WO2005002532A2 - Cosmetic agent containing at least one soluble copolymer having (meth)acrylamide units - Google Patents

Abstract

The invention relates to a cosmetic agent, which contains at least one water-soluble copolymer, which can be obtained by radically copolymerizing acrylamide and/or methacrylamide and additional water-soluble alpha , beta -ethylenically unsaturated compounds that can be copolymerized therewith, optionally in the presence of a water-soluble polymeric graft base.

Description

Cosmetic composition containing at least one water-soluble copolymer with (meth) acrylic acid amide units

description

The present invention relates to a cosmetic composition which contains at least one water-soluble copolymer which can be obtained by radical copolymerization of acrylic acid amide and / or methacrylic acid amide and further water-soluble α, β-ethylenically unsaturated compounds which can be copolymerized therewith, optionally in the presence of a water-soluble polymeric graft base.

Cosmetically and pharmaceutically acceptable water-soluble polymers are widely used in cosmetics and medicine. In soaps, creams and lotions, for example, they usually serve as formulating agents, e.g. as a thickener, foam stabilizer or water absorbent or to alleviate the irritating effects of other ingredients or to improve the dermal application of active ingredients. Your task in hair cosmetics is to influence the properties of the hair. In pharmacy, for example, they serve as coating agents or binders for solid pharmaceutical forms.

For hair cosmetics, film-forming polymers are used, for example, as conditioners to improve dry and wet combability, feel, gloss and appearance, and to give the hair antistatic properties. Water-soluble polymers with polar, frequently cationic functionalities are preferred, which have a greater affinity for the structurally determined negatively charged surface of the hair. The structure and mode of action of various hair treatment polymers are described in Cosmetic & Toiletries 103 (1988) 23. Commercially available conditioner polymers are e.g. cationic hydroxyethyl cellulose, cationic polymers based on N-vinylpyrrolidone, e.g. Copolymers of N-vinylpyrrolidone and quaternized N-vinylimidazole, acrylamide and diallyl-dimethylammonium chloride or silicone.

For example, vinyl lactam homo- and copolymers and carboxylate group-containing polymers are used to set hairstyles. Requirements for hair setting resins include, for example, strong strengthening with high air humidity, elasticity, washability from the hair, compatibility in the formulation and a pleasant grip on the hair treated with it.

It is often difficult to provide products with a complex property profile. There is a need for polymers for cosmetic compositions which are capable of forming essentially smooth, tack-free films which are suitable for the hair and the skin Give skin a pleasant grip and at the same time have a good conditioning effect or firming effect. In addition, cosmetic and pharmaceutical products are increasingly subject to aesthetic demands from consumers. A preference for clear, opaque formulations in the form of gels is currently observed with such products.

US 5,478,553 and US 5,632,977 describe hair setting compositions containing homo- or copolymers of N-vinylformamide. A suitable comonomer is u. a. also called acrylamide.

US Pat. No. 5,334,287 discloses graft polymers which can be obtained by radical-initiated polymerization of N-vinylcarboxamides, preferably N-vinylformamide, and, if appropriate, other monomers in the presence of monosaccharides, oligosaccharides and polysaccharides. In addition to a large number of other monomers, acrylamide and methacrylamide are also mentioned as additional monomers. A suitability of these graft copolymers as an active ingredient in cosmetic formulations is not mentioned.

WO 02/15854 describes the use of graft copolymers which can be obtained by radical graft copolymerization of at least one open-chain N-vinylamide compound and, if appropriate, at least one further monomer which can be copolymerized therewith on a polymeric graft base, for cosmetic applications.

The present invention has for its object to provide cosmetic and pharmaceutical compositions with good application properties. These are said to be capable of forming tack-free smooth films. In particular, they should have a good strengthening effect and are suitable for the production of products in the form of gels.

Surprisingly, it has now been found that this object is achieved by a cosmetic agent which contains at least one water-soluble copolymer which, by radical copolymerization of acrylic acid amide and / or methacrylic acid amide and other water-soluble α, β-ethylenically unsaturated compounds which can be copolymerized therewith, optionally in the presence of a water-soluble polymeric graft base is available. The invention therefore relates to a cosmetic or pharmaceutical composition containing

A) at least one water-soluble or water-dispersible copolymer which can be obtained by radical copolymerization of a) 5 to 90% by weight, based on the total weight of components a) to d), acrylic acid amide and / or methacrylic acid amide, b) 0 to 85% by weight, based on the total weight of components a) to d), of at least one α, β-ethylenically unsaturated amide group-containing compound of the general formula I.

R ¹ -NR ² R ³ where

R ^{1 stands} for a group of the formula CH ₂ = CR ⁴ - with R ⁴ = H or C _r C ₄ alkyl and R ² and R ³ independently of one another stand for H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, with the proviso that one of the radicals R ² and R ^{3 is} different from H, or R ² and R ³ together with the nitrogen atom to which they are attached represent a five- to eight-membered heterocycle, or R ^{2 is} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ³ independently of one another are H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ¹ and R ³ together with the amide group to which they are attached for a lactam are with 5 to 8 ring atoms, c) 0 to 40% by weight, based on the total weight of components a) to d), of at least one unsaturated water-soluble compound which is copolymerizable with components a) and b), the proportion by weight the sum of components b) and c) is at least 5% by weight, ge optionally in the presence of up to 25% by weight, based on the total weight of components a) to d), of at least one water-soluble component d) which is selected from d1) polyether-containing compounds, d2) polymers which contain at least 50% by weight. % Have repeat units derived from vinyl alcohol, d3) starch and starch derivatives, and mixtures thereof, and

B) at least one cosmetically acceptable carrier.

In the context of the present invention, the expression alkyl includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups include linear or branched Cι-C ₇ alkyl, CrC preferably ₃ alkyl and more preferably Cι-C ₄ - alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl , 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl , 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1 -Ethyl-2-meth-ylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl etc.

Suitable longer-chain C ₈ -C ₃ o-alkyl or C ₈ -C ₃ alkenyl groups are straight-chain and branched alkyl or alkenyl groups. Preferably, these are predominantly linear alkyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols, which may optionally also be mono-, di- or polyunsaturated. These include, for example, n-hexyl (en), n-heptyl (en), n-octyl (en), n-nonyl (en), n-decyl (en), n-undecyl (en), n-dodecyl (en ), n-tridecyl (en), n-tetradecyl (en), n-pentadecyl (en), n-hexadecyl (en), n-heptadecyl (en), n-octadecyl (en), n-nonadecyl (en) Etc.

Cycloalkyl is preferably C ₅ -C ₈ cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The term heterocycloalkyl for the purposes of the present invention encompasses saturated, cycloaliphatic groups with generally 4 to 7, preferably 5 or 6 ring atoms, in which 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from the elements oxygen, nitrogen and sulfur, and may be optionally substituted, where in the case of substitution these heterocyclo aliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1 substituent, selected from alkyl, aryl, COOR ^a, COO ^_ M ⁺ and NE e ^2, preferably alkyl, can wear. Examples of such heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, called tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, and tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl, tetrahydroflanyl. Aryl comprises unsubstituted and substituted aryl groups and is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl, tolyl, xylyl or mesityl. Substituted aryl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, SO ₃ H, sulfonate, NE ¹ E ² , alkylene-NE ¹ E ^Z , nitro, cyano or halogen.

Hetaryl is preferably pyrrolyl, pyrazolyl, imidazolyl, indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.

In the following, compounds which can be derived from acrylic acid and methacrylic acid are sometimes shortened by inserting the syllable "(meth)" into the compound derived from acrylic acid.

The agents according to the invention can advantageously be formulated as gels under normal conditions (20 ° C.). "Gel-like consistency" means agents that have a higher viscosity than a liquid and that are self-supporting, i.e. which retain a shape given to them without a form-stabilizing covering. In contrast to solid formulations, gel-like formulations can easily be deformed using shear forces. The viscosity of the gel-like agents are preferably in a range from greater than 600 to about 60,000 mPas.

