Adhesive block ethylenic copolymers, cosmetic compostions containing them and cosmetic use of these copolymers

Abstract

Linear block ethylenic copolymer, comprising: at least two blocks having different glass transition temperatures (Tg); at least one of these blocks having a glass transition temperature of less than equal to 20° C.; the said copolymer also having an adhesion or “tack” value of greater than 1N. Cosmetic composition comprising this copolymer. The copolymer improves the styling power and hold of a hair lacquer, increases the adhesion of a nail varnish and improves the hold and adhesion of a makeup composition.

1 . A linear, block ethylenic copolymer, comprising:
 at least two blocks having different glass transition temperatures, Tg;   at least one of these blocks having a glass transition temperature of less than or equal to 20° C.; and   at least one of the blocks being a hydrophilic block which comprises at least one hydrophilic monomer selected from the group consisting of a cationic monomer and an anionic monomer,   wherein said copolymer also having an adhesion or tack value of greater than 1N.   
     
     
         2 . The copolymer according to  claim 1 , which is a film-forming copolymer. 
     
     
         3 . The copolymer according to  claim 1 , wherein the adhesion or tack value is greater than 2N. 
     
     
         4 . The copolymer according to  claim 3 , wherein the adhesion or tack value is greater than 3N. 
     
     
         5 . The copolymer according to  claim 1 , wherein the difference in glass transition temperatures, Tg between the two blocks having different glass transition temperatures is from 40 to 120° C. 
     
     
         6 . The copolymer according to  claim 5 , wherein the difference in glass transition temperatures, Tg between the two blocks having different glass transition temperatures is from 40 to 110° C. 
     
     
         7 . The copolymer according to  claim 5 , in which the difference in glass transition temperatures, Tg, between the two blocks having different glass transition temperatures is from 40 to 100° C. 
     
     
         8 . The copolymer according to  claim 1 , wherein the number-average mass of the copolymer is from 10,000 to 500,000. 
     
     
         9 . The copolymer according to  claim 1 , wherein the proportion of the block with a glass transition temperature of less than or equal to 20° C. is from 99% to 40% by mass of the copolymer. 
     
     
         10 . The copolymer according to  claim 9 , wherein the proportion of the block with a glass transition temperature of less than or equal to 20° C. is from 95% to 55%. 
     
     
         11 . The copolymer according to  claim 1 , wherein the block with a Tg of less than or equal to 20° C. has a Tg from 20° C. to −100° C. 
     
     
         12 . The copolymer according to  claim 11 , wherein the block with a Tg of less than or equal to 20° C. has a Tg from 20° C. to −95° C. 
     
     
         13 . The copolymer according to  claim 1 , wherein the block with a Tg of less than or equal to 20° C. is a homopolymer or a copolymer and is totally or partly derived from one or more monomers, and wherein the homopolymers prepared from these monomers have glass transition temperatures of less than or equal to 20° C. 
     
     
         14 . The copolymer according to  claim 13 , wherein the block having a glass transition temperature of less than or equal to 20° C. is a homopolymer comprising a single type of monomer having a Tg≦20° C. 
     
     
         15 . The copolymer according to  claim 13 , wherein the one or more monomers is selected from the group consisting of
 an ethylenic hydrocarbon of 2 to 10 C;   an acrylate of formula CH 2 ═CHCOOR 1 , wherein R 1  representing a linear or branched 1 to 12 C alkyl group with the exception of a tert-butyl group, in which one or more hetero atoms chosen from O, N and S is optionally inserted, the said alkyl group also possibly being optionally substituted with one or more substituents chosen from hydroxyl groups and halogen atoms, or R 1  represents a C 1 -C 12  alkyl-POE with repetition of the oxyethylene unit from 5 to 30 times, for example methoxy POE, or R 1  represents a polyoxyethylene group comprising from 5 to 30 ethylene oxide units;   a methacrylate of formula:   
       
         
           
           
               
               
           
         
         wherein R 2  representing a linear or branched 3 to 12 C alkyl group, in which one or more hetero atoms chosen from O, N and S is(are) optionally inserted, the said alkyl group possibly also being optionally substituted with one or more substituents chosen from hydroxyl groups and halogen atoms; 
         a vinyl ester of formula:
   R 3 —CO—O—CH═CH 2    
 
         wherein R 3  represents a linear or branched 2 to 12 C alkyl group; 
         a vinyl ether of a 1 to 12 C alkyl; and 
         a N-(1 to 12 C)alkyl acrylamide. 
       
