초록

Thickeners for oil-containing compositions, particularly cosmetic and personal care compositions, are side chain crystalline polymers which are uniformly dispersed as a crystallized solid in the oil.

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What is claimed is: 1. A method of treating a substrate selected from human skin, human hair and human nails, the method comprising applying to the substrate a thickened oil composition which is free of water and which comprises (1) an oil, and (2) dispersed in the oil, a side chain crystalline (SC

What is claimed is: 1. A method of treating a substrate selected from human skin, human hair and human nails, the method comprising applying to the substrate a thickened oil composition which is free of water and which comprises (1) an oil, and (2) dispersed in the oil, a side chain crystalline (SCC) polymer which (a) has a crystalline melting point Tp, and an onset of melting temperature, To, such that (Tp-To) is less than Tp0.7; (b) is soluble in the oil at temperatures above Tp, (c) has been dispersed in the oil by a process which comprises (i) dissolving the polymer in the oil at the temperature above Tp, and (ii) cooling the solution to crystallize the polymer in the oil, and (d) is substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups; and the composition being at a temperature Ts which is below Tp, wherein the SCC polymer consists essentially of (i) 70-99% by weight of repeating units derived from at least one n-alkyl acrylate or methacrylate ester in which the n-alkyl group contains 16 to 22 carbon atoms, (ii) 1-30% by weight of repeating units derived from at least one acrylate or methacrylate ester in which the ester group contains a hydroxyl-substituted alkyl group containing less than 12 carbon atoms, and (iii) 0-29% by weight of repeating units derived from at least one acrylate or methacrylate ester in which the ester group contains an unsubstituted alkyl group containing less than 16 carbon atoms. 2. A method according to claim 1 wherein the composition is at a temperature Ts, where Ts is from 15 to 25�� C., and wherein the SCC polymer has a crystalline melting point, Tp, which is 10 to 30�� C. above Ts. 3. A method according to claim 1 wherein the SCC polymer has a heat of fusion of at least 20 J/g, and an onset-of melting-point To such that (Tp-To) is less than 10�� C. 4. A method according to claim 1 wherein the hydroxyl-substituted alkyl group is a hydroxyethyl, hydroxypropyl, or hydroxybutyl group. 5. A method according to claim 1 wherein the composition contains less than 1% by weight of surface active agents, based on weight of the oil. 6. A method according to claim 1 wherein each of the following conditions is fulfilled by the SCC polymer: (1) at most 1% of the carbon atoms are substituted by one or more fluorine atoms; (2) at most 0.2 mol % of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) at most 0.5% by weight of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) at most 1 mol % of the repeating units are derived from acrylamide (6) at most 0.2 mol % of the repeating units are derived from N-vinylpyrrolidone; (7) at most 0.2 mol % of the repeating units are derived from N-vinylimidazole. 7. A method according to claim 1 wherein each of the following conditions is fulfilled by the SCC polymer: (1) none of the carbon atoms are substituted by one or more fluorine atoms; (2) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) none of the repeating units are derived from acrylamide; (6) none of the repeating units are derived from N-vinylpyrrolidone; (7) none of the repeating units are derived from N-vinylimidazole. 8. A method of treating a substrate selected from human skin, human hair and human nails, the method comprising applying to the substrate a thickened oil composition which comprises (1) a silicone oil, and (2) uniformly dispersed in the oil as a crystallized solid, a side chain crystalline (SCC) polymer which contains units derived from a monomer containing silicon and which is substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups. 9. A method according to claim 8 wherein the SCC polymer is a block copolymer containing SCC blocks and polysiloxane blocks. 