In the context of the present invention, water-soluble monomers and polymers are understood to mean monomers and polymers which dissolve at least 1 g / l in water at 20 ° C. Water-dispersible polymers are understood to mean polymers which break down into dispersible particles using shear forces, for example by stirring.

The copolymers A) according to the invention and used for the production of the cosmetic compositions according to the invention preferably do not contain any monomers copolymerized with acid groups.

If the free-radical copolymerization of components a) and optionally b) and / or c) takes place in the presence of at least one compound of component d), copolymers A) with advantageous properties are obtained. This can result, for example, from at least partial grafting onto component d) as the graft base. However, mechanisms other than grafting are also conceivable. Component A) generally includes the radical copolymerization process products, including, for example, pure graft polymers, mixtures of graft polymers with ungrafted compounds of component d), homo- and copo- polymerizates of the monomers a) and optionally b) and / or c) and any mixtures can be understood. Proportions of ungrafted compounds of component d) can be advantageous depending on the intended use of the copolymers A). For example, they can have an effect as an emulsifier or protective colloid.

The copolymer A) contains 5 to 90% by weight, preferably 10 to 85% by weight, particularly preferably 15 to 80% by weight, based on the total weight of components a) to d), polymerized in acrylic acid amide and / or methacrylic acid amide ,

According to a preferred embodiment, the copolymer A) contains 5 to 85% by weight, particularly preferably 10 to 80% by weight, of at least one compound of component b) copolymerized.

The compounds of component b) are preferably selected from N-vinyl lactams, N-vinyl amides of saturated monocarboxylic acids, N-alkyl and N, N-dialkyl amides of α, β-ethylenically unsaturated monocarboxylic acids and mixtures thereof.

Preferred monomers b) are N-vinyl lactams and their derivatives, which may have, for example, one or more CrC ₆ alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, seα-butyl, tert-butyl, etc. These include, for example, 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 etc. Preferably, N-vinylpyrrolidone and N-vinylcaprolactam are used ,

N-vinylamides suitable as monomers b) are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinylyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl- N-methyl propionamide, N-vinyl butyramide and mixtures thereof. N-vinylformamide is preferably used.

Suitable monomers b) N-alkyl- and N, N-dialkylamides α, β-ethylenically unsaturated monocarboxylic acids are, for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N -tert.-butyl (meth) acrylamide, N, N-dimethyl- (meth) acrylamide, N, N-diethyl (meth) acrylamide, etc.

The aforementioned monomers b) can be used individually and in the form of mixtures. According to a preferred embodiment, the copolymer A) contains 3 to 30% by weight, particularly preferably 5 to 25% by weight, of at least one compound of component c) polymerized.

The compounds of component c) are preferably selected from α, -ethylenically unsaturated water-soluble compounds with nonionic, catogenic and cationic hydrophilic groups.

The cationogenic and / or cationic groups of component c) are preferably nitrogen-containing groups, such as primary, secondary and tertiary amino groups and quaternary ammonium groups. The nitrogen-containing groups are preferably tertiary amino groups or quaternary ammonium groups. Charged cationic groups can be derived from the amine nitrogen either by protonation, e.g. with carboxylic acids such as lactic acid or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, or by quaternization, e.g. with alkylating agents such as CrC-alkyl halides or sulfates. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Protonation or quaternization can generally take place both before and after the polymerization.

Suitable compounds c) are, for example, the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, preferably C ₂ -C ₁₂ amino alcohols. These can preferably be monoalkylated or dialkylated on the amine nitrogen C 1 -C ₈ . Examples of suitable acid components of these esters are acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Acrylic acid, methacrylic acid and mixtures thereof are preferably used. Tert-butylaminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate are preferred , N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminocyclohexyl (meth) acrylate etc. Preferably, N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate are used.

Suitable monomers c) of esters of vinyl alcohol with monocarboxylic acids are, for example, vinyl formate, vinyl acetate and vinyl propionate.

Suitable monomers c) vinyl- and allyl-substituted heteroaromatic compounds are, for example, N-vinylimidazole, N-vinyl-2-methylimidazole, etc. Suitable monomers c) are furthermore the amides of the abovementioned α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have a tertiary and a primary or secondary amino group. These include, for example, N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino ) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4 - (Dimethylamino) cyclohexyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] methacrylamide etc. N- [3- (dimethylamino) propyl-jacrylamide, N- [3- (dimethylamino) propyl] methacrylamide are preferred used.

Suitable monomers c) are also polyether acrylates, which in the context of this invention are generally understood to mean esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with polyetherols. Suitable polyetherols are linear or branched substances which have terminal hydroxyl groups and contain ether bonds. Generally they have a molecular weight in the range of about 150 to 20,000. Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers. Suitable alkylene oxides for the production of alkylene oxide copolymers are e.g. Ethylene oxide, propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene oxide. The alkylene oxide copolymers can contain the alkylene oxide units randomly distributed or copolymerized in the form of blocks. Ethylene oxide / propylene oxide copolymers are preferred. Preferred component c) are polyether acrylates of the general formula II

wherein

the order of the alkylene oxide units is arbitrary,

k and I independently of one another represent an integer from 0 to 500, the sum of k and I being at least 5,

R ^{5 represents} hydrogen or CC ₈ alkyl, and

R ^{6 represents} hydrogen or -CC ₁₈ alkyl,

Y represents O or NR ⁷ , where R ^{7 represents} hydrogen, CC ₈ -alkyl or C ₅ -C ₈ -cycloalkyl. K is preferably an integer from 1 to 500, in particular 3 to 250. I is preferably an integer from 0 to 100.

R ^s is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular hydrogen, methyl or ethyl.

R ⁶ in formula II is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl ,

Y in formula II is preferably O or NH.

Suitable polyether acrylates c) are, for example, the polycondensation products of the abovementioned α, β-ethylenically unsaturated mono- and / or dicarboxylic acids and their acid chlorides, amides and anhydrides with polyetherols. Suitable polyetherols can easily be prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule such as water or a short-chain alcohol R ⁶ -OH. The alkylene oxides can be used individually, alternately in succession or as a mixture. The polyether acrylates c) can be used alone or in

Mixtures can be used to produce the polymers used according to the invention.

Suitable polyether acrylates are also urethane (meth) acrylates with alkylene oxide groups. Such compounds are described in DE 198 38 851 (component e2)), to which reference is made in full here.

If desired, copolymers A) can contain at least one crosslinker, i.e. contain a compound with 2 or more than 2 ethylenically unsaturated double bonds in copolymerized form. Crosslinkers are preferably used in an amount of 0.01 to 10% by weight, particularly preferably 0.1 to 3% by weight, based on the total weight of components a) to d).

Crosslinking monomers which can be used are compounds having at least two ethylenically unsaturated double bonds, for example esters of ethylenically unsaturated carboxylic acids, such as acrylic acid or methacrylic acid and polyhydric alcohols, ethers of at least dihydric alcohols, for example vinyl ether or allyl ether. Examples of the underlying alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4 - Butanediol, but-2-en-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,10-decanediol, 1,2 -Dodecanediol, 1,12-dodecanediol, neopentyl glycol, 3-methyl-pentane-1,5-diol, 2,5-dimethyl-1, 3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1 , 2-cyclohexanediol,, 4-cyclohexanediol, 1,4-bis (hydroxymethyl) cyclohexane, hydroxypivalic acid neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) propaπ, 2,2-bis [4- ( 2-hydroxypropyl) phenyl] propane, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thio-pentane-1,5-diol, as well as polyethylene glycols, polypropylene glycols and polytetrahydrofurans with molecular weights of 200 to 10000 each, except for the homopolymer Ethylene oxide or propylene oxide can also be block copolymers of eth ylene oxide or propylene oxide or copolymers which contain built-in ethylene oxide and propylene oxide groups. Examples of underlying alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose. Of course, the polyhydric alcohols can also be used as the corresponding ethoxylates or propoxylates after reaction with ethylene oxide or propylene oxide. The polyhydric alcohols can also first be converted into the corresponding glycidyl ethers by reaction with epichlorohydrin.

