Gradient copolymer, composition including same and cosmetic make-up or care method

Abstract

Novel gradient copolymers including at least two different and specifically selected monomers, and cosmetic or skin-care compositions including same. The invention also relates to a cosmetic method for make-up or the care of keratin materials, in particular the skin of the body or of the face, the nails, the hair and/or the eyelashes, comprising the application of a cosmetic composition as defined above on said materials.

Claims

1. A gradient copolymer comprising at least two different monomers chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate.

2. The copolymer according to claim 1, wherein a first monomer chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate is present in an amount ranging from 1 to 99% by weight, relative to the weight of the final copolymer.

3. The copolymer according to claim 2, wherein said first monomer is present in an amount ranging from 30 to 70% by weight, relative to the weight of the final copolymer.

4. The copolymer according to claim 2, wherein a second monomer chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate, but different from said first monomer is present in an amount ranging from 1 to 99% by weight, relative to the weight of the final copolymer.

5. The copolymer according to claim 4, wherein said second monomer is present in an amount ranging from 30 to 70% by weight, relative to the weight of the final copolymer.

6. The copolymer according to claim 1, further comprising a third monomer different from said first and second monomers and being chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate, present in an amount ranging from 1 to 50% by weight, relative to the weight of the final copolymer.

7. The copolymer according to claim 6, wherein said third monomer is present in an amount ranging from 10 to 35% by weight, relative to the weight of the final copolymer.

8. The copolymer according to claim 1, wherein the total amount of monomers chosen from isobornyl acrylate, isobornyl methacrylate and isobutyl acrylate in the final copolymer ranges from 50 to 100% by weight, relative to the weight of the final copolymer.

9. The copolymer according to claim 1, wherein the total amount of monomers chosen from isobornyl acrylate, isobornyl methacrylate and isobutyl acrylate in the final copolymer ranges from 90 to 95% by weight, relative to the weight of the final copolymer.

10. The copolymer according to claim 1, comprising at least on of the following combinations of monomers: isobornyl acrylate and isobornyl methacrylate; isobornyl acrylate and isobutyl acrylate; isobornyl acrylate and isobutyl methacrylate; isobornyl acrylate and 2-ethylhexyl acrylate; isobornyl methacrylate and isobutyl acrylate; isobornyl methacrylate and isobutyl methacrylate; isobornyl methacrylate and 2-ethylhexyl acrylate; isobornyl acrylate, isobornyl methacrylate and 2-ethylhexyl acrylate; isobornyl acrylate, isobornyl methacrylate and isobutyl acrylate; isobornyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate; isobornyl acrylate, isobutyl methacrylate and isobutyl acrylate; and isobornyl methacrylate, isobutyl methacrylate and isobutyl acrylate.

11. The copolymer according to claim 1, further comprising at least one additional monomer, other than those chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate.

12. The copolymer according to claim 11, wherein the at least one additional monomer is present in an amount ranging from 2 to 50% by weight, relative to the weight of the final copolymer.

13. The copolymer according to claim 12, wherein the at least one additional monomer is present in an amount ranging from 5 to 10% by weight, relative to the weight of the final copolymer.

