one polymerizable molecule is chosen from compounds (a) to (d) below: ##STR00050##

35. The method of claim 21, wherein: the at least one compound of formula (I) is present in an amount ranging from 0.01% to 30% by weight, relative to the total weight of composition (A) or the composition (B), and/or the at least one polymerizable molecule is present in an amount ranging from 0.01% to 50% by weight, relative to a total weight of the composition (A) or the composition (B).

36. The method of claim 21, wherein the composition (A) or the composition (B) comprises at least one amine other than i) the flavin of formula (I), and other than ii) the at least one polymerizable molecule; wherein the at least one amine is chosen from aromatic, non-aromatic, saturated, unsaturated, oligomeric, polymeric, natural, or synthetic amines.

37. The method of claim 36, wherein the at least one amine is an amino acid chosen from compounds of formula (III) below: ##STR00051## organic or mineral acid or base salts thereof, optical isomers thereof, geometrical isomers thereof, tautomers thereof, or solvates thereof; wherein in formula (III): R.sub.A is chosen from a hydrogen atom, a (C.sub.1-C.sub.4)alkyl group, or (C.sub.1-C.sub.4)alkylcarbonyl group, forming, together with the radical R.sub.B, the nitrogen, and carbon atom that bear R.sub.A, R.sub.B and the nitrogen, respectively, a 5- to 10-membered monocyclic or bicyclic heterocycle; and R.sub.B is chosen from a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group optionally substituted with at least one group chosen from i) —Z—C(Z′)—Z″—R.sub.C, wherein Z, Z′, or Z″, which may be identical or different, are chosen from an oxygen atom, a sulfur atom, or N(R.sub.D), wherein R.sub.C and R.sub.D, which may be identical or different, are chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; ii) (hetero)aryl; iii) (di)(C.sub.1-C.sub.4)(alkyl)amino; iv) —C(Z)—Z″—R.sub.D, wherein Z′ is chosen from an oxygen atom, Z″ is chosen from an oxygen atom or a group N(R.sub.D), and R.sub.c is chosen from a hydrogen atom; v) —Z″—R.sub.C, with Z′″ being chosen from an a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group oxygen, sulfur or selenium atom, or an NH group, and with R.sub.C being chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group.

38. The method of claim 21, wherein the step of exposing the keratin materials to at least one artificial or natural light radiation comprises exposing the keratin materials to an artificial light radiation with a wavelength ranging from 360 nm to 600 nm; and wherein the artificial light radiation is generated using a device chosen from arc lamps, fluorescent lamps, incandescent lamps, light-emitting diodes (LED), organic light-emitting diodes (OLED), or lasers.