Further suitable crosslinkers are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C ₃ to C ₆ carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol , Cinnamon alcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. However, the monohydric, unsaturated, saturated alcohols can also be esterified with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.

Other suitable crosslinkers are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.

Also suitable are straight-chain or branched, linear or cyclic aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated to the aliphatic hydrocarbons, for example divinylbenzene, divinyltoluene, 1, 7-octadiene, 1,9-decadiene , 4-vinyl 1-cyclohexene, trivinylcyclohexane or polybutadienes with molecular weights from 200 to 20,000.

Amides of unsaturated carboxylic acids, such as e.g. Acrylic and methacrylic acid, itaconic acid, maleic acid, and N-allylamines of at least divalent amines, such as, for example, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1 , 6-diaminohexane, 1, 12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine. The amides of allyl amine and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above, are also suitable.

Triallylamine or corresponding ammonium salts, e.g. Triallylmethylammonium chloride or methyl sulfate, suitable as a crosslinking agent.

Furthermore, N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes, for example of urea, ethylene urea, propylene urea or tartaric acid diamide, e.g. N.N'-divinylethyleneurea or N, N'-divinylpropyleneurea can be used.

Other suitable crosslinkers are divinyl dioxane, tetraallylsilane or tetravinylsilane.

Particularly preferred crosslinking agents are, for example, methylenebisacrylamide, divinylbenzene, triallylamine and triallylammonium salts, divinylimidazole, N.N'-divinylethyleneurea, reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic acid esters and acrylic acid esters of polyalkylene oxides or polyhydric alcohols / with ethylene oxide or propylene oxide and / or epichlorohydrin have been reacted, and allyl or vinyl ethers of polyhydric alcohols, for example 1,2-ethanediol, 1,4-butanediol, diethylene glycol, trimethylolpropane, glycerol, pentaerythritol, sorbitan and sugars such as sucrose, glucose, mannose.

Pentaerythritol triallyl ether, allyl ethers of sugars such as sucrose, glucose, mannose, divinylbenzene, N, N'-methylenebisacrylamide, N, N'-divinylethylene urea, and (meth) acrylic acid esters of glycol, butanediol, trimethylolpropane or glycerol or are particularly preferred as crosslinking agents (Meth) acrylic acid esters of glycol, butanediol, trimethylolpropane or glycerol reacted with ethylene oxide and / or epichlorohydrin. N, N'-Methyl bisacrylamide, diallyltonic acid diamide, diallyl phthalate, diallyl urea, glycol di (meth) acrylate, allyl (meth) acrylate and polyallyl ether are very particularly preferred. According to a suitable embodiment, the copolymerization for the preparation of the copolymers A) takes place in the presence of at least one compound of component d).

According to a preferred embodiment, the amount of component d) used is 1 to 25% by weight, particularly preferably 3 to 20% by weight, based on the total weight of components a) to d).

The compounds of component d) used according to the invention essentially contain no carbon-carbon double bonds. According to a suitable embodiment, the compounds of component d) contain no groups containing silicon atoms.

Suitable polyether-containing compounds d1) are generally water-soluble or water-dispersible, nonionic polymers which have polyalkylene glycol groups. The proportion of polyalkylene glycol groups is preferably at least 40% by weight, based on the total weight of the compound d1). The aforementioned polyalkylene glycols, polyesters based on polyalkylene glycols and polyether urethanes can be used as the polyether-containing compound d1), for example.

Depending on the type of monomer building blocks used for their preparation, the polyether-containing compounds d1) contain the following structural units:

- (CH ₂ ) ₂ -O-, - (CH ₂ ) ₃ -0-, - (CH ₂ ) ₄ -O-, -CH ₂ -CH (R ⁸ ) -O-, wherein

R ^{8 is} C ^ C ^ alkyl, preferably CτC alkyl.

The compounds d1) can additionally have bridging groups which are selected, for example, from

-C (= O) -O-, -OC (= O) -O-, -C (= 0) -NR ^a -, -OC (= O) -NR ^a -, -NR ^b - (C = O ) -NR ^a -, in which R ^a and R independently of one another are hydrogen, C ₁ -C ₃ o-alkyl, preferably CrOralkyl or cycloalkyl.

Preferred polyethers d1) used are polymers of the general formula III with a molecular weight> 300

in which the variables have the following meaning independently of one another:

R ^{10 is} hydrogen, d-Cz ^ Alk 1, R ⁸ -C (= O) -, R ⁸ -NH-C (= O) -, polyalcohol radical;

R ^{11 is} hydrogen, dC ₂₄ alkyl, R ⁸ -C (= O) -, R ^B -NH-C (= O) -;

R ⁸ dC ₂₄ alkyl;

A -C (= O) -O, -C (= O) -B-C (= O) -O, -C (= O) -NH-B-NH-C (= O) -0;

B - (CH ₂ ) _t -, optionally substituted cycloalkylene, heterocycloalkylene or arylene;

n 1 to 200, preferably 1 to 100;

s 0 to 1000, preferably 0 to 100;

t 2 to 12, preferably 2 to 6;

u 1 to 1000, preferably 1 to 500;

0 to 1000, preferably 1 to 500;

w 0 to 1000, preferably 1 to 500;

0 to 1000, preferably 1 to 500;

0 to 1000, preferably 1 to 500;

z 0 to 1000, preferably 1 to 500.

The terminal primary hydroxyl groups of the polyethers prepared on the basis of polyalkylene oxides and the secondary OH groups of polyglycerol can both be freely available in unprotected form and etherified or esterified with alcohols with a chain length CC ₂₄ or with carboxylic acids with a chain length CC ₂₄ are or reacted with isocyanates to form urethanes. Polyether urethanes are preferably used.

As preferred representatives of the alkyl radicals mentioned above, branched or unbranched C Ci∑-, particularly preferably CC ₆ -alkyl chains are mentioned.

The molecular weight of the polyethers is in the range greater than 300 (by number average), preferably in the range from 300 to 100,000, particularly preferably in the range from 500 to 50,000, very particularly preferably in the range from 800 to 40,000.

Homopolymers of ethylene oxide or copolymers with an ethylene oxide content of 40 to 99% by weight are advantageously used. The proportion of ethylene oxide polymerized in is therefore 40 to 100 mol% for the ethylene oxide polymers to be used with preference. Propylene oxide, butylene oxide and / or isobutylene oxide are suitable as comonomers for these copolymers. For example, copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide are suitable. The ethylene oxide content of the copolymers is preferably 40 to 99 mol%, the propylene oxide content 1 to 60 mol% and the content of butylene oxide in the copolymers 1 to 30 mol%. In addition to straight-chain, branched homopolymers or copolymers can also be used as polyether-containing compounds d1).

Branched polymers can be prepared, for example, by using polyalcohol residues, e.g. on pentaerythritol, glycerol or on sugar alcohols such as D-sorbitol and D-mannitol but also on polysaccharides such as cellulose and starch, ethylene oxide and optionally also propylene oxide and / or butylene oxides. The alkylene oxide units can be randomly distributed in the polymer or in the form of blocks.

However, it is also possible to use polyesters of polyalkylene oxides and aliphatic or aromatic dicarboxylic acids, e.g. Oxalic acid, succinic acid, adipic acid and terephthalic acid with molecular weights from 1500 to 25000, e.g. described in EP-A-0 743 962 to be used as a polyether-containing compound. Furthermore, polycarbonates can also be obtained by reacting polyalkylene oxides with phosgene or carbonates, e.g. Diphenyl carbonate and polyurethanes can be used by reacting polyalkylene oxides with aliphatic and aromatic diisocyanates.

According to a preferred embodiment, a component d1) which comprises at least one polyether urethane is used to prepare the copolymers A). Suitable polyether urethanes are the condensation products of polyether polyols, such as polyether diols, with polyisocyanates, such as diisocyanates. Suitable polyether polyols are the aforementioned polyalkylene glycols, which are obtainable, for example, from the polymerization of cyclic ethers, such as tetrahydrofuran, or from the reaction of one or more alkylene oxides with a starter molecule which has two or more active hydrogen atoms.

