Amphoteric ethyl methacrylate copolymers and use thereof
The present invention relates to amphoteric copolymers which comprise ethyl methacrylate, if appropriate a N-vinyllactam compound, at least one monoethylenically unsaturated carboxylic acid and at least one compound with α,β-ethylenically unsaturated double bond and at least one cationogenic and/or cationic group in copolymerized form, to cosmetic and pharmaceutical compositions which comprise such copolymers, to preparation methods, and to the use of these copolymers.
1. A copolymer obtained by free-radical polymerization of a monomer mixture M comprising
a) 30 to 80% by weight of ethyl methacrylate or
30 to 80% by weight of a mixture of ethyl methacrylate and at least one compound of the general formula (I) different from ethyl methacrylate
in which
R 1 is H or CH 3 ,
R 2 is C 1 -C 4 -alkyl,
b) 0 to 40% by weight of at least one N-vinyllactam compound,
c) 5 to 35% by weight of at least one monoethylenically unsaturated carboxylic acid,
d) 0.1 to 30% by weight of at least one compound with a free-radically polymerizable, α,β-ethylenically unsaturated double bond and at least one cationogenic and/or cationic group per molecule,
e) 0 to 20% by weight if appropriate of further free-radically polymerizable monomers different from a), b), c) and d), where the fractions of components a) to e) add up to 100% by weight and where the monomer mixture M comprises at least 20% by weight of ethyl methacrylate,
wherein the ratio of the total molar amount of the carboxyl and carboxylate groups to the total molar amount of the cationogenic and cationic groups is at least 2.
2. The copolymer according to claim 1 , where a) is ethyl methacrylate or a mixture comprising or consisting of ethyl methacrylate and tert-butyl acrylate.
3. The copolymer according to claim 1 , where b) is chosen from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam and mixtures thereof.
4. The copolymer according to claim 1 , where c) consists of methacrylic acid or a mixture of methacrylic acid with at least one further monoethylenically unsaturated carboxylic acid.
5. The copolymer according to claim 1 , where c) consists of methacrylic acid or a mixture of methacrylic acid and acrylic acid.
6. The copolymer according to claim 4 , where the weight ratio of methacrylic acid to the further monoethylenically unsaturated carboxylic acids is at least greater than 1.
7. The copolymer according to claim 1 , where d) is chosen from the group of compounds with a free-radically polymerizable, α,β-ethylenically unsaturated double bond and at least one amino and/or ammonium group.
8. The copolymer according to claim 7 , where the at least one amino group of component d) is chosen from primary, secondary and tertiary amino groups.
9. The copolymer according to claim 1 , where d) is chosen from the group consisting of
d1) esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols which may be mono- or dialkylated on the amine nitrogen,
d2) amides of α,β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group,
d3) N,N-diallylamine,
d4) N,N-diallyl-N-alkylamines and derivatives thereof,
d5) vinyl- and allyl-substituted nitrogen heterocycles,
d6) vinyl- and allyl-substituted heteroaromatic compounds and mixtures thereof.
10. The copolymer according to claim 1 obtainable by free-radical polymerization of a monomer mixture M comprising
a) 30 to 70% by weight of component a)
b) 10 to 40% by weight of component b)
c) 10 to 25% by weight of component c)
d) 0.5 to 5% by weight of component d).
11. The copolymer according to claim 1 obtainable by free-radical polymerization of a monomer mixture M comprising
a) 50 to 80% by weight of component a)
b) 0% by weight of component b)
c) 15 to 35% by weight of component c)
d) 0.5 to 12% by weight of component d).
12. The copolymer according to claim 1 , where
a) is ethyl methacrylate,
b) is N-vinylpyrrolidone or N-vinylcaprolactam or mixture thereof,
c) is methacrylic acid or a mixture of methacrylic acid and acrylic acid and
d) is monomer chosen from the group consisting of N-[3-(dimethyl-amino)propyl]meth)acrylamide, N-(tert-butyl)aminoethyl methacrylate, vinylimidazole and mixtures thereof.
13. A cosmetic or pharmaceutical composition comprising
A) at least one copolymer according to claim 1 and
B) at least one cosmetically or pharmaceutically acceptable carrier.
14. The composition according to claim 13 , where the component B) is chosen from
i) water,
ii) water-miscible organic solvents, preferably C 2 -C 4 -alkanols, in particular ethanol,
iii) oils, fats, waxes,
iv) esters of C 6 -C 30 -monocarboxylic acids with mono-, di- or trihydric alcohols which are different from iii),
v) saturated acyclic and cyclic hydrocarbons,
vi) fatty acids,
vii) fatty alcohols,
viii) propellant gases
and mixtures thereof.
15. The composition according to claim 13 , comprising at least one additive different from the components A) and B) which is chosen from cosmetically active ingredients, emulsifiers, surfactants, preservatives, perfume oils, thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, photoprotective agents, bleaches, gel formers, care agents, colorants, tinting agents, tanning agents, dyes, pigments, bodying agents, humectants, regreasing agents, collagen, protein hydrolyzates, lipids, antioxidants, antifoams, antistats, emollients and softeners.
16. The composition according to claim 13 , additionally comprising at least one nonionic, one anionic or one ampholytic polymer.
17. The composition according to claim 16 , where the anionic polymer is a polyurethane.
18. The composition according to claim 13 , where acid groups, in particular carboxyl groups, present in the composition are at least partially neutralized by silicone polymers comprising amino groups.
19. The composition according to claim 13 in the form of a gel, foam, spray, mousse, ointment, cream, emulsion, suspension, lotion, milk or paste.
20. The composition according to claim 13 , where the composition has a fraction of volatile organic components of at most 80% by weight, preferably at most 55% by weight.
21. A skin-cleansing composition, a composition for the care and protection of the skin, a nailcare composition, a preparation for decorative cosmetics, or a hair-treatment composition comprising the copolymer according to claim 1 .
22. The hair-treatment composition according to claim 21 , wherein said hair-treatment composition is a setting agent and/or a conditioner.
23. The hair-treatment composition according to claim 22 , wherein said hair-treatment composition is in the form of a hair gel, shampoo, setting foam, hair tonic, hair spray or hair foam.
24. An auxiliary in pharmacy comprising the copolymer according to claim 1 .
25. A method of preparing copolymers according to claim 1 comprising the steps
a) free-radical polymerization of the monomer mixture M comprising the components a), b), c), d) and if appropriate e) at a pH in the range from 5 to 8, preferably 6.5 to 7.5,
b) adjustment of the pH when polymerization is complete to a value in the range from 5 to 7, preferably 5.5 to 6.5,
c) steam distillation of the polymerization solution,
d) if appropriate adjustment of the pH of the distilled polymerization solution to a value in the range from 7.5 to 9.0, preferably 8.0 to 8.5 after the steam distillation.
26. The auxiliary in pharmacy according to claim 24 , wherein said copolymer is or in a coating for solid drug forms, for modifying rheological properties, a surface-active compound, an adhesive, or a coating for the textile, paper, printing or leather industry.