39. A method for preparing a composition (B′), wherein the method comprises: mixing the following ingredients to obtain a mixture: i) at least one compound of formula (I), ##STR00052## ii) at least one polymerizable molecule chosen from compounds of formula (II), (IIa), (IIb) or (IIc) below, ##STR00053## and iii) optionally, at least one amine and/or at least one alcohol other than i) the compounds of formula (I), and other than ii) the at least one polymerizable molecule; and exposing the mixture to an artificial or natural light radiation for at least 2 minutes; wherein in formula (I): R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which may be identical or different, are chosen from a hydrogen atom, a halogen atom, or a group chosen from hydroxyl, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkylthio, (di)(C.sub.1-C.sub.6)(alkyl)amino, nitro(so); R.sup.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.8)alkyl group optionally substituted with a group chosen from i) hydroxyl, ii) R.sup.6—C(Y″)—O—, wherein R.sup.6 is chosen from a hydrogen atom, a (C.sub.1-C.sub.4)alkyl group, or an aryl(C.sub.1-C.sub.4)alkyl group, and Y″ is chosen from an oxygen atom, a sulfur atom, or N(R.sup.7), wherein R.sup.7 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, iii) phosphoric (HO).sub.2P(O)—O—, iv) —O—[(HO)P(O)—O].sub.n-Suc-Het, wherein Suc is chosen from a divalent sugar group, and Het is chosen from a heteroaryl group, and n is an integer equal to 0, 1, or 2; X is chosen from a nitrogen atom or a methylene group C(R.sup.8), wherein R.sup.8 is chosen from a hydrogen atom or a (C1-C4)alkyl group; X′ is chosen from an oxygen atom or a group NR9, wherein R9 is chosen from a hydrogen atom or a (C1-C6)alkyl group; and Y and Y′, which may be identical or different, are chosen from an oxygen atom, a sulfur atom, or a group NR.sup.10, wherein R.sup.10 is chosen from a hydrogen atom or a (C1-C6)alkyl group; wherein in formulae (II), (IIa), (IIb) and (IIc): R.sub.1 and R.sub.2, which may be identical or different, are chosen from a hydrogen atom, a (C.sub.1-C.sub.8)alkyl group, or a (C.sub.2-C.sub.8)alkenyl group, wherein the (C.sub.1-C.sub.8)alkyl and the (C.sub.2-C.sub.8)alkenyl groups are: optionally interrupted with at least one heteroatom chosen from O, S, or N(R.sub.5), wherein R.sub.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, and/or optionally substituted with at least one radical chosen from the following radicals: hydroxyl, (di)(C.sub.1-C.sub.4)(alkyl)amino, (C.sub.1-C.sub.4)alkoxy, or —C(Y′.sub.1)—Y′.sub.2—R′.sub.4; R.sub.3 is chosen from a hydrogen atom, a (C.sub.1-C.sub.8)alkyl group, a (C.sub.2-C.sub.8)alkenyl group, or a —C(Y′.sub.1)—Y′.sub.2—R′.sub.4 group; Y.sub.1, Y.sub.2, Y′.sub.1 and Y′.sub.2, which may be identical or different, are chosen from an oxygen atom, a sulfur atom, or N(R.sub.5), wherein R.sub.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group; and R.sub.4 and R′.sub.4, which may be identical or different, are chosen from a hydrogen atom or a (C.sub.1-C.sub.16)alkyl group optionally substituted with at least one radicals, which may be identical or different, chosen from the following radicals: a) amino (NH.sub.2), or mono- or di(C.sub.1-C.sub.4)alkylamino, b) hydroxyl (OH), c) SO.sub.3H, d) carboxyl (CO.sub.2H), e) cyano, f) (poly)(halo)(C.sub.1-C.sub.4)alkyl, g) (C.sub.1-C.sub.4)alkoxycarbonyl; wherein the alkyl radical is optionally interrupted with a heteroatom; Z is a radical R.sub.4 or a radical (Z′) of formula: ##STR00054## wherein in formula (Z′): Y.sub.1a, Y.sub.2a, R.sub.1a, R.sub.2a and R.sub.3a have, respectively and independently, the same meanings as that of Y1, Y2, R1, R2 and R3; alk is a divalent (C.sub.1-C.sub.16)alkylene radical optionally interrupted with an oxygen atom, a sulfur atom, or an NH group, the divalent (C.sub.1-C.sub.16)alkylene radical being optionally substituted with at least one radical chosen from hydroxyl or a radical of formula (Z″): ##STR00055## wherein in formula (Z″): Y.sub.1b, Y.sub.2b, Y.sub.2c, R.sub.1b, R.sub.2b and R.sub.3b have, respectively and independently, the same meanings as that of Y.sub.1, Y.sub.2, R.sub.1, R.sub.2 and R.sub.3; ALK is a (C.sub.1-C.sub.6)alkylene radical (divalent radical); and p is equal to 0 or 1; ##STR00056## in formula (Z′), the symbol represents the point of attachment between alk and Y.sub.2; and ##STR00057## in formula (Z″), the symbol represents the point of attachment between (Y.sub.2)p and ALK.