14. The copolymer according to claim 11, wherein the additional monomer is chosen, alone or as a mixture, from: (i) (meth)acrylates of formula CH.sub.2═CHCOOR or CH.sub.2═C(CH.sub.3)COOR wherein R is chosen from: a linear or branched alkyl group comprising 1 to 30 carbon atoms in which is optionally inserted at least one heteroatom chosen from O, N, S and P, said alkyl group being optionally substituted by at least one substituent chosen from —OH, halogen atoms chosen from Cl, Br, I and F, —NR.sub.4R.sub.5 groups, wherein R.sub.4 and R.sub.5, which are identical or different, are each independently chosen from hydrogen, linear or branched C.sub.1 to C.sub.6 alkyl groups, phenyl groups; and polyoxyalkylene groups composed of the repetition of 5 to 30 oxyalkylene units; a C.sub.3 to C.sub.12 cycloalkyl group, said cycloalkyl group optionally comprising, in its chain, at least one heteroatom chosen from O, N, S and/or P and optionally substituted by at least one substituent chosen from —OH and halogen atoms chosen from Cl, Br, I and F; a C.sub.4 to C.sub.20 aryl group or a C.sub.5 to C.sub.30 aralkyl group wherein the alkyl is C.sub.1 to C.sub.8 alkyl; (ii) (meth)acrylamides of formula CH.sub.2═CHCONR.sub.4R.sub.5 or CH.sub.2═C(CH.sub.3)CONR.sub.4R.sub.5 wherein R.sub.4 and R.sub.5, which are identical or different, are each independently chosen from hydrogen atoms and: a) linear or branched alkyl groups comprising from 1 to 18 carbon atoms in which is optionally inserted at least one heteroatom chosen from O,N, S and P; said alkyl group being optionally substituted by at least one substituent chosen from hydroxyl groups, halogen atoms chosen from Cl, Br, I and F and Si(R.sub.4R.sub.5) groups, wherein R.sub.4 and R.sub.5, which are identical or different, are each independently chosen from C.sub.1 to C.sub.6 alkyl groups and phenyl groups; b) a C.sub.3 to C.sub.12 cycloalkyl group and heterocycloalkyl groups having an alkyl portion of 1 to 4 carbon atoms, c) C.sub.4 to C.sub.20 aryl groups, d) C.sub.5 to C.sub.30 aralkyl groups, wherein said alkyl portion has C.sub.1 to C.sub.8 alkyl groups, (iii) monomers possessing at least one ethylenic unsaturation comprising at least one functional group chosen from carboxylic acids, phosphoric acids, sulfonic acids and anhydrides and the salts thereof; (iv) vinyl ethers of formula R.sub.6O—CH═CH.sub.2and vinyl esters of formula R.sub.6—COO—CH═CH.sub.2 wherein R.sub.6 represents a linear or branched alkyl group comprising from 1 to 22 atoms, a cyclic alkyl group comprising from 3 to 6 carbon atoms and an aromatic group; (v) vinyl compounds of formula CH.sub.2═CH—R.sub.9, CH.sub.2═CH—CH.sub.2—R.sub.9 or CH.sub.2═C(CH.sub.3)—CH.sub.2—R.sub.9 wherein R.sub.9 is chosen from a hydroxyl group, a halogen group chosen from C1 and F, an NH.sub.2 group, an OR.sub.10 group, wherein R.sub.10 is chosen from a phenyl group and a C.sub.1 to C.sub.12 alkyl group such that the monomer is a vinyl or allyl ether, an acetamide group (NHCOCH.sub.3), an OCOR.sub.11 group, wherein R.sub.11 is a linear or branched alkyl group of 2 to 12 carbons such that the monomer is a vinyl or allyl ester, and a group chosen from: a linear or branched alkyl group of 1 to 18 carbon atoms in which is optionally inserted one or more heteroatoms chosen from O, N, S and P, said alkyl group additionally being optionally substituted by at least one substituent chosen from hydroxyl groups, halogen atoms chosen from Cl, Br, I and F and Si(R.sub.4R.sub.5) groups, wherein R.sub.4 and R.sub.5, which are identical or different, are each independently represent a C.sub.1 to C.sub.6 alkyl group or a phenyl group; a C.sub.3 to C.sub.12 cycloalkyl group, a C.sub.3 to C.sub.20 aryl group, a C.sub.4 to C.sub.30 aralkyl group (C.sub.1 to C.sub.8 alkyl groups), a 4- to 12-membered heterocyclic group comprising at least one heteroatom chosen from O, N and S, the ring being aromatic or nonaromatic, a heterocycloalkyl group wherein said alkyl portion comprises of 1 to 4 carbon atoms, (vi) styrene and its derivatives; (vii) monomers possessing ethylenic unsaturation comprising at least one silicon atom and salts and mixtures thereof.

15. The copolymer according to claim 11, wherein the at least one additional monomer is chosen from methyl (meth)acrylates, n-propyl (meth)acrylates, isopropyl (meth)acrylates, n-butyl (meth)acrylates, t-butyl (meth)acrylates, cyclohexyl (meth)acrylates, methoxyethyl (meth)acrylates, ethoxyethyl (meth)acrylates, trifluoroethyl (meth)acrylates, dimethylaminoethyl (meth)acrylates, diethylaminoethyl (meth)acrylates, 2-hydroxypropyl (meth)acrylates and 2-hydroxyethyl (meth)acrylates, acrylic acid, methacrylic acid, (meth)acrylamide, methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltris-(trimethylsiloxy) silane, and salts and mixtures thereof.