Suitable polyisocyanates are selected from compounds with 2 to 5 isocyanate groups, isocyanate prepolymers with an average number of 2 to 5 isocyanate groups, and mixtures thereof. These include e.g. aliphatic, cycloaliphatic and aromatic di-, tri- and polyisocyanates. Suitable diisocyanates are e.g. Tetramethylene diisocyanate, hexamethylene diisocyanate, 2,3,3-trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate, 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and their isomer mixtures (eg 80% 2.4 - And 20% 2,6-isomer), 1,5-naphthylene diisocyanate, 2,4- and 4,4'-diphenylmethane diisocyanate. A suitable triisocyanate is e.g. Triphenylmethane-4,4 ', 4 "-triisocyanate. Also suitable are isocyanate prepolymers and polyisocyanates which can be obtained by adding the abovementioned isocyanates to polyfunctional compounds containing hydroxyl or amine groups. Polyisocyanates which are formed by biuret or isocyanurate formation are also suitable. Preferred hexamethylene diisocyanate, trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof are used.

Polymers d2) which have at least 50% by weight of vinyl alcohol units are furthermore preferably suitable as the round graft. These polymers preferably contain at least 70% by weight, very particularly preferably 80% by weight, of polyvinyl alcohol units. Such polymers are usually produced by polymerization of a vinyl ester and subsequent at least partial alcoholysis, aminolysis or hydrolysis. Vinyl esters of linear and branched C Ci ₂ carboxylic acids are preferred; vinyl acetate is very particularly preferred. The vinyl esters can of course also be used in a mixture.

Comonomers of the vinyl ester for the synthesis of the graft base d2) are, for example, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, 3-methyl-1- vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate, diallylammonium chloride, styrene, alkylstyrenes in question.

Further suitable comonomers for the preparation of the graft base d2) are, for example, monoethylenically unsaturated C ₃ -C ₆ -carboxylic acids such as, for example, acrylic acid, methacrylic acid, crotonic acid, fumaric acid, and their esters, amides and nitriles such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxy propyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, Hydroxypropylmeth- acrylate, Hydroxyisobutylacrylat, Hydroxyisobutylmethacrylat, monomethyl maleate, dimethyl maleate, monoethyl maleate , Ethyl maleate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, maleic anhydride and its half esters, alkylene glycol (meth) acrylates, acrylamide, methacrylamide, N-dimethylacrylamide, N-tert.-butylacrylamide, acrylonitrile, methacrylonitrile, vinyl ethers such as methyl, ethyl Butyl or dodecyl vinyl ether, cationic monomers such as dialkylaminoalkyl (meth) acrylates and dialkylaminoalkyl (meth) acrylamides such as dimethyaminomethyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the salts of the z Ultimately mentioned monomers with carboxylic acids or mineral acids as well as the quaternized products.

Preferred graft bases d2) are polymers which are produced by homopolymerization of vinyl acetate and subsequent at least partial hydrolysis, alcoholysis or aminolysis.

The graft base d2) is prepared by known processes, for example solution, precipitation, suspension or emulsion polymerization, using compounds which form free radicals under the polymerization conditions. The polymerization temperatures are usually in the range from 30 to 200 ° C., preferably 40 to 110 ° C. Suitable initiators are, for example, azo and peroxy compounds and the customary redox initiator systems, such as combinations of hydrogen peroxide and reducing compounds, for example sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. These systems can optionally also contain small amounts of a heavy metal salt.

To prepare the graft base d2), the ester groups of the original monomers and optionally further monomers are at least partially cleaved after the polymerization by hydrolysis, alcoholysis or aminolysis. In the following, this process step is generally referred to as saponification. The saponification is carried out in a manner known per se by adding a base or acid, preferably by adding a sodium or potassium hydroxide solution in water and / or alcohol. Methanolic sodium or potassium hydroxide solutions are particularly preferably used. The saponification is carried out at temperatures in the range from 10 to 80 ° C., preferably in the range from 20 to 60 ° C. The degree of saponification depends on the Amount of base or acid used, the saponification temperature, the saponification time and the water content of the solution.

Particularly preferred graft bases d2) are polymers which are prepared by homopolymerization of vinyl acetate and subsequent at least partial saponification. Such polymers containing polyvinyl alcohol available under the name Mowiol ^®.

Starch and / or starch derivatives d3) are preferably used as component d). These include substances that contain saccharide structures. Such natural substances are, for example, saccharides of plant or animal origin or products which have been produced by metabolization by microorganisms, and their degradation products. Suitable graft bases d3) are, for example, oligosaccharides, polysaccharides, oxidatively, enzymatically or hydrolytically degraded polysaccharides, oxidatively hydrolytically degraded or oxidatively enzymatically degraded polysaccharides, chemically modified oligosaccharides or polysaccharides and mixtures thereof. Preferred products are the compounds mentioned in US Pat. No. 5,334,287 in column 4, line 20 to column 5, line 45.

Suitable commercially available products are the C- ^Pur® and C- ^Dry® brands from Cerestar.

If desired, mixtures of compounds of component d) can be used. Advantages are e.g. Mixtures containing at least one compound d2) and at least one compound d3).

The copolymer A) according to the invention and used in the agents according to the invention is preferably obtainable by radical copolymerization of

a) 10 to 45% by weight, based on the total weight of components a) to d), of methacrylic acid amide,

b) 60 to 90% by weight, based on the total weight of components a) to d) vinylpyrrolidone and / or vinylcaprolactam,

c) 0 to 25% by weight, based on the total weight of components a) to d) of at least one of a) and b) different, copolymerizable therewith copolymerizable unsaturated water-soluble compound, optionally in the presence of up to 20% by weight on the total weight of components a) to d), polymers d2) and / or starch and starch derivatives d3). The copolymer A) is particularly preferably obtainable by free-radical polymerization of

a) 30 to 40% by weight of methacrylic acid amide,

b) 30 to 60% by weight of vinyl pyrrolidone,

in the presence of 1 to 20% by weight of polymers d2) and / or starch and starch derivatives d3).

Furthermore, the copolymer A) is particularly preferably obtainable by free-radical polymerization of

a) 30 to 40% by weight of methacrylic acid amide,

b) 20 to 60% by weight vinyl pyrrolidone and 1 to 20% by weight vinyl caprolactam.

Also preferred is the copolymer A), obtainable by radical polymerization of

a) 30 to 40% by weight of methacrylic acid amide,

b) 20 to 60% by weight of vinylpyrrolidone and c) 1 to 20% by weight of at least one water-soluble compound which is different from a) and b) and can therefore be copolymerized.

The copolymers A) are prepared by customary processes known to those skilled in the art, preferably by solution polymerization.

The polymerization temperatures are preferably in a range from about 30 to 120 ° C., particularly preferably 40 to 100 ° C. The polymerization is usually carried out under atmospheric pressure, but it can also take place under reduced or elevated pressure. A suitable pressure range is between 1 and 5 bar.

To prepare the polymers, the monomers can optionally be polymerized in the presence of component d) both with the aid of initiators which form free radicals and by the action of high-energy radiation, which should also be understood to mean the action of high-energy electrons. The peroxo and / or azo compounds customary for this purpose can be used as initiators for the radical polymerization, for example alkali metal or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert- Butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permaleinate, cumene hydroperoxide, diisopropyl peroxidicarbamate, bis- (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl peroxide, tert-butyl peroxide, Di-tert-ayl peroxide, tert-butyl hydroperoxide, azo-bis-isobutyronitrile, azo-bis (2-amidonopropane) dihydrochloride or 2-2'-azo-bis (2-methyl-butyronitrile). Initiator mixtures or redox initiator systems, such as, for example, ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate, are also suitable.