40. A multi-compartment device comprising: one or two compartments containing: a first ingredient i) comprising at least one compound of formula (I), ##STR00058## and a second ingredient ii) comprising at least one polymerizable molecule chosen from compounds of formula (II), (IIa), (IIb) or (IIc); ##STR00059## and a separate compartment comprising an artificial-light-emitting device providing an artificial light radiation with a wavelength ranging from 360 nm to 600 nm; wherein the first ingredient i) and the second ingredient ii) are contained together in one compartment or separately in two compartments; wherein in formula (I): R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which may be identical or different, are chosen from a hydrogen atom, a halogen atom, or a group chosen from hydroxyl, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkylthio, (di)(C.sub.1-C.sub.6)(alkyl)amino, nitro(so); R.sup.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.8)alkyl group optionally substituted with at least one group chosen from i) hydroxyl, ii) R.sup.6—C(Y″)—O— with R.sup.6 being chosen from a hydrogen atom, a (C.sub.1-C.sub.4)alkyl group, or an aryl(C.sub.1-C.sub.4)alkyl group, and Y″ is chosen from an oxygen atom, a sulfur atom, or N(R.sup.7), wherein R.sup.7 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, iii) phosphoric (HO).sub.2P(O)—O—, iv) —O—[(HO)P(O)—O].sub.n-Suc-Het, wherein Suc is chosen from a divalent sugar group, and Het is chosen from a heteroaryl group, n being an integer equal to 0, 1 or 2; X is chosen from a nitrogen atom or a methylene group C(R8), wherein R8 is chosen from a hydrogen atom or a (C1-C4)alkyl group; X′ is chosen from an oxygen atom or a group NR9, wherein R9 is chosen from a hydrogen atom or a (C1-C6)alkyl group; and Y and Y′, which may be identical or different, are chosen from an oxygen atom, a sulfur atom, or a group NR10, wherein R10 is chosen from a hydrogen atom or a (C1-C6)alkyl group; and in formulae (II), (IIa), (IIb) and (IIc): R.sub.1 and R.sub.2, which may be identical or different, are chosen from a hydrogen atom, a (C.sub.1-C.sub.8)alkyl group, or a (C.sub.2-C.sub.8)alkenyl group, wherein the (C.sub.1-C.sub.8)alkyl and the (C.sub.2-C.sub.8)alkenyl groups are: optionally interrupted with at least one heteroatom chosen from 0, S, or N(R.sub.5), wherein R.sub.5 is chosen from a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group, and/or optionally substituted with at least one radical chosen from the following radicals: hydroxyl, (di)(C.sub.1-C.sub.4)(alkyl)amino, (C.sub.1-C.sub.4)alkoxy or —C(Y′.sub.1)—Y′.sub.2—R′.sub.4; R3 is chosen from a hydrogen atom, a (C1-C8)alkyl group, a (C2-C8)alkenyl group, or a —C(Y′1)—Y′2—R′4 group; Y1, Y2, Y′1 and Y′2, which may be identical or different, are chosen from an oxygen atom, a sulfur atom, or N(R5), wherein R5 is chosen from a hydrogen atom or a (C1-C4)alkyl group; and R4 and R′4, which may be identical or different, are chosen from a hydrogen atom or a (C.sub.1-C.sub.16)alkyl group optionally substituted with at least one radical, which may be identical or different, chosen from the following radicals: a) amino (NH.sub.2), or mono- or di(C.sub.1-C.sub.4)alkylamino, b) hydroxyl (OH), c) SO.sub.3H, d) carboxyl (CO.sub.2H), e) cyano, f) (poly)(halo)(C.sub.1-C.sub.4)alkyl, or g) (C.sub.1-C.sub.4)alkoxycarbonyl; wherein the alkyl radical is optionally interrupted with at least one heteroatom; Z is chosen from a radical R.sub.4 or a radical (Z′) of formula: ##STR00060## wherein in formula (Z′): Y1a, Y2a, R1a, R2a and R3a have, respectively and independently, the same meanings as that of Y1, Y2, R1, R2 and R3; alk is a divalent (C.sub.1-C.sub.16)alkylene radical optionally interrupted with an oxygen atom, a sulfur atom, or an NH group, wherein the divalent (C.sub.1-C.sub.16)alkylene radical is optionally substituted with one or more radicals chosen from hydroxyl or a radical of formula (Z″): ##STR00061## wherein in formula (Z″): Y.sub.1b, Y.sub.2b, Y.sub.2c, R.sub.1b, R.sub.2b and R.sub.3b have, respectively and independently, the same meanings as that of Y.sub.1, Y.sub.2, R.sub.1, R.sub.2 and R.sub.3, ALK is a (C.sub.1-C.sub.6)alkylene radical (divalent radical), and p is equal to 0 or 1; ##STR00062## in formula (Z′), the symbol represents the point of attachment between alk and Y.sub.2; and ##STR00063## in formula (Z″), the symbol represents the point of attachment between (Y.sub.2)p and ALK.

Description

EXAMPLES

[0285] The process according to the invention makes it possible to obtain polymeric compounds which may be generated in keratin fibers or else externally to keratin fibers and then applied to said fibers.