     
     
         16 . The copolymer according to  claim 13 , wherein the block with a glass transition temperature of less than or equal to 20° C. further comprises one or more other different monomers or additional monomers. 
     
     
         17 . The copolymer according to  claim 15 , wherein said one or more other different monomers or additional monomers is selected from the group consisting of:
 a vinyl compound of formula:
   CH 2 ═CH—R 4 , 
   wherein R 4  is a hydroxyl group; a group   
       
         
           
           
               
               
           
         
         a C 3  to C 8  cycloalkyl group; a C 6  to C 20  aryl group; a C 7  to C 30  aralkyl group; a 4- to 12-membered heterocyclic group containing one or more hetero atoms chosen from O, N and S; a heterocyclyl-alkyl group; said cycloalkyl, aryl, aralkyl, heterocyclic or heterocyclylalkyl group being optionally substituted with one or more substituents chosen from hydroxyl groups, halogen atoms and linear or branched 1 to 4 C alkyl groups that optionally has one or more hetero atoms chosen from O, N, S and P, and said alkyl groups are optionally substituted with one or more substituents chosen from hydroxyl groups and halogen atoms; 
         an acrylate of formula:
   CH 2 ═CH—COOR 5    
 
         in which R 5  is a tert-butyl group; a C 3  to C 8  cycloalkyl group; a C 6  to C 20  aryl group; a C 7  to C 30  aralkyl group; a 4- to 12-membered heterocyclic group having one or more hetero atoms chosen from O, N and S; a heterocyclylalkyl group; said cycloalkyl, aryl, aralkyl, heterocyclic or hetero-cyclylalkyl group being optionally substituted with one or more substituents chosen from hydroxyl groups, halogen atoms and linear or branched 1 to 4 C alkyl groups which that optionally has one or more hetero atoms chosen from O, N, S and P, said alkyl groups being optionally substituted with one or more substituents chosen from hydroxyl groups and halogen atoms; 
         a methacrylate of formula
   CH 2 ═C(CH 3 )—COOR 6    
 
       
       wherein R 6  is a linear or branched 1 to 4 C alkyl group, said alkyl group being optionally substituted with one or more substituents chosen from hydroxyl groups and halogen atoms; a C 3  to C 6  cycloalkyl group; a C 6  to C 20  aryl group; a C 7  to C 30  aralkyl group; a 4- to 12-membered heterocyclic group containing one or more hetero atoms chosen from O, N and S; a heterocyclylalkyl group; said cycloalkyl, aryl, aralkyl or heterocyclic or heterocyclylalkyl group being optionally substituted with one or more substituents chosen from hydroxyl groups, halogen atoms and linear or branched 1 to 4 C alkyl groups in which that optionally have one or more hetero atoms chosen from O, N, S and P, said alkyl groups being optionally substituted with one or more substituents chosen from hydroxyl groups and halogen atoms;
 a (meth)acrylamide of formula: 
 
       
         
           
           
               
               
           
         
       
       wherein R 7  and R 8  are identical or different, each represent a hydrogen atom or a linear or branched alkyl group of 1 to 12 carbon atoms. 
     
     
         18 . The copolymer according to  claim 16 , wherein said one or more other different monomers or additional monomers is present in an amount of less than or equal to 50% by weight of the block with a Tg of less than or equal to 20° C. 
     
     
         19 . The copolymer according to  claim 18 , wherein said one or more other different monomers or additional monomers is present in an amount of less than or equal to 45% by weight of the block with a Tg of less than or equal to 20° C. 
     
