PROCESS FOR TREATING KERATIN FIBRES WITH A PHOTOCROSSLINKABLE POLYVINYL ALCOHOL

Abstract

The invention relates to a cosmetic process for treating keratin fibres, comprising: (i) a step of applying to the keratin fibres a cosmetic composition containing a polyvinyl alcohol polymer comprising:an alcohol unitoptionally an acetate unita photocrosslinkable unita hydrophobic unit; (ii) a step of irradiating the composition on the keratin fibres to crosslink said polymer. The invention also relates to the novel polyvinyl alcohol polymer used in said process. The treated keratin fibres have good cosmetic properties in terms of a soft feel and disentangling, which properties are persistent after one or more shampoo washes.

Claims

1-31. (canceled)

32. A cosmetic process for treating keratin fibres, comprising: (i) a step of applying to the keratin fibres a cosmetic composition comprising at least one polyvinyl alcohol polymer; (ii) a step of irradiating the composition on the keratin fibres to crosslink said polymer; steps (i) and (ii) being performed at the same time or in the order of step (i) followed by step (ii); wherein the at least one polyvinyl alcohol polymer comprises: a) at least one alcohol unit of formula (I) ##STR00027## b) optionally at least one acetate unit of formula (II) ##STR00028## c) at least one photocrosslinkable unit of formula (P) ##STR00029## wherein * represents a bond that connects the part of the radical to the rest of the polymer, and wherein Q represents a styrylpyridinium group of formula (Q1) or (Q2) below: ##STR00030## wherein R.sup.1 and R.sup.3, which may be identical or different, represent a halogen atom or a (C.sub.1-C.sub.6)alkyl group; or alternatively two contiguous groups R.sup.1 or R.sup.3 form, together with the carbon atoms that bear them, a benzo group; R.sup.2 represents a hydrogen atom, a (C.sub.1-C.sub.6)alkyl group optionally substituted with one or more halogen atoms or hydroxyl; q and r represent an integer between 0 and 4 inclusive; and k represents an anionic counterion chosen from halide ions, perchlorates, tetrafluoroborates, methylsulfate, phosphates, sulfates, methanesulfonates, or p-toluenesulfonate; * represents a bond that connects the part of the radical to the rest of the polymer, d) and at least one hydrophobic unit of formula (H1) or (H2) ##STR00031## wherein: * represents a bond that connects the part of the radical to the rest of the polymer, A represents a monovalent aromatic group of formula (A1) or (A2) below: ##STR00032## wherein R1, R2, R3, R4 and R5, which may be identical or different, represent H, OH, ORa, SRa, CO.sub.2H, OCORb, NRcRd, a C1-C4 alkyl radical optionally interrupted with one or more heteroatoms O or S, or a divalent group N(Re), Ra representing a C1-C6 alkyl group; Rb representing a C1-C6 alkyl or benzyl group; Rc and Re representing a C1-C4 alkyl group; Rd representing H or a C1-C4 alkyl group; * represents a bond that connects the part of the radical to the rest of the polymer; n=0 or 1; wherein when n=0, then R1, R2, R3 and R4 do not all represent a hydrogen atom; X represents a divalent radical CHC(Rf)-; Rf represents H or a C1-C6 alkyl radical; R.sub.10 represents H or a phosphate group PO(OH).sub.2, D represents a divalent group of formula (D1) or (D2) below: ##STR00033## wherein R1, R2, R3 and R4, which may be identical or different, represent H, a C1-C4 alkyl radical, ora C1-C4 alkoxy radical, ##STR00034## wherein R1, R2, R3, R4, R5, R6, R7, and R8, which may be identical or different, represent H, a C1-C4 alkyl radical or a C1-C4 alkoxy radical; Y represents 0 or N(Rj)-, Rj represents a C1-C4 alkyl group; and T represents a divalent hydrocarbon-based group containing from 2 to 6 carbon atoms.

33. The process according to claim 32, wherein the polymer contains at least one hydrophobic unit of formula (H1), wherein the hydrophobic unit of formula (H1) contains a group of formula (A1) chosen from formulas (1)-(29): ##STR00035## ##STR00036## ##STR00037## ##STR00038## wherein * represents a bond that connects the part of the radical to the rest of the polymer.