10. A method according to claim 8 wherein the SCC polymer has a crystalline melting point, Tp, of 40-80�� C. 11. A method according to claim 8 wherein the SCC polymer has a heat of fusion of at least 20 J/g and an onset-of-melting point, To, such that (Tp-To) is less than 10�� C. 12. A method according to claim 8 wherein each of the following conditions is fulfilled by the SCC polymer: (1) at most 1% of the carbon atoms are substituted by one or more fluorine atoms; (2) at most 0.2 mol % of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) at most 0.5% by weight of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) at most 1 mol % of the repeating units are derived from acrylamide (6) at most 0.2 mol % of the repeating units are derived from N-vinylpyrrolidone; (7) at most 0.2 mol % of the repeating units are derived from N-vinylimidazole. 13. A method according to claim 8 wherein each of the following conditions is fulfilled by the SCC polymer: (1) none of the carbon atoms are substituted by one or more fluorine atoms; (2) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) none of the repeating units are derived from acrylamide; (6) none of the repeating units are derived from N-vinylpyrrolidone; (7) none of the repeating units are derived from N-vinylimidazole. 14. A cosmetic composition comprising (a) a mixture of two or more polymers, at least one of the polymers being a side chain crystalline (SCC) polymer which (i) has a melting point from 40�� C. to 80�� C., (ii) consists of repeating units which are derived from at least one n-alkyl acrylate or methacrylate in which the n-alkyl group contains 18 to 50 carbon atoms, (iii) is substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups, and (iii) is capable of forming a hydrophobic film at room temperature, and (b) at least one oil; the mixture of polymers being uniformly dispersed in the oil as a crystallized solid. 15. A cosmetic composition according to claim 14 which comprises a mixture of two or more side chain crystalline (SCC) polymers. 16. A process for thickening a cosmetic composition comprising an oil phase, the process comprising dispersing in the oil phase a mixture of two or more side chain crystalline (SCC) polymers, at least one of the SCC polymers being solid at ambient temperature and having a melting temperature of 40 to 50�� C.; at least one of the SCC polymers being solid at ambient temperature and having a melting temperature at least equal to 50�� C.; at least one of the SCC polymers consisting of repeating units which are derived from an n-alkyl acrylate or methacrylate in which the n-alkyl group contains 18 to 50 carbon atoms; and at least one of the SCC polymers being substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups. 17. A process for thickening a cosmetic composition comprising an oil phase, the process comprising dispersing in the oil phase a mixture of (a) an SCC polymer comprising units derived from stearyl acrylate, and (b) an SCC polymer comprising units derived from behenyl acrylate, at least one of the SCC polymers being substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups. 18. A process according to claim 17 wherein the SCC polymer derived from stearyl acrylate is a homopolymer of stearyl acrylate, and the SCC polymer derived from behenyl acrylate is a homopolymer of behenyl acrylate. 19. A lipstick comprising: at least one oil phase structured by a mixture of two or more side chain crystalline (SCC) polymers, at least one of the SCC polymers being solid at ambient temperature and having a melting temperature of 40 to 50�� C.; at least one of the SCC polymers being solid at ambient temperature and having a melting temperature at least equal to 50�� C.; and at least one of the SCC polymers being substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups. 20. A lipstick comprising: at least one oil phase structured by a mixture of (a) a homopolymer of stearyl acrylate, and (b) a homopolymer of behenyl acrylate. 21. A method of treating a substrate selected from human skin, human hair and human nails, the method comprising applying to the substrate a thickened oil composition which is free of water and which comprises (1) an oil, and (2) uniformly dispersed in the oil as a crystallized solid, a side chain crystalline (SCC) polymer which (a) has a crystalline melting point, Tp, and an onset of melting temperature, To, such that (Tp-To) is less than Tp0.7, and (b) is substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups. 22. A method according to claim 21 wherein the SCC polymer consists essentially of (i) 20-99% by weight of repeating units derived from at least one n-alkyl acrylate or methacrylate ester in which the n-alkyl group contains 16 to 22 carbon atoms, (ii) 1-30% by weight of repeating units derived from at least one acrylate or methacrylate ester in which the ester group contains a hydroxyl-substituted alkyl group containing less than 12 carbon atoms, and (iii) 0-29% by weight of repeating units derived from at least one acrylate or methacrylate ester in which the ester group contains an unsubstituted alkyl group containing less than 16 carbon atoms. 