The polymerization can also be carried out by exposure to ultraviolet radiation, if appropriate in the presence of UV initiators. For the polymerization under the action of UV rays, the photoinitiators or sensitizers which are usually suitable for this are used. These are, for example, compounds such as benzoin and benzoin ether, α-methylbenzoin or α-phenylbenzoin. So-called triplet sensitizers, such as benzyl diketals, can also be used. In addition to high-energy UV lamps, such as carbon arc lamps, mercury vapor lamps or, for example, serve as UV radiation sources

Xenon lamps also have low-UV light sources, such as fluorescent tubes with a high proportion of blue.

The amounts of initiator or initiator mixtures used, based on the monomers used, are generally between 0.01 and 10% by weight, preferably between 0.1 and 5% by weight.

The polymerization can take place, for example, in bulk. In bulk polymerization using a graft base d), this can be dissolved in at least one monomer and possibly further comonomers, and after the addition of a polymerization initiator, the mixture can be polymerized out. The polymerization can also be carried out semi-continuously by initially introducing a portion, for example 10%, of the mixture to be polymerized from the graft base d), at least one monomer from group a), possibly further comonomers and initiator, the mixture being heated to the polymerization temperature and after which Starting the polymerization adds the rest of the mixture to be polymerized after the progress of the polymerization. The polymers can also be obtained by placing the graft base d) in a reactor, heating to the polymerization temperature and adding and polymerizing at least one monomer from group a), possibly further comonomers and polymerization initiator either all at once, batchwise or, preferably, continuously. Polymerization in a solvent is preferred. Suitable solvents are water and mixtures of water with water-miscible solvents, for example alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol, and glycols, such as ethylene - Glycol, propylene glycol and butylene glycol as well as the methyl or ethyl ether of the dihydric alcohols, diethylene glycol, triethylene glycol, glycerin and dioxane.

To adjust the molecular weight, the polymerization can be carried out in the presence of at least one regulator. The usual compounds known to the person skilled in the art, e.g. Sulfur compounds, e.g. Mercaptoethanol, 2-ethyl-hexylthioglycolate, thioglycolic acid or dodecyl mercaptan as well as tribromochloromethane or other compounds which have a regulating effect on the molecular weight of the polymers obtained are used. Silicon-free controllers are preferably used.

Copolymers A) which contain base groups can be partially or completely neutralized. Polymers with amine groups can also be converted into cationic groups by quaternizing agents, for example using alkylating agents such as C 1 -C ₄ -alkyl halides or sulfates. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. The salts of the polymers obtained generally have better water solubility or dispersibility in water than the non-neutralized or quaternized polymers.

If an organic solvent is used in the preparation of the polymers, this can be carried out by customary processes known to those skilled in the art, e.g. by distillation under reduced pressure.

The polymer solutions can be dried by various drying methods, e.g. Spray drying, fluidized spray drying, roller drying or freeze drying in

Powder form are transferred. Spray drying is preferably used. The polymer dry powders obtained in this way can advantageously be dissolved or

Redisperse in water again in an aqueous solution or dispersion.

Powdery copolymers have the advantage of better storage stability, easier transportation and generally have a lower tendency to infest germs.

The invention also relates to copolymers A). The cosmetically acceptable carrier B) is preferably selected from

i) water,

ii) water-miscible organic solvents, preferably dC ₄ alkanols,

iii) oiling, greasing, waxing,

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 and mixtures thereof.

The agents according to the invention have, for example, an oil or fat component B) which is selected from: hydrocarbons of low polarity, such as mineral oils; linear saturated hydrocarbons, preferably with more than 8 carbon atoms, such as tetra-decane, hexadecane, octadecane, etc .; cyclic hydrocarbons such as decahydronaphthalene; branched hydrocarbons; animal and vegetable oils; To grow; Wax esters; Petroleum jelly; Esters, preferably esters of fatty acids, such as the esters of CrC ₂₄ mono alcohols with dC ₂₂ monocarboxylic acids, such as isopropyl isostearate, n-propyl myristate, iso-propyl myristate, n-propyl palmitate, iso-propyl palmitate, hexacosanyl palmitate, octacosanyl , Triacontanyl palmitate, dotriacontanyl palmitate, tetratriacontanyl palmitate, hexancosanyl stearate, octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, tetratriacontanyl stearate; Salicylates, such as dC _{1 (r} salicylates, for example octyl salicylate; benzoate esters, such as C ₁₀ -C ₁₅ -alkyl benzoates, benzyl benzoate; other cosmetic esters, such as fatty acid triglycerides, propylene glycol monolaurate, polyethylene glycol monolaurate, Cι ₀ -Cι ₅ etc. alkyllactates and mixtures thereof.

Suitable silicone oils B) are, for example, linear polydimethylsiloxanes, poly (methylphenylsiloxanes), cyclic siloxanes and mixtures thereof. The number average molecular weight of the polydimethylsiloxanes and poly (methylphenylsiloxanes) is preferably in a range from about 1000 to 150,000 g / mol. Preferred cyclic siloxanes have 4- to 8-membered rings. Suitable cyclic siloxanes are commercially available, for example, under the name cyclomethicone. Preferred oil or fat components B) are selected from paraffin and paraffin oils; Petroleum jelly; natural fats and oils, such as castor oil, soybean oil, peanut oil, olive oil, sunflower oil, sesame oil, avocado oil, cocoa butter, almond oil, peach kernel oil, castor oil, cod liver oil, pork lard, walnut, spermacet oil, sperm oil, wheat germ oil, macadamia oil nut oil, night oil oil, night oil oil Fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cetyl alcohol; Fatty acids such as myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid and various saturated, unsaturated and substituted fatty acids; Waxes such as bee wax, carnauba wax, candililla wax, walrus and mixtures of the oil or fat components mentioned above.

Suitable cosmetically and pharmaceutically acceptable oil or fat components B) are described in Karl-Heinz Schrader, Fundamentals and Recipes for Cosmetics, 2nd edition, Verlag Hüthig, Heidelberg, pp. 319-355, to which reference is made here.

Suitable hydrophilic carriers B) are selected from water, 1-, 2- or polyhydric alcohols with preferably 1 to 8 carbon atoms, such as ethanol, π-propanol, isopropanol, propylene glycol, glycerol, sorbitol, etc.

The cosmetic agents according to the invention can be skin cosmetic, dermatological or hair cosmetic agents.

The agents according to the invention are preferably in the form of a gel, foam, spray, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.

The cosmetically or pharmaceutically active agents according to the invention can additionally contain cosmetically and / or dermatologically active substances and auxiliaries.

Suitable cosmetically and / or dermatologically active substances are, for example, coloring substances, skin and hair pigmentation agents, tinting agents, tanning agents, bleaching agents, keratin-hardening substances, antimicrobial substances, light filter substances, repellent substances, hyperemising substances, keratolytic and keratoplastic agents, antioxidant substances, antioxidant substances, antioxidant substances Keratinizing substances, antioxidant or active substances as radical scavengers, skin-moisturizing or moisturizing substances, moisturizing substances, anti-inflammatory or anti-allergic active substances and mixtures thereof. Artificially tanning agents that are suitable for tanning the skin without natural or artificial radiation with UV rays are, for example, dihydroxyacetone, alloxan and walnut shell extract. Suitable keratin-hardening substances are generally active substances, as are also used in antiperspirants, such as, for example, potassium aluminosulfurate, aluminum hydroxychloride, aluminum lactate, etc. Antimicrobial active substances are used to destroy microorganisms or to inhibit their growth and thus serve both as a preservative and as a deodorizing substance, which reduces the development or intensity of body odor. These include, for example, customary preservatives known to the person skilled in the art, such as p-hydroxybenzoic acid ester, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are, for example, zinc ricinoleate, triclosan, undecylenic acid alkylolamides, citric acid triethyl ether, chlorohexyl ester, chlorhexyl ester are substances that absorb UV rays in the UV-B and / or UV-AB range. Suitable UV filters are, for example, 2,4,6-triaryl-1,3,5-triazines, in which the aryl groups can each carry at least one substituent, which is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and Ethoxycarbonyl and mixtures thereof. Also suitable are p-aminobenzoic acid esters, cinnamic acid esters, benzophenones, camphor derivatives and pigments which block UV rays, such as titanium dioxide, talc and zinc oxide. Suitable repellent agents are compounds that are able to deter or drive away certain animals, especially insects, from humans. These include, for example, 2-ethyl-1,3-hexanediol, N, N-diethyl-m-toluamide, etc. Suitable hyperemising substances that stimulate blood circulation to the skin are, for example, essential oils such as mountain pine, lavender, rosemary, Juniper berries, horse chestnut extract, birch leaf extract, hay flower extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil, etc. Suitable substances with a keratolytic and keratoplastic action include salicylic acid, calcium thioglycolate, sulfuric acid, thioglycolic acid, thioglycolic acid and their active ingredients Examples include sulfur, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate, zinc pyrithione, aluminum pyrithione, etc. Suitable anti-inflammatory drugs that counteract skin irritation include allantoin, bisabolol, dragosantol, chamomile extract, panthenol, etc.