16. The copolymer according to claim 11, wherein the at least one additional monomer is chosen, alone or as a mixture, from carbon-based or silicone macro-monomers having at least one polymerizable end group and their salts.

17. The copolymer according to claim 16, wherein said carbon-based or silicone macro-monomers having at least one polymerizable end group and salts thereof, are chosen from (i) linear or branched C.sub.8-C.sub.22alkyl (meth)acrylate homopolymers and copolymers comprising a polymerizable end group chosen from vinyl and (meth)acrylate groups; (ii) polyolefins comprising an end group habing ethylenic unsaturation; (iii) polydimethylsiloxanes comprising a mono(meth)acrylate end group.

18. The copolymer according to claim 1, comprising at least one monomer having a Tg of less than or equal to 20° C.

19. The copolymer according to claim 18, comprising at least one monomer having a Tg of less than −120° C. to 15° C.

20. The copolymer according to claim 18, wherein the at least one monomer with a Tg ≦20° C. is present in an amount ranging from 1 to 99% by weight, relative to the total weight of the copolymer.

21. The copolymer according to claim 20, wherein the at least one monomer with a Tg ≦20° C. is present in an amount ranging from 25 to 75% by weight, relative to the total weight of the copolymer.

22. The copolymer according to claim 1, comprising at least one monomer having a Tg of greater than or equal to 20° C.

23. The copolymer according to claim 22, comprising at least one monomer having a Tg ranging from 40 to 140° C.

24. The copolymer according to claim 22, wherein the at least one monomer with a Tg ≧20° C. is present in an amount of 1 to 99% by weight, relative to the total weight of the copolymer.

25. The copolymer according to claim 24, wherein the at least one monomer with a Tg ≧20° C. is present in an amount of 25 to 75% by weight, relative to the total weight of the copolymer.

26. The copolymer according to claim 1, wherein the copolymer is soluble in isododecane at 25° C., 1 atm., at a concentration of at least 1% by weight.

27. The copolymer according to claim 1, wherein the copolymer is soluble in isododecane at 25° C., 1 atm., at a concentration of at least 10% by weight.

28. The copolymer according to claim 1, wherein the copolymer has a weight polydispersity index of less than or equal to 3.

29. The copolymer according to claim 1, wherein the copolymer has a weight polydispersity index ranging from 1.2 to 1.8.

30. The copolymer according to claim 1, wherein the copolymer has, on a liquid curve, a difference V.sup.1/2 max −V.sup.1/2 min, wherein V is elution volume, of less than or equal to 3.5.

31. The copolymer according to claim 30, wherein the copolymer has a difference V.sup.1/2 max −V.sup.1/2 min ranging from 1.1 to 2.0.

32. A cosmetic or dermatological composition comprising, in a physiologically acceptable medium, at least one gradient copolymer comprising at least two different monomers chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate.

33. The composition according to claim 32, wherein the copolymer is present in an amount ranging from 0.1 to 95% by weight, relative to the total weight of the composition.

34. The composition according to claim 32, wherein the copolymer is present in an amount ranging from 5 to 70% by weight, relative to the total weight of the composition.

35. The composition according to claim 32, comprising at least one fatty phase which comprises oils and/or solvents having an overall solubility parameter according to the Hansen solubility space of less than or equal to 20 (MPa).sup.1/2.

36. The composition according to claim 32, comprising at least one oil and/or solvent chosen from volatile or nonvolatile oils which can be chosen from optionally branched, carbon-based, hydrocarbon or fluorinated, natural or synthetic oils, alone or as a mixture; ethers and esters having more than 6 carbon atoms; ketones having more than 6 carbon atoms; aliphatic fatty monoalcohols having 6 to 30 carbon atoms, wherein the hydrocarbon chain does not comprise a substituent group.

37. The composition according to claim 32, wherein the at least one oil and/or solvent is chosen from volatile or nonvolatile alkanes chosen from decane, heptane, dodecane, isododecane, isohexa-decane, cyclohexane and mixtures thereof.

38. The composition according to claim 32, comprising at least from 0.01 to 95% by weight of at least one oil and/or solvent, relative to the total weight of the composition.