     
         20 . The copolymer according to  claim 16 , wherein the block with a Tg of less than or equal 10 to 20° C. is formed from a copolymer comprising a first monomer wherein the Tg of the corresponding homopolymer is in the range from more than 20° C. to 200° C., and of a second monomer wherein the Tg of the corresponding homopolymer is in the range from 20° C. to −100° C. 
     
     
         21 . The copolymer according to  claim 1 , wherein said hydrophilic block is a block with a glass transition temperature of greater than 20° C. 
     
     
         22 . The copolymer according to  claim 1 , said hydrophilic block is a block with a glass transition temperature of less than or equal to 20° C. 
     
     
         23 . The copolymer according to  claim 1 , wherein said hydrophilic block comprises one or more hydrophilic monomers whose corresponding homopolymers have glass transition temperatures of greater than 20° C. and one or more other non-hydrophilic monomers whose homopolymers have Tg values of less than or equal to 20° C. 
     
     
         24 . The copolymer according to  claim 21 , wherein said hydrophilic block comprises from 70% to 100% of hydrophilic monomers wherein the Tg values of the corresponding homopolymers are greater than 20° C. 
     
     
         25 . The copolymer according to  claim 21 , wherein said hydrophilic block comprises from 10% to less than 70% of hydrophilic monomers wherein the Tg values of the corresponding homopolymers are greater than 20° C. 
     
     
         26 . The copolymer according to  claim 26 , wherein the hydrophillic monomer is selected from the group consisting of 2-vinylpyridine; 4-vinylpyridine; dimethylaminoethyl methacrylate; diethylaminoethyl methacrylate; dimethylaminopropylacrylamide; and salts thereof. 
     
     
         27 . The copolymer according to  claim 26 , wherein the hydrophillic monomer is at least one member selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, maleic anhydride, itaconic acid, fumaric acid, maleic acid, styrenesulphonic acid, acrylamidopropanesulphonic acid, vinylbenzoic acid, vinylphosphonic acid, and salts thereof. 
     
     
         28 . The copolymer according to  claim 1 , wherein the copolymer is at least one member selected from the group consisting of a diblock copolymer, triblock copolymer, and multiblock copolymer having more than three blocks. 
     
     
         29 . The copolymer according to  claim 28 , wherein the copolymer is a multiblock copolymer, wherein one or two blocks have a Tg of less than or equal to 20° C. and the other blocks have a Tg of greater than 20° C. and less than 20° C. 
     
     
         30 . A cosmetic composition comprising the copolymer according to  claim 1 . 
     
     
         31 . The cosmetic composition according to  claim 30 , comprising from 0.1% to 60% by weight of the copolymer. 
     
     
         32 . The cosmetic composition according to  30 , further comprising a physiologically acceptable medium in which the copolymer is in dissolved or dispersed form. 
     
     
         33 . The cosmetic composition according to  claim 32 , wherein the physiologically acceptable medium comprises one or more suitable solvents forming a hydrophilic phase, wherein the one or more suitable solvents is selected from the group consisting of water, hydrophillic organic solvent, alcohol, linear lower monoalcohols having from 2 to 5 carbon atoms, branched lower monoalcohols having from 2 to 5 carbon atoms, ethanol, isopropanol, n-propanol, polyol, glycerol, diglycerol, propylene glycol, sorbitol, pentylene glycol and polyethylene glycol. 
     
     
         34 . The cosmetic composition according to  claim 33 , wherein the hydrophilic phase further comprises hydrophilic C 2  ethers, C 2  to C 4  aldehydes, or mixtures thereof. 
     
     
         35 . The cosmetic composition according to  34 , wherein said physiologically acceptable medium further comprises a fatty phase comprising fatty substances that are liquid or solid at zoom temperature, wherein the fatty substances are of animal, plant, mineral or synthetic origin. 
     
     
         36 . The cosmetic composition according to  claim 35 , further comprising one or more cosmetically acceptable organic solvents. 
     