34. The process according to claim 32, wherein the polymer contains at least one hydrophobic unit of formula (H2), wherein the hydrophobic unit of formula (H2) contains: a) a group of formula (D1) chosen from formulas (32)-(34): ##STR00039## or; b) a group of formula (D2) chosen from formulas (35)-(36): ##STR00040## wherein * represents a bond that connects the part of the radical to the rest of the polymer.

35. The process according to claim 32, wherein the group Q of the unit (P) represents the group: ##STR00041## wherein k represents an anionic counterion chosen from halide ions, perchlorates, tetrafluoroborates, methylsulfate, phosphate, sulfate, methanesulfonates or p-toluenesulfonate.

36. The process according to claim 32, wherein the polymer comprises at least one unit of formula (II) present in the polyvinyl alcohol in an amount ranging from 0.1 mol % to 40 mol % relative to the polymer

37. The process according to claim 32, wherein the polymer comprises a photocrosslinkable unit (P) in an amount ranging from 0.2 mol % to 10 mol % relative to the polymer.

38. The process according to claim 32, wherein the polymer comprises a hydrophobic unit (H1) and/or (H2) in an amount ranging from 0.2 mol % to 50 mol % relative to the polymer.

39. The process according to claim 32, wherein said polymer has a weight-average molecular weight ranging from 10,000 to 200,000 g/mol.

40. The process according to claim 32, wherein the polymer is present in the cosmetic composition in an amount ranging from 0.1% to 40% by weight, relative to the total weight of the composition derived from the extemporaneous mixture.

41. The process according to claim 32, wherein the irradiation is irradiation with radiation in the UVA domain.

42. A polyvinyl alcohol polymer comprising: a) at least one alcohol unit of formula (I) ##STR00042## b) optionally at least one acetate unit of formula (II) ##STR00043## c) at least one photocrosslinkable unit of formula (P) ##STR00044## wherein * represents a bond that connects the part of the radical to the rest of the polymer, and wherein Q represents a styrylpyridinium group of formula (Q1) or (Q2) below: ##STR00045## wherein R.sup.1 and R.sup.3, which may be identical or different, represent a halogen atom or a (C.sub.1-C.sub.6)alkyl group; or alternatively two contiguous groups R.sup.1 or R.sup.3 form, together with the carbon atoms that bear them, a benzo group; R.sup.2 represents a hydrogen atom, a (C.sub.1-C.sub.6)alkyl group optionally substituted with one or more halogen atoms or hydroxyl; q and r represent an integer between 0 and 4 inclusive; and X.sup. represents an anionic counterion chosen from halide ions, perchlorates, tetrafluoroborates, methylsulfate, phosphates, sulfates, methanesulfonates, or p-toluenesulfonate; * represents a bond that connects the part of the radical to the rest of the polymer, d) and at least one hydrophobic unit of formula (H1) or (H2) ##STR00046## wherein: * represents a bond that connects the part of the radical to the rest of the polymer, A represents a monovalent aromatic group of formula (A1) or (A2) below: ##STR00047## wherein R1, R2, R3, R4 and R5, which may be identical or different, represent H, OH, ORa, SRa, CO.sub.2H, OCORb, NRcRd, a C1-C4 alkyl radical optionally interrupted with one or more heteroatoms O or S, or a divalent group N(Re), Ra representing a C1-C6 alkyl group; Rb representing a C1-C6 alkyl or benzyl group; Rc and Re representing a C1-C4 alkyl group; Rd representing H or a C1-C4 alkyl group; * represents a bond that connects the part of the radical to the rest of the polymer; n=0 or 1; wherein when n=0, then R1, R2, R3 and R4 do not all represent a hydrogen atom; X represents a divalent radical CHC(Rf)-; Rf represents H or a C1-C6 alkyl radical; R.sub.10 represents H or a phosphate group PO(OH).sub.2, D represents a divalent group of formula (D1) or (D2) below: ##STR00048## wherein R1, R2, R3 and R4, which may be identical or different, represent H, a C1-C4 alkyl radical, ora C1-C4 alkoxy radical, ##STR00049## wherein R1, R2, R3, R4, R5, R6, R7, and R8, which may be identical or different, represent H, a C1-C4 alkyl radical or a C1-C4 alkoxy radical; Y represents O or N(Rj)-, Rj represents a C1-C4 alkyl group; and T represents a divalent hydrocarbon-based group containing from 2 to 6 carbon atoms.