39. The composition according to claim 38, comprising at least from 30 to 80% by weight of at least one oil and/or solvent, relative to the total weight of the composition.

40. The composition according to claim 32, further comprising a constituent chosen from a hydrophilic medium comprising water or a mixture of water and of hydrophilic organic solvent; waxes; gums; coloring materials; fillers; polymers; vitamins, thickeners, gelling agents, trace elements, softening agents, sequestering agents, fragrances, basifying or acidifying agents, preservatives, sunscreens, surfactants, antioxidants, agents for combating hair loss, antidandruff agents, propellants, ceramides and mixtures thereof.

41. The composition according to claim 32, wherein the composition is in a form chosen from a suspension, a dispersion, a solution a gel, an emulsion, a cream, a foam, a dispersion of vesicles, a two-phase or multiphase lotion, a spray, a powder, a paste and in the anhydrous form, for example of an anhydrous paste.

42. The composition according to claim 41, wherein the composition is in a form chosen from an organic solution; oil-in-water (O/W), water-in-oil (W/O), or a multiple (W/O/W or polyol/O/W or O/W/O) emulsion, a cream, a foam, a dispersion of vesicles comprising ionic or nonionic lipids; a soft paste; and an anhydrous paste.

43. The composition according to claim 32, wherein the composition is chosen from a makeup composition; a product for the lips; a concealer; a blusher, a mascara, an eyeliner; a product for making up the eyebrows, a lip pencil, an eye pencil; a product for the nails; a product for making up the body; a product for making up the hair; a composition for protecting or caring for the skin of the face, of the neck, of the hands or of the body; an antisun or artificial tanning composition; and a hair composition.

44. The composition according to claim 43, wherein the composition is chosen from a foundation, a face powder or an eyeshadow.

45. The composition according to claim 44, wherein the composition is in the form chosen from a foundation, a face powder, an eyeshadow, a lipstick, a lip care product, a nail varnish, a nail care product, hair mascara, hair lacquer, a composition for combating wrinkles or fatigue, a moisturizing composition, a treating composition and a hair composition, form the form retention of the hairstyle or the shaping of the hair.

46. A cosmetic process for making up or caring for keratinous substances, comprising the application, to said substances, of a cosmetic composition comprising, in a physiologically acceptable medium, at least one gradient copolymer comprising at least two different monomers chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate.

47. A cosmetic process according to claim 46, wherein the keratinous substances are chosen from the skin of the body or face, the nails, the hair and the eyelashes.

48. A cosmetic process for making up the skin of the face and/or lips, comprising the application, to said substances, of a foundation or lipstick cosmetic composition comprising, in a physiologically acceptable medium, at least one gradient copolymer comprising at least two different monomers chosen from isobornyl acrylate, isobornyl methacrylate, isobutyl acrylate, isobutyl methacrylate and 2-ethylhexyl acrylate.

49. The copolymer according to claim 2, wherein said first monomer is isobornyl acrylate and is present in an amount ranging from comprising from 30 to 70% by weight, relative to the weight of the final copolymer and wherein said second monomer is isobornyl methacrylate and is present in an amount ranging from comprising from 30 to 70% by weight, relative to the weight of the final copolymer; and wherein the total amount of monomers isobornyl acrylate and isoboryl methacrylate in the final copolymer ranges from 50 to 100% by weight, relative to the weight of the final copolymer.

50. The copolymer according to claim 49, which further comprises isobutyl acrylate as a third monomer in an amount of 10 to 35% by weight, relative to the weight of the final copolymer.

51. The copolymer according to claim 49, which further comprises 2-ethylhexyl acrylate as a third monomer in an amount of 10 to 35% by weight, relative to the weight of the final copolymer.

Description

EXAMPLE 1

(1) 3.5 g of isobornyl acrylate (1.7×10.sup.−2 mol), 3.5 g of isobornyl methacrylate (1.6×10.sup.−2 mol), 3 g of isobutyl acrylate (2.3×10.sup.−2 mol) and 10 g of butyl acetate are mixed in a 100 ml three-necked flask equipped with a reflux condenser and placed under an argon flow.

(2) This mixture is degassed by bubbling with argon for 15 minutes and then 40 mg of CuBr, 49 mg of PMDETA (N,N,N′,N′,N″-pentamethyldiethylenetriamine) and 55.6 mg of ethyl 2-bromoisobutyrate are added. The reaction mixture is brought to 100° C. for 2 hours and then filtered through alumina.