Example 1

[0286] Preparation of a Composition (B) or (B′) Intended to be Applied to Keratin Fibers:

[0287] An aqueous composition constituted of sodium riboflavin 5′-monophosphate hydrate (3 g %), L-arginine (3 g %), itaconic acid (38 g %) and water (pH adjusted to 7 with NaOH) was irradiated with a 1000 W xenon arc lamp for 3 hours to create a polymer composition (B), which was then applied to the fiber.

Example 2

[0288] The following compositions were prepared according to the following table:

TABLE-US-00002 g % ingredients Sodium salt of riboflavin 5′- monophosphate Itaconic Locks* hydrate L-arginine acid Irradiation  1 — — — — NO (comparative)  2 — — — — YES (comparative)  3 3 — — — NO (comparative)  4 — 3 — — NO (comparative)  5 — — — 40 NO (comparative)  6 3 — — — YES (comparative)  7 — 3 — — YES (comparative)  8 — — — 40 YES (comparative)  9 3 3 — — NO (comparative) 10 3 — — 40 NO (comparative) 11 — 3 — 40 NO (comparative) 12 3 3 — — YES (comparative) 13 — 3 — 40 YES (comparatif) 14 3 — — 40 YES (invention) 15 3 3 — 40 NO (comparative) 16 3 3 — 40 YES (invention) 17 — — 1 — NO (comparative) 18 — — 1 — YES (comparative) 19 0.1 0.1 1 — YES (invention) *The locks numbered 1 to 19 are made using locks of damaged hair (bleached hair). The word “NO” implies that the processes were performed without natural daylight and without artificial light.

Preparation of the Samples

[0289] 2.7 g of locks of 20 cm SA20 bleached hair, which were washed and dried beforehand, were used. 1.5 g of each formula were applied for each gram of dry hair. The samples were left on for 15 minutes, wrapped in a thin transparent plastic film. The film was removed and the hair was irradiated using a 1000 W xenon arc lamp for 15 minutes, and then rinsed with excess water at 37° C., combed and dried under a hood at 60° C. for 10 minutes. The placebo samples were prepared in an identical manner, except that the sample was covered with aluminum foil instead of transparent film (to protect it from irradiation). After drying, the samples were combed (comb passed through five times) and then left suspended vertically.

Test Method

[0290] Effect of a Ponytail

[0291] The more the hair is damaged, the more the folding of the sample remains marked on the hair after the stress has been removed.

[0292] The locks were folded in two (the root toward the end of the hair) and fixed using an elastic band so as to make a loop of about 3 cm, i.e. the length of the loop is 3 cm or, in other words, the elastic band is 3 cm from the bottom of the loop. The looped locks were suspended with the loop at the bottom in a glove box at 80% RH and 26° C. for 2 hours. The locks were removed from the glove box, the elastic band was removed and the locks were suspended vertically. The fold angle was measured according to the reporter's principle (see FIG. 1) immediately after removing the elastic band (initial angle) and then at the end of the study (final angle after 14 hours).

[0293] Results

[0294] Angle reduction=final angle−initial angle

[0295] The greater the angle reduction, the more the fold imprint disappears and the more longitudinal the lock.

TABLE-US-00003 Initial angle (°) Final angle (°) Angle reduction  1 130 140 10 (comparative)  2 140 150 10 (comparative)  3 130 130  0 (comparative)  4 130 140 10 (comparative)  5 130 140 10 (comparative)  6 130 140 10 (comparative)  7 130 130  0 (comparative)  8 120 130 10 (comparative)  9 130 140 10 (comparative) 10 130 140 10 (comparative) 11 130 150 20 (comparative) 12 120 130 10 (comparative) 13 130 140 10 (comparative) 14 140 170 30 (invention) 15 130 140 10 (comparative) 16 140 180* 40* (invention) 17 130 140 10 (comparative) 18 130 140 10 (comparative) 19 140 170 30 (invention) *Maximum relaxation (no fold present)

[0296] After removing the elastic band, the locks numbered 14, 16 and 19 (present invention) show a better return longitudinal shape, i.e. the fold imprint is no longer visible on these locks. This is not the case for the other comparative locks (1 to 13 and 15, 17 and 18). In addition, it is seen that the damaged locks treated via the process of the invention are perceived as being identical to a natural lock, indicating that the process of the invention has repaired the damaged hair.

