PHOTODIMERIZABLE POLYMERS COMPRISING AT LEAST ONE POLYOXYALKYLENE GROUP, COMPOSITION COMPRISING SAME AND COSMETIC TREATMENT PROCESS

Abstract

The present invention relates to particular photodimerizable polymers comprising at least one polyoxyalkylene group, and also to a composition comprising at least one of these polymers. The present invention also relates to a cosmetic process for treating keratin materials, in particular keratin fibres, preferably human keratin fibres such as the hair, comprising the application to said keratin materials of at least one of these particular photodimerizable polymers.

Claims

1. Photodimerizable polymer (P) comprising at least one photodimerizable pendant group and at least one polyoxyalkylene pendant group, wherein the photodimerizable pendant group(s) are chosen from monovalent radicals of formulae (I) and (II) below: ##STR00038## and also the geometrical isomers thereof, in which formulae (I) and (II): Y and Z denote, independently of each other, a nitrogen atom or a C(R) group with R representing a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group such as methyl; A represents a bond or a divalent group chosen from (C.sub.1-C.sub.5)alkylene, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio)carbonyl and (C.sub.2-C.sub.5)alkenylene radicals and combinations thereof; B represents a monovalent group chosen from (C.sub.1-C.sub.5)alkyl radicals, aryl radicals, optionally cationic heteroaryl radicals, cycloalkyl radicals, optionally cationic heterocycloalkyl radicals, (thio)carbonyl radicals and (C.sub.2-C.sub.5)alkenyl radicals and combinations thereof; X represents a divalent group chosen from (C.sub.2-C.sub.5)alkylene, arylene, heteroarylene, cycloalkylene, heterocycloalkylene, (thio)carbonyl and (C.sub.2-C.sub.5)alkenylene radicals and combinations thereof; p represents an integer between 1 and 5 inclusive, in particular between 1 and 3; preferably, p is equal to 1; ##STR00039## represents the bond which connects the part of the monovalent radical to the rest of the molecule; and each of the groups mentioned may optionally be substituted with one or more halogen atoms or groups chosen from the following: (C.sub.1-C.sub.6)alkyl, hydroxyl, amino, (di)(C.sub.1-C.sub.6)alkylamino, phenyl, carboxyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkoxy(thio)carbonyl, hydrogeno(thio)carbonyl, sulfonato ROS(O).sub.2 or RS(O).sub.2O.sup., amide RRNC(O) or RC(O)N(R) or acyl RC(O), ammonium RRN.sup.+ with R, R and R, which may be identical or different, representing a hydrogen atom or a (C.sub.1-C.sub.4)alkyl group.

2. Polymer according to claim 1, characterized in that the photodimerizable pendant group(s) are chosen from monovalent radicals of the following compounds: stilbene, styrylpyridinium (stilbazolium) of formulae (A1) and (A2) below, and the geometrical isomers thereof: ##STR00040## in which: 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 else two contiguous R.sup.1 or R.sup.3 groups form, together with the carbon atoms bearing 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 such as chlorine or hydroxyl; preferably, R.sup.2 represents a (C.sub.1-C.sub.6)alkyl group such as methyl, ethyl or propyl; q and r represent an integer between 0 and 4 inclusive; and Q.sup. represents an anionic counter ion preferably chosen from halide ions such as chlorides, bromides and iodides, perchlorates, tetrafluoroborates, methyl sulfate, phosphates, sulfates, methanesulfonates, p-toluenesulfonate; and ##STR00041## represents the bond which connects the part of the monovalent radical to the rest of the molecule, it being understood that the pendant group A2 can be connected to the rest of the molecule via R.sup.2; preferably, the ##STR00042## bond is on the phenyl in the para position of the styryl group on A1 or connected to the rest of the molecule via R.sup.2 on A2; preferentially, the styryl group of A1 and A2 is in the para position of the pyridinium group; styrylazolium of formulae (B1 and B2) below, and the geometrical isomers thereof: ##STR00043## in which: A represents a sulfur atom, an oxygen atom, or a group NR.sub.2 or C(R.sup.2).sub.2; and ##STR00044## Q.sup., r, q, R.sup.1, R.sup.2 and R.sup.3 being as defined previously, preferably, the ##STR00045## bond is on the phenyl in the para position of the stryryl group, styrylpyrazine, chalcone, (thio)cinnamate and (thio)cinnamamide, maleimide, (thio)coumarin, thymine, uracil, butadiene, anthracene, pyridone, pyrrolizinone, acridizinium salts, furanone, phenylbenzoxazole, and derivatives thereof.

3. Polymer according to claim 1, characterized in that the polyoxyalkylene pendant group(s) comprise one or more polyoxyalkylene groups chosen from the groups of the following formula:
[OX].sub.nOR in which, X represents an alkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, n denotes an integer ranging from 10 to 1000, preferably from 20 to 200, and more preferentially from 25 to 150, and R represents a linear or branched alkyl chain containing from 1 to 6 carbon atoms.