43. The polymer according to claim 42, wherein the polymer contains at least one hydrophobic unit of formula (H1), wherein the hydrophobic unit of formula (H1) contains a group of formula (A1) chosen from formulas (1)-(29): ##STR00050## ##STR00051## ##STR00052## ##STR00053## wherein * represents a bond that connects the part of the radical to the rest of the polymer.

44. The polymer according to claim 42, wherein the polymer contains at least one hydrophobic unit of formula (H2), wherein the hydrophobic unit of formula (H2) contains: a) a group of formula (D1) chosen from formulas (32)-(34): ##STR00054## or; b) a group of formula (D2) chosen from formulas (35)-(36): ##STR00055## wherein * represents a bond that connects the part of the radical to the rest of the polymer.

45. The polymer according to claim 42, wherein the group Q of the unit (P) represents the group: ##STR00056## wherein k is an anionic counterion chosen from halide ions, perchlorates, tetrafluoroborates, methylsulfate, phosphate, sulfate, methanesulfonates, or p-toluenesulfonate.

46. The polymer according to claim 42, wherein it comprises at least one unit of formula (II) present in the polyvinyl alcohol in an amount ranging from 0.1 mol % to 40 mol % relative to the polymer.

47. The polymer according to claim 42, wherein the polymer comprises a photocrosslinkable unit (P) in an amount ranging from 0.2 mol % to 10 mol %.

48. The polymer according to claim 42, wherein the polymer comprises a hydrophobic unit (H1) or (H2) in an amount ranging from 0.2 mol % to 50 mol %, relative to the polymer.

49. The polymer according to claim 42, wherein said polymer has a weight-average molecular weight ranging from 10 000 to 200 000 g/mol.

50. The composition comprising, in a physiologically acceptable medium, a at least one polyvinyl alcohol polymer comprising: a) at least one alcohol unit of formula (I) ##STR00057## b) optionally at least one acetate unit of formula (II) ##STR00058## c) at least one photocrosslinkable unit of formula (P) ##STR00059## wherein * represents a bond that connects the part of the radical to the rest of the polymer, and wherein Q represents a styrylpyridinium group of formula (Q1) or (Q2) below: ##STR00060## wherein R.sup.1 and R.sup.3, which may be identical or different, represent a halogen atom or a (C.sub.1-C.sub.6)alkyl group; or alternatively two contiguous groups R.sup.1 or R.sup.3 form, together with the carbon atoms that bear them, a benzo group; R.sup.2 represents a hydrogen atom, a (C.sub.1-C.sub.6)alkyl group optionally substituted with one or more halogen atoms or hydroxyl; q and r represent an integer between 0 and 4 inclusive; and X.sup. represents an anionic counterion chosen from halide ions, perchlorates, tetrafluoroborates, methylsulfate, phosphates, sulfates, methanesulfonates, or p-toluenesulfonate; * represents a bond that connects the part of the radical to the rest of the polymer, d) and at least one hydrophobic unit of formula (H1) or (H2) ##STR00061## wherein: * represents a bond that connects the part of the radical to the rest of the polymer, A represents a monovalent aromatic group of formula (A1) or (A2) below: ##STR00062## wherein R1, R2, R3, R4 and R5, which may be identical or different, represent H, OH, ORa, SRa, CO.sub.2H, OCORb, NRcRd, a C1-C4 alkyl radical optionally interrupted with one or more heteroatoms O or S, or a divalent group N(Re), Ra representing a C1-C6 alkyl group; Rb representing a C1-C6 alkyl or benzyl group; Rc and Re representing a C1-C4 alkyl group; Rd representing H or a C1-C4 alkyl group; * represents a bond that connects the part of the radical to the rest of the polymer; n=0 or 1; wherein when n=0, then R1, R2, R3 and R4 do not all represent a hydrogen atom; X represents a divalent radical CHC(Rf)-; Rf represents H or a C1-C6 alkyl radical; R.sub.10 represents H or a phosphate group PO(OH).sub.2, D represents a divalent group of formula (D1) or (D2) below: ##STR00063## wherein R1, R2, R3 and R4, which may be identical or different, represent H, a C1-C4 alkyl radical, ora C1-C4 alkoxy radical, ##STR00064## wherein R1, R2, R3, R4, R5, R6, R7, and R8, which may be identical or different, represent H, a C1-C4 alkyl radical or a C1-C4 alkoxy radical; Y represents O or N(Rj)-, Rj represents a C1-C4 alkyl group; and T represents a divalent hydrocarbon-based group containing from 2 to 6 carbon atoms.