23. A method according to claim 21 wherein the hydroxyl-substituted alkyl group is a hydroxyethyl, hydroxypropyl, or hydroxybutyl group. 24. A method according to claim 21 wherein the SCC polymer has an onset of melting temperature, To, such that (Tp-To) is less than Tp0.6. 25. A method according to claim 21 wherein the composition is at a temperature Ts, where Ts is from 15 to 25�� C., and wherein the SCC polymer has a crystalline melting point, Tp, which is 10 to 30�� C. above Ts. 26. A method according to claim 21 wherein the SCC polymer has a heat of fusion of at least 20 J/g, and an onset-of-melting point To such that (Tp-To) is less then 10�� C. 27. A method according to claim 21 wherein Tp is 40 to 80�� C. 28. A method according to claim 21 wherein the composition contains less than 1% by weight of surface active agents, based on weight of the oil. 29. A method according to claim 21 wherein each of the following conditions is fulfilled by the SCC polymer: (1) at most 1% of the carbon atoms are substituted by one or more fluorine atoms; (2) at most 0.2 mol % of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) at most 0.5% by weight of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) at most 1 mol % of the repeating units are derived from acrylamide (6) at most 0.2 mol % of the repeating units are derived from N-vinylpyrrolidone; (7) at most 0.2 mol % of the repeating units are derived from N-vinylimidazole. 30. A method according to claim 21 wherein each of the following conditions is fulfilled by the SCC polymer: (1) none of the carbon atoms are substituted by one or more fluorine atoms; (2) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) none of the repeating units are derived from acrylamide; (6) none of the repeating units are derived from N-vinylpyrrolidone; (7) none of the repeating units are derived from N-vinylimidazole. 31. A method of treating a substrate selected from human skin, human hair and human nails, the method comprising applying to the substrate a thickened oil composition which is free from water and which comprises (1) an oil, and (2) dispersed in the oil, a side chain crystalline (SCC) polymer which (a) has a crystalline melting point Tp, and an onset of melting temperature, To, such that (Tp-To) is less than Tp0.7; (b) is soluble in the oil at temperatures above Tp, (c) has been dispersed in the oil by a process which comprises (i) dissolving the polymer in the oil at the temperature above Tp, and (ii) cooling the solution to crystallize the polymer in the oil, and (d) is substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups; and the composition being at a temperature Ts which is below Tp. 32. A method according to claim 31 wherein the composition is at a temperature Ts, where Ts is from 15 to 25�� C., and wherein the SCC polymer has a crystalline melting point, Tp, which is 10 to 30�� C. above Ts. 33. A method according to claim 31 wherein the SCC polymer consists essentially of (i) 70-99% by weight of repeating units derived from at least one n-alkyl acrylate or methacrylate ester in which the n-alkyl group contains 16 to 22 carbon atoms, (ii) 1-30% by weight of repeating units derived from at least one acrylate or methacrylate ester in which the ester group contains a hydroxyl-substituted alkyl group containing less than 12 carbon atoms, and (iii) 0-29% by weight of repeating units derived from at least one acrylate or methacrylate ester in which the ester group contains an unsubstituted alkyl group containing less than 16 carbon atoms. 34. A method according to claim 31 wherein the hydroxyl-substituted alkyl group is a hydroxyethyl, hydroxypropyl, or hydroxybutyl group. 35. A method according to claim 31 wherein the SCC polymer has an onset of melting temperature, To, such that (Tp-To) is is less than Tp0.6. 