4. Polymer according to claim 1, characterized in that it has a natural or synthetic backbone chosen from polysaccharides, poly(vinyl) polymers and polydiorganosiloxanes, preferably from polyvinyl alcohols and poly(vinyl acetate)s, which are preferably partially hydrolysed.

5. Polymer according to claim 1, 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 claim 1, characterized in that the total amount of the polyoxyalkylene 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 claim 1.

8. Composition according to claim 7, characterized in that the total amount of the photodimerizable polymer(s) (P) ranges from 0.01% to 50% by weight, preferably from 0.1% to 25% by weight and better still from 1% to 20% by weight, relative to the total weight of the composition.

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

10. Cosmetic process for treating keratin materials, in particular keratin fibres, preferably human keratin fibres such as the hair, comprising: (a) a step of applying to said keratin materials one or more photodimerizable polymers (P), as defined according to claim 1, (b) followed by an optional drying step, (c) followed by a step of exposing said keratin materials to natural or artificial light radiation.

11. Process according to claim 10, characterized in that the light radiation is artificial; preferably, the artificial light radiation is produced at a wavelength of between 280 nm and 700 nm and more preferentially between 300 nm and 500 nm.

Description

EXAMPLES

Example I: Synthesis of a Photocrosslinkable mPEG-PVA-SbQ Polymer According to the Invention

[0271] 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.

##STR00034##

[0272] First step: synthesis of the PVA-SbQ polymer according to the publication: Synthesis of hydrophobized and photo-crosslinkable pre-polymer based on polyvinyl alcohol in Reactive & Functional Polymer, 1995, 28, 55-60.

[0273] The PVA-SbQ polymer was synthesized according to the following synthetic reaction

##STR00035##

[0274] The amounts of the reaction compounds used in this synthesis are expressed (in grams) in the table below:

TABLE-US-00002 TABLE 2 Solutions Compounds Amount (g) PVA solution PVA, Mowiol 4-98 115.42 85% H.sub.3PO.sub.4 23.26 H.sub.2O 2242 SbQ-4 solution SbQ-4 29.20 H.sub.2O 115.50

[0275] 115.42 g of polyvinyl alcohol (PVA, Mowiol 4-98) were dissolved in 2242 g of water with stirring (80 rpm) at 90 C. The reaction medium was brought to 20 C. and left stirring (20 rpm) overnight. 23.26 g of phosphoric acid (85%) were then slowly added to the medium. A light shield (aluminium foil) was then placed around the reactor.

[0276] In parallel, 29.20 g of SbQ-4 were dissolved in 115.5 g of water, in the absence of light, before being added to the reaction medium (i.e. the above PVA solution). The medium was then left stirring (100 rpm) for 5 days, protected from light.

[0277] After 3 days, a sample (15 g) of the reaction medium was taken and precipitated from 120 g of acetone. The yellow solid thus obtained was then washed 4 times with acetone before being dried under vacuum. NMR analysis confirmed that the product obtained was the desired PVA-SbQ polymer.

[0278] The remaining reaction medium was used for the second step below, without prior purification.

[0279] Second step: grafting of PEG groups

[0280] The mPEG-PVA-SbQ polymer was synthesized according to the following synthetic reaction

##STR00036##

[0281] The amounts of the reaction compounds used in this synthesis are expressed (in grams) in the table below:

TABLE-US-00003 TABLE 3 Amount (g) PVA-SbQ polymer synthesized in the first step 1499.72 mPEG5K propionaldehyde 120.93 85% H.sub.3PO.sub.4 5.20 H.sub.2O 514.30

[0282] 120.93 g of mPEG5K propionaldehyde were dissolved in water and phosphoric acid, in the absence of light. The solution was heated at 50 C. for 1 h before being cooled to room temperature and degassed.

[0283] The PVA-SbQ previously obtained was then added to the mixture, with stirring (300 rpm) and in the absence of light. After 7 days, 10 mL of the reaction medium were precipitated from 50 mL of an MEK/acetone (80/20) mixture. The solid obtained was then dissolved in 15 mL of methanol before being precipitated again from 32 mL of MEK/acetone (80/20) mixture.

[0284] The solid product thus obtained was dried under vacuum at room temperature to give the desired mPEG-PVA-SbQ polymer.

Example II: Evaluation of the Disentangling Properties

a. Preparation of the Formulations

[0285] Formulation A according to the present invention and comparative formulations B1 and B2 were prepared from the ingredients mentioned in the table below, expressed as percentages of active material.