(3) A solution of the polymer in butyl acetate (50% of dry matter DM) is obtained.

(4) The butyl acetate can be distilled off and can be substituted by isododecane (10 g). A solution of the polymer in isododecane (50% DM) is then obtained.

EXAMPLE 2

(5) 3.5 g of isobornyl acrylate, 3.5 g of isobornyl methacrylate, 3 g of 2-ethylhexyl acrylate and 10 g of butyl acetate are mixed in a 100 ml three-necked flask equipped with a reflux condenser and placed under an argon flow.

(6) This mixture is degassed by bubbling with argon for 15 minutes and then 40 mg of CuBr, 49 mg of PMDETA (N,N,N′,N′,N″-pentamethyldiethylenetriamine) and 55.6 mg of ethyl 2-bromoisobutyrate are added. The reaction mixture is brought to 100° C. for 2 hours and then filtered through alumina.

(7) A solution of the polymer in butyl acetate (50% of dry matter DM) is obtained.

(8) The butyl acetate can be distilled off and can be substituted by isododecane (10 g). A solution of the polymer in isododecane (50% DM) is then obtained.

EXAMPLE 3

(9) 5 g of isobornyl acrylate, 5 g of isobutyl acrylate and 10 g of butyl acetate are mixed in a 100 ml three-necked flask equipped with a reflux condenser and placed under an argon flow.

(10) This mixture is degassed by bubbling with argon for 15 minutes and then 40 mg of CuBr, 49 mg of PMDETA (N,N,N′,N′,N″-pentamethyldiethylenetriamine) and 55.6 mg of ethyl 2-bromoisobutyrate are added. The reaction mixture is brought to 100° C. for 2 hours and then filtered through alumina.

(11) A solution of the polymer in butyl acetate (50% of dry matter DM) is obtained.

(12) The butyl acetate can be distilled off and can be substituted by isododecane (10 g). A solution of the polymer in isododecane (50% DM) is then obtained.

EXAMPLE 4

(13) A nail varnish is prepared which comprises: 40% by weight of solution of the polymer of example 1 in butyl acetate with a DM of 50% q.s. for 100% of organic solvents (butyl acetate and ethyl acetate).

EXAMPLE 5

(14) An anhydrous foundation is prepared which comprises (% by weight):

(15) TABLE-US-00001 Polyethylene wax 12% Volatile silicone oils 25% Phenyl trimethicone 20% Poly (methyl methacrylate) microspheres 12% Solution of the polymer of example 2 in 12% isododecane with a DM of 50% (i.e., 6% of polymer dry matter) Isododecane q.s. for 100%
Preparation:

(16) The waxes are melted and then, when all is clear, the phenyl trimethicone is added with stirring and the silicone oils are added; subsequently the microspheres, the isododecane and the polymer are added. The mixture is homogenized for 15 minutes and then the resulting composition is cast and left to cool. An anhydrous foundation is obtained.

EXAMPLE 6

(17) A lipstick stick is prepared which comprises:

(18) TABLE-US-00002 Polyethylene wax 15% Solution of the polymer of example 3 in 20% isododecane with a DM of 50% (i.e., 10% of polymer dry matter) Hydrogenated polyisobutene (Parleam from 25% Nippon Oil Fats) Pigments 10% Isododecane q.s. for 100%

(19) The composition obtained exhibits good cosmetic properties after application to the lips.

EXAMPLE 7

(20) A foundation composition is prepared which comprises (% by weight):

(21) Phase A

(22) TABLE-US-00003 Cetyl dimethicone copolyol (Abil EM 90 from 3 g Goldschmidt) Isostearyl diglyceryl succinate (Imwitor 0.6 g 780K from Condea) Pigments (oxides of iron and of titanium) 10 g Polyamide (Nylon 12) powder 8 g Solution of the polymer of example 1 in 17 g isododecane with a DM of 50% (i.e., 8.5% of polymer dry matter) Fragrance q.s. Isododecane 10 g
Phase B

(23) TABLE-US-00004 Magnesium sulfate 0.7 g Preservative q.s. Water q.s. for 100 g

(24) The composition obtained exhibits good cosmetic properties.