Example 3

[0297] Comparative Study (Vs. WO2016/126121)
The use of the same yeast (Saccharomyces cerevisiae) as described in WO2016/126121 is not possible since the details of the supplier are not given neither any procedure to prepare the yeast nor the extraction procedure of the riboflavin. After a literature search it was concluded that the concentration of riboflavin in S. cerevisiae is between 0.8-1.5 μM. Thus the higher concentration of 1.5 μM has been used to do the comparative study. Therefore, a composition comprising 20% by weight of S. cerevisiae comprises an equivalent quantity of riboflavin of 1.13 g×10.sup.−4% by weight. A particular reference for the cytosolic concentration of riboflavin in S. cerevisiae is Biosynthesis of Vitamin B2 (Riboflavin), Annual Review of Nutrition, Vol. 20:153-167 (Volume publication date July 2000)-https://doi.org/10.1146/annurev.nutr.20.1.153
In this study, pentaerythritol tetraacrylate has been used as a polymerizable molecule:

##STR00032##

The following formulations were prepared. The ingredients were mixed, stirred for one hour in an closed amber vial before use.

TABLE-US-00004 Qsp 5% Penta- Triton Formu- erythritol X-100.sup.5 lation tetra- Benzo- in Number Riboflavin.sup.1 acrylate.sup.2 Urea.sup.3 phenone.sup.4 EtOH Water 1 1 g 5 g — — 50 g 100 g 2 1 g — 0.5 g 0.5 g 50 g 100 g 3 1.13 × 10.sup.−4 g — 0.5 g 0.5 g 50 g 100 g .sup.1Sigma-Aldrich - Ref. R7649 .sup.2Sigma-Aldrich - Ref. 408263 .sup.3Sigma-Aldrich - Ref. U4884 .sup.4BASF- Ref. Uvinul 40 .sup.5Sigma-Aldrich - Ref. X-100

Preparation of Hair Swatches

[0298]

TABLE-US-00005 Formulation Example number Irradiation 1 (Invention) 1 Natural light 2 (Invention) 1 Artificial light 3 (Comparative) 2 Natural light 4 (Comparative) 2 Artificial light 5 (Comparative) 3 Natural light 6 (Comparative) 3 Artificial light
The hair swatches (2.7 g, 27 cm length) were placed on a piece of aluminium foil. 5.4 g of each formulation was applied onto each hair swatch. The swatches were covered with a transparent plastic film to reduce evaporation. Examples 1, 3, and 5 were exposed to natural light for 60 minutes. After 30 of the 60 minutes the swatches were turned over to ensure each side of the swatches was exposed to at least 30 minutes of natural light. The irradiance of natural light was measured at 64 microW/cm.sup.2 using a Thor PM100D Optical Power Meter.
Examples 2, 4 and 6 were irradiated with a home-made array of LED lights emitting light at 450 nm for 60 minutes. The array of LEDs were positioned 5 cm above the swatch and the irradiance measured at 26 mW/cm.sup.2). After 30 of the 60 minutes the swatches were turned over to ensure each side of the swatches was irradiated to at least 30 minutes.
After exposure to the light all the swatches were suspended vertically, covered with a towel and left to dry.

Shampooing

[0299] The swatches were subjected to 5 repeat washes. Washing consisted of placing the swatch in a bath containing 100 mL of 3% sodium lauryl ether sulfate (SLES) for 1 minute then rinsing for 10 seconds under tap water. The process is repeated 4 times using fresh SLES solution each time. At the end of the fifth wash and rinse the swatches were dried in a professional helmet hairdryer at 60° C.

Hair Repair Test—Repeat Combing (Anti Breakage)

[0300] The swatches were suspended vertically and combed 30 times with a fine toothed comb at a speed of 30 cm/sec. The amount of broken hair was collected and weighed. The lower the weight of hair collected the better the formulation is at reducing the breakage of hair i.e. repairing the hair.

Results

[0301]

TABLE-US-00006 Amount of Example broken hair (g) 1 (Invention) 0.0813 2 (Invention) 0.0532 3 (Comparative) 0.1336 4 (Comparative) 0.1174 5 (Comparative) 0.1683 6 (Comparative) 0.1749
The results show that hair treated according to Examples 1 and 2 with 1% riboflavin and pentaerythritol tetraacrylate have been repaired since there is less hair breakage during the repeated combing. Example 2 using the LED array gave better results than natural light.