TABLE-US-00004 TABLE 4 A B1 B2 (invention) (comparative) (comparative) mPEG-PVA-SbQ 6% (obtained in Example I) PVA-SbQ 6% Propyl-PVA-SbQ 6% Distilled water qs 100% qs 100% qs 100%
b. Protocol

[0286] Formulations A, B1 and B2 thus obtained were applied to 2.5 g locks of 27 cm long sensitized hair (AS20) and moistened at a rate of 0.5 g of formulation per gram of hair. Blow-drying was then performed on each of the locks using a 30 cm diameter round brush and a hair dryer.

[0287] During the blow-drying, the tangential force of the brush as it passed through the lock was measured for each of the locks using a Lloyd machine (Ametek LS1 measuring machine) for 30 seconds.

c. Results

[0288] The sums of the tensile forces measured for 30 seconds for each of the locks are expressed in the table below.

TABLE-US-00005 TABLE 5 Force (N) measured Force (N) measured at after five shampoo t.sub.0 washes A (invention) 479 633 B1 (comparative) 1453 1266 B2 (comparative) 1208 1094 Control - sensitized but 2015 untreated lock

[0289] The results obtained above show that hair treated with the formulation of the invention, comprising a photodimerizable polymer (P) comprising at least one polyoxyalkylene pendant group (mPEG-PVA-SbQ), has better disentangling properties than hair treated with the comparative formulations, not containing the particular polymer (P). Specifically, the force of resistance to the passage of the brush, measured after applying formulation A, is significantly lower than the force measured for the comparative formulations, which makes brushing much easier.

Example III: Compositions According to the Invention

[0290] Compositions A1 and A2 according to the present invention were prepared from the ingredients mentioned in the table below, expressed as weight percentages of active material.

TABLE-US-00006 TABLE 6 A1 A2 [00037] 6 6 Xanthan gum 1.5 2 Mixture of amino silicones (Belsil ADM 0.074 LOG1 from Wacker) Water qs 100% qs 100%

[0291] Compositions A1 and A2 thus obtained give the hair improved conditioning properties.

Example IV: Evaluation of the Disentangling Properties and of the Flexibility of the Hair

a. Preparation of the Formulations

[0292] Formulation A3 according to the present invention and comparative formulations C.sub.1, C.sub.2, C.sub.3 and C.sub.4 were prepared from the ingredients mentioned in the table below, expressed as percentages of active material.

TABLE-US-00007 TABLE 7 A3 C1 C2 C3 C4 (inv.) (Comp.) (Comp.) (Comp.) (Comp.) mPEG-PVA- 5 SbQ (obtained in Example I) PVA-SbQ 5 3.24 5 PEG-90 5 1.76 2.72 Distilled water qs qs qs qs qs 100% 100% 100% 100% 100%
b. Protocol

[0293] Formulations A3, C.sub.1, C.sub.2, C.sub.3 and C.sub.4 thus obtained were applied to 2.5 g locks of 25 cm long sensitized hair (AS20) and moistened at a rate of 0.4 g of formulation per gram of hair. Blow-drying was then performed on each of the locks using a 30 cm diameter round brush and a hair dryer.

[0294] The locks then underwent an artificial light irradiation at a wavelength of 405 nm.

[0295] Then, the locks are washed 5 times with a standard shampoo (DOP), blow-dried, washed 5 times again with a standard shampoo (DOP) and blow-dried.

[0296] 10 experts evaluated by touch and naked eye, the flexibility of treated hair locks compared to untreated hair locks, and gave a score between 1 and 10; wherein 1=the hair is similar to untreated hair and 10=the flexibility of the hair has been particularly improved compared to untreated hair.

[0297] The disentangling properties have also been evaluated. The treated locks were plunged completely into a beaker (800 ml) of distilled water 3 times to entangle the hair, and then wrung out with fingers. A comb is then passed along the entire length of the treated lock and the distance the comb has run from the root to the tip before being stopped by a knot has been measured.

c. Results

[0298] The results are summarized in the tables below.

TABLE-US-00008 TABLE 8 Flexibility Formulations Average score A3 (inv.) 10 0 C1 (Comp.) 2.7 0.5 C2 (Comp.) 2.3 0.5 C3 (Comp.) 5.7 0.5 C4 (Comp.) 5.3 0.5

TABLE-US-00009 TABLE 9 Disentangling properties Formulations Distance (in cm) before being stopped A3 (inv.) The comb has not been stopped C1 (Comp.) 10 cm C2 (Comp.) 13 cm C3 (Comp.) 20 cm C4 (Comp.) 19 cm

[0299] The results obtained above show that the formulation A3 of the invention, comprising a photodimerizable polymer (P) comprising at least one polyoxyalkylene pendant group (mPEG-PVA-SbQ), provides much better flexibility and disentangling properties to the hair than the comparative formulations which contain either the PVA-SbQ polymer alone or the PEG polymer alone or a mixture of the PVA-SbQ polymer and the PEG polymer.