The cosmetic compositions according to the invention can contain at least one cosmetically or pharmaceutically acceptable polymer different from compounds of component A) as a cosmetic and / or pharmaceutical active ingredient (as well as optionally as an auxiliary). These generally include anionic, cationic, amphoteric and neutral polymers. Examples of anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes, such as Luviset PUR ^® from. BASF, and poly-ureas. Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example LuvimerR 100 ^® ), copolymers of ethyl acrylate and methacrylic acid (for example Luviumer ^® MAE), copolymers of N-tert.-butyl acrylate, ethyl acrylate, acrylic acid (Ultrahold ^® 8 , strong), copolymers of vinyl acetate, crotonic acid and optionally other vinyl esters (eg Luviset ^® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, eg carboxy-functional, t-butyl acrylate, methacrylic acid (eg Luviskol ^® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as C ₄ -C ₃₀ alkyl esters of meth (acrylic acid), C -C ₃₀ alkyl vinyl esters, C ₄ -C ₃₀ alkyl vinyl ethers and hyaluronic acid. Examples of anionic polymers are also vinyl acetate / crotonic acid copolymers, such as are, for example, under the names Resyn ^® (National Starch) and Gafset ^® (GAF) and Vi ylpyrrolidon / vinyl acrylate copolymers, obtainable for example under the trademark Luviflex ^® (BASF). Other suitable polymers are the commercially available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymer and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyester.

Other suitable polymers are cationic polymers named poly quaternium according to INCI, for example, copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^® FC, Luviquat ^® HM, Luviquat ^® MS, Luviquat Care ^®), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat ^® PQ 11), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinyl imidazolium salts (Luviquat Hold ^®); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamido copolymers (Polyquatemium-7) and chitosan. Suitable cationic (quaternized) polymers are also Merquat ^® (polymer based on dimethyl yldiallylammonium chloride), Gafquat ^® (quaternary polymers which are formed by reaction of polyvinylpyrrolidone with quaternary ammonium compounds), Polymer J ^® (hydroxyethyl cellulose with cationic groups) and cationic polymers vegetable base ,. eg guar polymers, such as the Jaguar ^® brands from Rhodia.

Other suitable polymers are also neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, polyaspartic derivatives, cellulose derivatives derivatives. These include, for example, Luviflex ^® Swing (partially saponified copolymer of polyvinyl acetate and polyethylene glycol, from BASF). Suitable polymers are also nonionic, water-soluble or wasserdispergier- bare polymers or oligomers, such as polyvinylcaprolactam, including Luviskol Plus ^® (BASF), or polyvinyl pyrrolidone and their copolymers, in particular with Vinylestern such as vinyl acetate, for example, Luviskol ^® VA 37 (BASF); Polyamides, for example based on itaconic acid and aliphatic diamines, as described, for example, in DE-A-43 33238.

Suitable polymers are also amphoteric or zwitterionic polymers such as those sold under the names Amphomer ^® (National starlings) available octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-Hydroxypropylmeth acrylate and zwitterionic polymers, as described for example in DE-A- 39 29 973, DE-A-21 50 557, DE-A-28 17 369 and DE-A-37 08451. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are available under the name Amersette® ^® (AMERCHOL), and acrylate copolymers of hydroxyethyl methacrylate, Methylmeth-, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon ^®).

Suitable polymers are also nonionic, siloxane-containing, water soluble or dispersible polymers, for example, polyether siloxanes, such as Tegopren ^® (Fa. Goldschmidt) or Belsil ^® (Fa. Wacker).

The formulation base of pharmaceutical agents according to the invention preferably contains pharmaceutically acceptable excipients. The excipients known to be usable in the field of pharmacy, food technology and related fields are pharmaceutically acceptable, in particular those listed in relevant pharmacopoeias (e.g. DAB Ph. Eur. BP NF) as well as other excipients whose properties do not conflict with a physiological application.

Suitable auxiliaries can be: lubricants, wetting agents, emulsifying and suspending agents, preservatives, antioxidants, anti-irritants, chelating agents, emulsion stabilizers, film formers, gelling agents, odor masking agents, resins, hydrocolloids, solvents, solubilizers, neutralizing agents, permeation compounds, accelerators, ammonium, pigments Refatting and overfatting agents, ointment, cream or oil base materials, silicone derivatives, stabilizers, sterilants, blowing agents, drying agents, opacifiers, thickeners, waxes, plasticizers, white oils. A relevant design is based on professional knowledge, such as that found in Fiedler, HP Lexicon of auxiliary materials for pharmacy, cosmetics and related areas, 4th ed., Aulendorf: ECV-Editio-Kantor-Verlag, 1996, are shown.

To produce the dermatological agents according to the invention, the active substances can be mixed or diluted with a suitable auxiliary (excipient). Excipients can be solid, semi-solid or liquid materials that can serve as vehicles, carriers or media for the active ingredient. If desired, further auxiliaries are admixed in the manner known to the person skilled in the art.

According to a first preferred embodiment, the agents according to the invention are a skin cleanser.

Preferred skin cleaning agents are soaps with a liquid to gel-like consistency, such as transparent soaps, luxury soaps, deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, paste-like soaps, lubricating soaps and washing pastes, liquid washing, showering and bathing preparations, such as washing lotions, shower baths and -gels, foam baths, oil baths and scrub preparations.

According to a further preferred embodiment, the agents according to the invention are cosmetic agents for the care and protection of the skin, nail care agents or preparations for decorative cosmetics.

It is particularly preferably skin care products, intimate hygiene products, foot care products, light protection agents, repellents, shaving agents, hair removal agents, anti-acne agents, make-ups, mascara, lipsticks, eyeshadows, eye pencils, eyeliner, blushes and eyebrow pencils.

The skin care products according to the invention are in particular W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-wrinkle creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, care lotions and moisturizing lotions.

Skin cosmetic and dermatological agents based on the previously described polymers A) have advantageous effects. The polymers can contribute, among other things, to moisturizing and conditioning the skin and to improving the feeling on the skin. The polymers can also act as thickeners in the formulations. By adding the polymers according to the invention, a considerable improvement in skin tolerance can be achieved in certain formulations.

Skin cosmetic and dermatological agents preferably contain at least one copolymer A) in a proportion of about 0.001 to 30% by weight, preferably 0.01 to 20 wt .-%, very particularly preferably 0.1 to 12 wt .-%, based on the total weight of the agent.

Light stabilizers based on copolymers A) in particular have the property of increasing the residence time of the UV-absorbing ingredients in comparison to conventional auxiliaries such as polyvinylpyrrolidone.

Depending on the field of application, the agents according to the invention can be in a form suitable for skin care, such as applied as a cream, foam, gel, stick, mousse, milk, spray (pump spray or spray containing blowing agent) or lotion.