36. A method according to claim 31 wherein the SCC polymer has a heat of fusion of at least 20 J/g, and an onset-of-melting point To such that (Tp-To) is less than 10�� C. 37. A method according to claim 31 wherein the composition contains less than 1% by weight of surface active agents, based on weight of the oil. 38. A method according to claim 31 wherein each of the following conditions is fulfilled by the SCC polymer. (1) at most 1% of the carbon atoms are substituted by one or more fluorine atoms; (2) at most 0.2 mol % of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) at most 0.5% by weight of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) at most 1 mol % of the repeating units are derived from acrylamide (6) at most 0.2 mol % of the repeating units are derived from N-vinylpyrrolidone; (7) at most 0.2 mol % of the repeating units are derived from N-vinylimidazole. 39. A method according to claim 31 wherein each of the following conditions is fulfilled by the SCC polymer: (1) none of the carbon atoms are substituted by one or more fluorine atoms; (2) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) none of the repeating units are derived from acrylamide; (6) none of the repeating units are derived from N-vinylpyrrolidone; (7) none of the repeating units are derived from N-vinylimidazole. 40. A method according to claim 21 wherein the side chain crystalline (SCC) polymer (a) has a crystalline melting point, Tp, and an onset of melting temperature, To, such that Tp-To, is less than Tp0.7, and (b) comprises repeating units in which the side chains comprise linear polymethylene moieties containing 18 to 50 carbon atoms, and (c) is substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups. 41. A method of treating a substrate selected from human skin, human hair and human nails, the method comprising applying to the substrate a thickened oil composition which comprises (1) an oil, and (2) dispersed in the oil, a side chain crystalline (SCC) polymer which (a) has a crystalline melting point Tp, and an onset of melting temperature, To, such that (Tp-To) is less than Tp0.7; (b) consists of repeating units in which the side chains comprise linear polymethylene moieties containing 18 to 50 carbon atoms, (c) is substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups, and (d) has been dispersed in the oil by a process which comprises (i) dissolving the polymer in the oil at the temperature above Tp, and (ii) cooling the solution to crystallize the polymer in the oil; the composition being at a temperature Ts which is below Tp. 42. A method according to claim 41 wherein the composition is a water-in-oil emulsion or an oil-in-water emulsion. 43. A method according to claim 41 wherein the composition is free from water. 44. A method according to claim 41 wherein the composition is at a temperature Ts, where Ts is from 15 to 25�� C., and wherein the SCC polymer has a crystalline melting point, Tp, which is 10 to 30�� C. above Ts. 45. A method according to claim 41 wherein the SCC polymer has an onset of melting temperature, To, such that (Tp-To) is less than Tp0.6. 46. A method according to claim 41 wherein the SCC polymer has an onset of melting temperature, To, such that (Tp-To) is less than 10�� C. 47. A method according to claim 41 wherein the SCC polymer has a heat of fusion of at least 20 J/g. 48. A method according to claim 41 wherein the composition contains less than 1% by weight of surface active agents, based on weight of the oil. 49. A method according to claim 41 wherein each of the following conditions is fulfilled by the SCC polymer: (1) at most 1% of the carbon atoms are substituted by one or more fluorine atoms; (2) at most 0.2 mol % of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) at most 0.5% by weight of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) at most 1 mol % of the repeating units are derived from acrylamide (6) at most 0.2 mol % of the repeating units are derived from N-vinylpyrrolidone; (7) at most 0.2 mol % of the repeating units are derived from N-vinylimidazole. 50. A method according to claim 41 wherein each of the following conditions is fulfilled by the SCC polymer: (1) none of the carbon atoms are substituted by one or more fluorine atoms; (2) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) none of the repeating units are derived from acrylamide; (6) none of the repeating units are derived from N-vinylpyrrolidone; (7) none of the repeating units are derived from N-vinylimidazole. 51. A method according to claim 21 wherein the composition is a nail varnish, lipstick, deodorant stick, a hairdressing preparation, foam bath, bath oil or mascara. 