Description

EXAMPLE 1

Polyvinyl Alcohol Polymer Functionalized with SbQ and Vanillin Groups (P1)

[0124] ##STR00022##

[0125] 20 g of polyvinyl alcohol (Selvol 540 from Sekisui) and 200 ml of a solvent mixture (50/50 weight/weight water/isopropanol) were placed in a reactor. The mixture was heated at 80 C. until dissolution of the polyvinyl alcohol was complete. 5 ml of 1M HCl and 1 g of vanillin and 1 g of N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate (CA No. 74401-04-0) were then added. The reaction medium was maintained at 80 C. for 8 hours. The product was purified three times by precipitation from 600 ml of acetone. The purified product was placed in water/isopropanol aqueous-alcoholic solution (50/50 weight/weight) at 10% by weight of polymer (solution S1). The polymer obtained comprises 20% by weight of group derived from vanillin and 15% by weight of SbQ group derived from N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate.

EXAMPLE 2

Polyvinyl Alcohol Polymer Functionalized with SbQ and 3,4-dihydroxybenzaldehyde Groups (P2)

[0126] ##STR00023##

[0127] The polymer was prepared according to the procedure described in Example 1, using: 20 g of polyvinyl alcohol (Selvol 540 from Sekisui)

[0128] 1 g of 3,4-dihydroxybenzaldehyde

[0129] 1 g of N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate

[0130] Solvent: water/isopropanol (40/60 weight/weight): 200 ml

[0131] The polymer obtained comprises 18% by weight of group derived from 3,4-dihydroxybenzaldehyde and 15% by weight of SbQ group derived from N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate. After purification, the polymer was dissolved at 10% by weight in a water/isopropanol mixture (50/50 weight/weight).

[0132] A solution S2 of polymer 2 was thus obtained.

EXAMPLE 3

Polyvinyl Alcohol Polymer Functionalized with SbQ and Terephthaldehyde Groups (P3)

[0133] ##STR00024##

[0134] The polymer was prepared according to the procedure described in Example 1, using: 20 g of polyvinyl alcohol (Selvol 540 from Sekisui)

[0135] 1 g of 3,4-dihydroxybenzaldehyde

[0136] 1 g of N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate

[0137] 0.5 g of terephthaldehyde

[0138] Solvent: water/isopropanol (200/50): 250 ml

[0139] by first adding HCl and the SbQ, and maintaining the reaction mixture at 80 C. for 6 hours, followed by adding the terephthaldehyde. The formation of a hydrogel is observed.

[0140] The polymer obtained comprises 2.5% by weight (i.e. 0.8 mol %) of group derived from terephthaldehyde and 1% by weight (i.e. 0.98 mol %) of SbQ group derived from N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate.

EXAMPLE 4 (Outside the Invention)

Polyvinyl Alcohol Polymer Functionalized with SbQ Groups (P4)

[0141] ##STR00025##

[0142] The polymer was prepared according to the procedure described in Example 1, using:

[0143] 20 g of polyvinyl alcohol (Selvol 540 from Sekisui)

[0144] 1 g of N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate

[0145] Solvent: 200 ml of water

[0146] The polymer obtained comprises 15% by weight of SbQ group derived from N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate.