In addition to the polymers A) and suitable carriers, the skin cosmetic preparations can also contain other active ingredients and auxiliaries customary in skin cosmetics, as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaches, colorants, tinting agents, tanning agents, collagen, protein hydrolyzates, stabilizers, pH regulators , Dyes, salts, thickeners, gelling agents, consistency agents, silicones, humectants, refatting agents and other common additives.

Preferred oil and fat components of the skin cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as paraffins, silicone oils and aliphatic hydrocarbons with more than 8 carbon atoms, animal and vegetable oils, such as sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as triglycerides of C ₆ -C ₃₀ fatty acids, wax esters, such as jojoba oil, fatty alcohols, petroleum jelly, hydrogenated lanolin and acetylated lanolin, and mixtures thereof.

The polymers according to the invention can also be mixed with conventional polymers if special properties are to be set.

To set certain properties such as To improve the feel, the spreading behavior, the water resistance and / or the binding of active ingredients and auxiliary substances such as pigments, the skin cosmetic and dermatological preparations can also contain conditioning substances based on silicone compounds. Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.

The cosmetic or dermatological preparations are produced by customary methods known to the person skilled in the art. The cosmetic and dermatological agents are preferably in the form of emulsions, in particular in the form of water-in-oil (W / O) or oil-in-water (OMQ emulsions). However, it is also possible to choose other types of formulation, for example hydrodispersions , Gels, oils, oleogels, multiple emulsions, for example in the form of W / OΛ / V or OW / O emulsions, anhydrous ointments or ointment bases, etc.

Emulsions are prepared by known methods. In addition to the copolymer A), the emulsions generally contain customary constituents, such as fatty alcohols, fatty acid esters and in particular fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water. The selection of additives specific to the type of emulsion and the preparation of suitable emulsions is described, for example, in Schrader, basics and formulations of cosmetics, Hüthig Buch Verlag, Heidelberg, 2nd edition, 1989, third part, to which express reference is hereby made.

A suitable emulsion, e.g. for a skin cream etc., generally contains an aqueous phase which is emulsified in an oil or fat phase by means of a suitable emulsifier system.

The proportion of the emulsifier system in this type of emulsion is preferably about 4 and 35% by weight, based on the total weight of the emulsion. The proportion of the fat phase is preferably about 20 to 60% by weight. The proportion of the aqueous phase is preferably about 20 and 70%, in each case based on the total weight of the

Emulsion. The emulsifiers are those which are usually used in this type of emulsion. They are selected, for example, from: C ₁₂ -C ₁₈ sorbitan fatty acid esters; Esters of hydroxystearic acid and C ₂ -C ₃ o-fatty alcohols; Mono- and diesters of C ₂ -C ₁₈ fatty acids and glycerol or polyglycerol; Condensates of ethylene oxide and propylene glycols; oxypropylenated / oxyethylated C ₁₂ -C ₁₈ fatty alcohols; polycyclic alcohols such as sterols; high molecular weight aliphatic alcohols such as lanolin; Mixtures of oxypropylene / polyglycerolated alcohols and magnesium isostearate; Succinestem of polyoxyethylene or polyoxypropylene fatty alcohols; and mixtures of magnesium, calcium, lithium, zinc or aluminum lanolate and hydrogenated lanolin or lanolin alcohol.

Preferred fat components which can be contained in the fat phase of the emulsions are: hydrocarbon oils, such as paraffin oil, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in these oils; animal or vegetable oils, such as sweet almond oil, avocado oil, calophylum oil, lanolin and derivatives thereof, castor oil, sesame oil, olive oil, jojoba oil, karite oil, hoplostethus oil; mineral oils whose distillation begins at atmospheric pressure at approx. 250 ° C and whose distillation end point is 410 ° C, such as petroleum jelly oil; Esters of saturated or unsaturated fatty acids, such as alkyl myristates, for example i-propyl, butyl or cetyl myristate, hexadecyl stearate, ethyl or i-propyl palmitate, octanoic or decanoic acid triglycerides and cetyl ricinoleate.

The fat phase can also contain silicone oils soluble in other oils, such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.

To promote the retention of oils, waxes can also be used in addition to the polymers A), such as Carnauba wax, candililla wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.

In general, the water-in-oil emulsions are prepared by placing the fat phase and the emulsifier in a batch container. It is heated at a temperature of about 50 to 75 ° C., then the oil-soluble active substances and / or auxiliaries are added and, with stirring, water is added which has previously been heated to about the same temperature and in which, if appropriate, the water-soluble ones Ingredients previously solved. The mixture is stirred until an emulsion of the desired fineness is obtained and then allowed to cool to room temperature, stirring less if necessary.

According to a further preferred embodiment, the agents according to the invention are a shower gel, a shampoo formulation or a bath preparation.

Such formulations contain at least one polymer A) and usually anionic surfactants as base surfactants and amphoteric and / or nonionic surfactants as cosurfactants. Further suitable active substances and / or auxiliary substances are generally selected from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants as well as thickeners / gel formers, skin conditioners and humectants.

These formulations preferably contain 2 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight, of surfactants, based on the total weight of the formulation. All anionic, neutral, amphoteric or cationic surfactants commonly used in personal cleansing agents can be used in the washing, showering and bathing preparations.

Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isothionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, in particular alkali metal alkali metal sulfates, for example alkali metal alkali metal sulfates Sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.

These include e.g. Sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate,

Ammonium lauryl sulfosuccinate, sodium dodecyl benzene sulfonate, triethanolamine dodecyl benzene sulfonate.

Suitable amphoteric surfactants are e.g. Alkyl betaines, alkylamidopropyl betaines,

Alkyl sulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or propionates, alkyl amphodiacetates or dipropionates.

For example, cocodimethylsulfopropylbetaine, laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate can be used.

Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols with 6 to 20 carbon atoms in the alkyl chain, which can be linear or branched, with ethylene oxide and / or propylene oxide. The amount of alkylene oxide is about 6 to 60 moles per mole of alcohol. Alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkylpolyglycosides or sorbitan ether esters are also suitable.

In addition, the washing, showering and bathing preparations can contain conventional cationic surfactants, such as e.g. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.

In addition, other conventional cationic polymers can also be used, for example copolymers of acrylamide and dimethyldiallylammonium chloride (Polyquaternium-7), cationic cellulose derivatives (Polyquaternium-4, -10), guar hydroxypropyltrimethylammonium chloride (INC !: Hydroxylpropyl Guar Hydroxypropyltrimonium Chloride), copolymers made of N-vinylpyrrolidone and quaternized N-vinylimidazole (polyquaterinium 16, -44, -46), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Polyquaternium-11) and others.

Furthermore, the shower gel / shampoo formulations can include thickeners, e.g. Cooking salt, PEG-55, propylene glycol oleates, PEG-120 methyl glucose dioleates and others, as well as preservatives, other active ingredients and additives and water.

According to a further preferred embodiment, the agents according to the invention are a hair treatment agent.

Hair treatment compositions according to the invention preferably contain at least one copolymer A) in an amount in the range from about 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the composition.

The hair treatment compositions according to the invention are preferably in the form of a foaming agent, hair mousse, hair gel, shampoo, hair spray or hair foam. Hair sprays include both aerosol sprays and pump sprays without propellant. Hair foams include both aerosol foams and pump foams without propellant.

Preferred hair treatment agents are in the form of a gel. Such a hair treatment composition contains, for example:

a) 0.1 to 20% by weight, preferably 1 to 10% by weight, of at least one polymer A), as previously defined,

b) 0 to 40% by weight of at least one carrier (solvent) which is selected from C ₂ -C ₅ alcohols, in particular ethanol,

c) 0.01 to 5% by weight, preferably 0.2 to 3% by weight, of at least one thickener,

d) 0 to 50% by weight of a blowing agent,

e) 0 to 10% by weight, preferably 0.1 to 3% by weight, of at least one of a) different fixing polymer, preferably a water-soluble nonionic polymer,

f) 0 to 1% by weight of at least one refatting agent, preferably selected from glycerol and glycerol derivatives, g) 0 to 30% by weight of further active ingredients and / or auxiliaries, for example at least one silicone compound,

h) water ad 100 wt .-%.