     
         37 . The cosmetic composition according to  claim 36 , wherein said physiologically acceptable medium further comprises one or more auxiliary film-forming agents selected from the group consisting of a plasticizer and coalescer. 
     
     
         38 . The cosmetic composition according to  claim 30 , further comprising one or more dyestuffs selected from the group consisting of a water-soluble dye and pulverulent dyestuff, pigment, nacre, and flake. 
     
     
         39 . The composition according to  claim 30 , further comprising fillers. 
     
     
         40 . The cosmetic composition according to  claim 30 , further comprising one or more ingredients commonly used in cosmetics selected from the group consisting of a vitamin, thickener, grace element, softener, sequestering agent, fragrance, acidifying agent, basifying agent, preserving agent, sunscreen, surfactant, antioxidant, agent for preventing hair loss, antidandruff agent, propellant, and mixtures thereof. 
     
     
         41 . The cosmetic composition according to  claim 30 , which is in a form selected from the group consisting of a suspension, a dispersion, a solution, a gel, an emulsion, an oil-in-water emulsion, a water-in-oil emulsion, and a multiple emulsion. 
     
     
         42 . The cosmetic composition according  claim 30 , which is a product selected from the group consisting of a hair product, a lacquer, and a shampoo. 
     
     
         43 . The cosmetic composition according to  claim 30 , wherein the composition is selected from the group consisting of a makeup composition and a nail varnish. 
     
     
         44 . A process for making up or caring for keratin materials, comprising contacting the cosmetic composition according to  claim 30  to the keratin materials. 
     
     
         45 . A method to improve the styling power and the hold of a hair lacquer, comprising
 contacting the copolymer according to  claim 1  with the hair lacquer.   
     
     
         46 . A method to increase the adhesion of a nail varnish, comprising
 contacting the copolymer according to  claim 1  with the nail varnish.   
     
     
         47 . A method to improve the hold and adhesion of a makeup composition, comprising
 contacting the copolymer according to  claim 1  with the makeup composition.   
     
     
         48 . The copolymer according to  claim 1 , wherein the number-average mass of the copolymer is from 50,000 to 200,000. 
     
     
         49 . The copolymer according to  claim 9 , wherein the proportion of the block with a glass transition temperature of less than or equal to 20° C. is from 90% to 50% by mass of the copolymer. 
     
     
         50 . The copolymer according to  claim 11 , wherein the block with a Tg of less than or equal to 20° C. has a Tg from 20 to −90° C. 
     
     
         51 . The copolymer according to  claim 18 , wherein said one or more other different monomers or additional monomers is present in an amount of less than or equal to 40% by weight of the block with a Tg of less than or equal to 20° C. 
     
     
         52 . The copolymer according to  claim 16 , wherein the block with a Tg of less than or equal 10 to 20° C. is formed from a copolymer comprising a first monomer wherein the Tg of the corresponding homopolymer is in the range from more than 20° C. to 120° C., and of a second monomer wherein the Tg of the corresponding homopolymer is in the range from 20° C. to −100° C. 
     
     
         53 . The copolymer according to  claim 22 , wherein said hydrophilic block comprises from 80% to 100% of hydrophilic monomers wherein the Tg values of the corresponding homopolymers are greater than 20° C. 
     
     
         54 . The copolymer according to  claim 22 , wherein said hydrophilic block comprises from 20% to 65% of hydrophilic monomers wherein the Tg values of the corresponding homopolymers are greater than 20° C. 
     
     
         55 . The cosmetic composition according to  claim 30 , comprising from 5% to 50% by weight of the copolymer. 
     
     
         56 . The cosmetic composition according to  claim 30 , comprising from 1% to 40% by weight of the copolymer. 
     
     
         57 . The cosmetic composition according to  claim 30 , which is in a form selected from the group consisting of a cream, a paste, a mousse, a dispersion of vesicles, an ionic lipid, a nonionic lipid, a two-phase lotion, a multi-phase lotion, a spray, a powder, a soft paste, and an anhydrous paste.