EXAMPLE 5 (Outside the Invention)

Polyvinyl Alcohol Polymer Functionalized with SbQ Groups (P5)

[0147] ##STR00026##

[0148] sold by the company Polysciences, Inc. under the catalogue reference 22570-75 with a degree of grafting with SbQ groups derived from N-methyl-4-(p-formylstyryl)pyridinium methyl sulfate of 4.1 mol %; molecular weight: 45 000.

Comparative Examples 6 to 10

Evaluation of the Cosmetic Properties of the Polymers Applied to the Hair

[0149] The five compositions described below were prepared (weight percentages).

TABLE-US-00001 Ex. 6 Ex. 7 Ex. 8* Ex. 9* Ex. 10* Polymer 1 10 Polymer 2 10 Polymer 4 10 Polymer 5 10 PVA 10 Water qs 100 qs 100 qs 100 50/50 qs 100 qs 100 water/isopropanol (weight/weight) *examples outside the invention

[0150] A mixture of 40% by weight of bleaching powder sold under the name Platifiz Precision by L'Oreal and 60% of aqueous hydrogen peroxide solution at 0.6% by weight was applied to locks of hair of curly type IV, in a bath ratio equal to 4, and the treated locks were then heated on a hotplate at 33 C. for 30 minutes. The locks were then rinsed with tap water and left to dry in a ventilated oven at 70 C. for one hour. This protocol was repeated a second time.

[0151] The polymer composition to be evaluated was applied to the locks thus bleached, using a brush, with a bath ratio equal to 1, on each side of the lock of hair. The lock was then exposed under a Sina UV Lamp & Dryer56 W UV lamp for 6 minutes and was then dried on a hotplate at 50 C. for 15 minutes. The treated locks were then left at room temperature for 24 hours.

[0152] 1 g of DOP camomile shampoo sold by La Scad was then applied per 2.8 g of locks, and the locks were massaged for 10 seconds, left to stand for three minutes and then rinsed with water at 37 C., 10 passes. The locks were then dried in a ventilated oven at 70 C. for 1 hour. Shampoo was applied five times in total.

[0153] The following cosmetic properties were then evaluated:

[0154] Feel: the feel by finger of the treated locks was evaluated by three people trained in sensory evaluation on hair, on softness tactile criteria.

[0155] Disentangling: disentangling using a comb was performed after immersing the lock for 10 seconds in water, with 5 passes of a small-toothed plastic comb (7 teeth/cm, tooth diameter of about 800 m).

[0156] The evaluation was made in the following manner:

[0157] ++: cosmetic property evaluated as effective

[0158] +: cosmetic property evaluated as moderately effective

[0159] 0: cosmetic property evaluated as ineffective

[0160] The following results were obtained:

TABLE-US-00002 Before shampooing After 5 shampoo washes Feel Feel Feel Feel wet dry wet dry Examples (softness) Disentangling (softness) (softness) Disentangling (softness) 6 (P1) ++ + ++ ++ ++ ++ Invention 7 (P2) ++ + ++ ++ + ++ Invention 8* (P4) + 0 + 0 0 0 Comparative 9* (P5) + 0 + 0 0 0 Comparative 10* 0 0 0 0 0 0 (PVA) Comparative

[0161] It is seen from the results of the table that polymers P1 and P2 of the invention make it possible to improve the feel and the disentangling, before and even after five shampoo washes, versus PVA alone, or polymers P4 and P5 outside the invention which do not comprise hydrophobic chains.

[0162] The results obtained show that the polymers according to the invention give improved feel and disentangling properties.

EXAMPLE 11

[0163] The following composition is prepared (weight percentage):

TABLE-US-00003 Polymer 3 (Example 3) 6% Water/isopropanol (50/50) qs 100%

[0164] The composition is applied to the hair and left to dry for 15 minutes at room temperature, and the hair is then exposed to light under a Sina UV Lamp & Dryer56 W UV lamp for 6 minutes.

[0165] The hair thus treated has a soft feel and good disentangling, including after shampooing.