52. A method of treating a substrate selected from human skin, human hair and human nails, the method comprising applying to the substrate a thickened oil composition which is free of water, which is a nail varnish, lipstick, deodorant stick, a hairdressing preparation, foam bath, bath oil or mascara, and which comprises (1) an oil, and (2) dispersed in the oil, a side chain crystalline (SCC) polymer which (a) has a crystalline melting point Tp, and an onset of melting temperature, To, such that (Tp-To) is less than Tp0.7; (b) is soluble in the oil at temperatures above Tp, (c) has been dispersed in the oil by a process which comprises (i) dissolving the polymer in the oil at the temperature above Tp, and (ii) cooling the solution to crystallize the polymer in the oil, and (d) is substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups; and the composition being at a temperature Ts which is below Tp. 53. A method according to claim 52 wherein the composition is at a temperature Ts, where Ts is from 15 to 25�� C., and wherein the SCC polymer has a crystalline melting point, Tp, which is 10 to 30�� C. above Ts. 54. A method according to claim 52 wherein the SCC polymer has an onset of melting temperature, To, such that Tp-To is less than Tp0.. 55. A method according to claim 52 wherein the SCC polymer has a heat of fusion of at least 20 J/g, and an onset-of-melting point To such that (Tp-To) is less than 10�� C. 56. A method of treating a substrate selected from human skin, human hair and human nails, the method comprising applying to the substrate a thickened oil composition which is a nail varnish, lipstick, deodorant stick, a hairdressing preparation, foam bath, bath oil or mascara, and which comprises (1) an oil, and (2) dispersed in the oil, a side chain crystalline (SCC) polymer which (a) has a crystalline melting point Tp, and an onset of melting temperature, To, such that (Tp-To) is less than Tp0.7; (b) is soluble in the oil at temperatures above Tp, and (c) consists essentially of (i) 70-99% by weight of repeating units derived from at least one n-alkyl acrylate or methacrylate ester in which the n-alkyl group contains 16 to 22 carbon atoms, (ii) 1-30% by weight of repeating units derived from at least one acrylate or methacrylate ester in which the ester group contains a hydroxyl-substituted alkyl group containing less than 12 carbon atoms, and (iii) 0-29% by weight of repeating units derived from at least one acrylate or methacrylate ester in which the ester group contains an unsubstituted alkyl group containing less than 16 carbon atoms; (d) is substantially free of fluorine atoms, carboxylic acid groups, carboxylic acid salt groups, sulfonic acid groups, sulfonic acid salt groups, amido groups, pyrrolidino groups and imidazole groups; and (e) has been dispersed in the oil by a process which comprises (i) dissolving the polymer in the oil at the temperature above Tp, and (ii) cooling the solution to crystallize the polymer in the oil; the composition being at a temperature Ts which is below Tp. 57. A method according to claim 56 wherein the hydroxyl-substituted alkyl group is a hydroxyethyl, hydroxypropyl, or hydroxybutyl group. 58. A method according to claim 52 wherein the composition contains less than 1% by weight of surface active agents, based on weight of the oil. 59. A method according to claim 52 wherein each of the following conditions is fulfilled by the SCC polymer: (1) at most 1% of the carbon atoms are substituted by one or more fluorine atoms; (2) at most 0.2 mol % of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) at most 0.5% by weight of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) at most 1 mol % of the repeating units are derived from acrylamide (6) at most 0.2 mol % of the repeating units are derived from N-vinylpyrrolidone; (7) at most 0.2 mol % of the repeating units are derived from N-vinylimidazole. 60. A method according to claim 52 wherein each of the following conditions is fulfilled by the SCC polymer: (1) none of the carbon atoms are substituted by one or more fluorine atoms, (2) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (3) none of the repeating units contain a carboxyl group, a carboxyl salt group, a sulfonic acid group, or a sulfonic acid salt group; (4) the polymer has an acidity of less than 0.07 meq/g; (5) none of the repeating units are derived from acrylamide; (6) none of the repeating units are derived from N-vinylpyrrolidone; (7) none of the repeating units are derived from N-vinylimidazole.