All gel formers customary in cosmetics can be used as gel formers (thickeners). These include slightly cross-linked polyacrylic acid, e.g. Carbomer (INCI) or Acrylates / C 10-30 Alkyl Acrylate Crosspolymer (INCI), Acrylates / Beheneth-25 methacrylate copolymer (INCI), PVM / MA Decadiene Crosspolymer, cellulose derivatives, e.g. Hydroxypropyl cellulose, hydroxyethyl cellulose, cationically modified celluloses, polysaccharides, e.g. Xanthum Gummi, Hydroxypropyl Starch Phosphate, Potato Starch Modified, Caprylic / Capric Triglyceride, Sodium acrylates Copolymer, Polyquaternium- 32 (and) Paraffmum Liquidu (INCI), Sodium Acrylates Copolymer (and) Paraffinum Liquidum (and) PPG- 1 Trideceth-6, Acrylamidopropyl Trimonium Chloride / Acrylamide Copolymer, Steareth-10 Allyl Ether Acrylates Copolymer, Polyquaternium-37 (and) Paraffinum Liquidum (and) PPG- Trideceth-6, Polyacrylamide and C13-14 Isoparaffin and Laureth-7, C13-14 Isoparaffin and Mineral Oil and Sodium Polyacrylate and Polyacrylamide and Polysorbate 85, C13-14 Isoparaffin and Isostearyl Isostearate and Sodium Polyacrylate and Polyacrylamide and Polysorbate 60, Acrylates / Aminoacrylates / C 0-30 Alkyl PEG-20 Itaconate Copolymer, Acrylates / Steareth-20 Itaconate Copolymer, Acrylates / Ceteth-20 Itaconate Copolymer, Polyquaternium 37 (and) Propylene Glycole Dicaprate Dicaprylate (and) PPG-1 Trideceth-6, Polyquatemium-7, Polyquatemium-44.

The hair treatment compositions can also be in the form of hair sprays or hair foams. Hair sprays and hair foams preferably comprise predominantly or exclusively water-soluble or water-dispersible components. If the compounds used in the hair sprays and hair foams according to the invention are water-dispersible, they can be used in the form of aqueous microdispersions with particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm. The solids contents of these preparations are usually in a range from about 0.5 to 20% by weight. These microdispersions generally do not require any emulsifiers or surfactants to stabilize them.

Preferred hair treatment agents are in the form of an aqueous dispersion or in the form of an alcoholic or aqueous-alcoholic solution. Examples of suitable alcohols are ethanol, propanol, isopropanol and mixtures thereof.

Furthermore, the hair treatment compositions according to the invention can generally contain customary cosmetic auxiliaries, for example plasticizers, such as glycerol and glycol; emollients; perfumes; surfactants; UV absorbers; dyes; antistatic agents; Combing agents; Preservatives; and defoamers.

If the compositions according to the invention are formulated as a hairspray, they contain a sufficient amount of a blowing agent, for example a low-boiling hydrocarbon or ether, such as propane, butane, isobutane or dimethyl ether. Compressed gases such as nitrogen, air or carbon dioxide can also be used as blowing agents. The amount of blowing agent can be kept low so as not to unnecessarily increase the VOC content. It is then generally not more than 55% by weight, based on the total weight of the composition. If desired, however, higher VOC contents of 85% by weight and above are also possible.

The polymers A) described above can also be used in combination with other hair polymers in the compositions. Suitable polymers are those described above.

The other hair polymers are preferably present in amounts of up to 10% by weight, based on the total weight of the composition.

A preferred hair treatment agent in the form of a hair spray or hair foam contains:

a) 0.5 to 20% by weight, preferably 1 to 10% by weight, of at least one polymer A), as previously defined,

b) 50 to 99.5% by weight, preferably 55 to 99% by weight, of a carrier (solvent) selected from water and water-miscible solvents, preferably C ₂ -C ₅ alcohols, in particular ethanol, and mixtures thereof,

c) 0 to 70 wt .-%, preferably 0.1 to 50 wt .-%, of a blowing agent, preferably selected from dimethyl ether and alkanes, such as. B. propane / butane mixtures,

d) 0 to 10% by weight, preferably 0.1 to 10% by weight, of at least one hair polymer different from a), preferably a water-soluble or dispersible polymer,

e) 0 to 0.5% by weight, preferably 0.001 to 2% by weight, of at least one water-soluble or water-dispersible silicone compound,

and optionally further active substances and / or auxiliary substances, as previously defined. The component according to the invention can contain, as component e), at least one nonionic, siloxane-containing, water-soluble or water-dispersible polymer, in particular selected from the previously described polyether siloxanes. The proportion of this component is then generally about 0.001 to 2% by weight, based on the total weight of the composition.

The copolymers A) are advantageously suitable as auxiliaries in pharmacy, preferably as or in coating compositions for the textile, paper, printing and leather industries.

The invention is illustrated by the following non-limiting examples.

Examples

General preparation instructions: solution polymerization (example 10)

Feed 1: Monomer mixture of: 240 g (50% aqueous solution) acrylamide and 533.4 g (15% aqueous solution) methacrylamide

Feed 2: monomer mixture of: 120 g vinyl pyrrolidone and 80 g vinyl caprolactam

Feed 3: initiator solution from: 20 g of Wako V 50 [2,2'-azobis (2-amidinopropane) - dihydrochloride] and 180 g of water

Feed 4: initiator solution from: 10 g of Wako V 50 [2,2'-azobis (2-amidinopropane) - dihydrochloride] and 90 g of water

10% of feed 1, 20% of feed 2 and 10% of feed 3 were placed in 490 g of water in a stirring apparatus with reflux condenser, internal thermometer and four separate feed devices and the mixture was heated to approx. 60 ° C. with stirring. After polymerisation, recognizable by the start of a viscosity 35

increase, the remainder of feed 1 was added at 65 ° C. within three hours, the remainder of feed 2 within 1.5 hours and the remainder of feed 3 within 4 hours. After the end of the addition, polymerization was continued for a further two hours at this temperature. Feed 4 was then added to the postpolymerization within 30 minutes at 65.degree. C. and after the end of the addition, postpolymerization was continued for about two hours at this temperature and for a further two hours at a temperature of 80 to 90.degree. An approximately 30% aqueous microdispersion is obtained. To stabilize the solution with 100 ppm of Euxyl ^® K 100 from Schülke & Mayr (5-chloro-2-methyl-3- (2H) -isothiazolone / 2-methyl-3- (2H) -isothiazolone / benzyl alcohol) added. When using water / ethanol mixtures, there is no need to use a stabilizer.

Powdery products can be obtained by spray drying or freeze drying. In analogy, all products in the list below were polymerized.

Table 1

Expl AM MAM VP VCap VFA DMAA 350-MA Q-DMA C-Dry EMA MD1934 PVOH

350-MA polyethylene glycol methacrylate (Mπ = 350)

Q-DMAEMA dimethylaminoethyl methacrylate dimethyl sulfate

C-Dry MD1934 degraded starch (dextrose equivalents DE = 38; Cerestar)

PVOH partially saponified polyvinyl alcohol (MowiolR4-88, Clariant)

Application properties

Standard formulation:

A gel is formulated from 0.5% by weight of a commercially available polyacrylic acid thickener (Carbopol 940, Carbopol Ultrez 21, from Noveon) or 5.0% by weight of Aculyn 28 (from Rohm & Haas), neutralized with triethanolamine (TEA), that shows essentially no conditioning or setting effect when applied to the hair. The performance properties are shown in Table 2, Comparative Example A.

Comparative Examples B-D:

3% by weight of a commercially available hair polymer (eg B: polyacrylic acid amide, C: polyvinylformamide, D: polyvinylpyrrolidone) are added to the gel formulation from the standard formulation. The application properties are shown in Table 2. The products still need improvement with regard to their stickiness.

According to the invention:

3% by weight of copolymers 1 to 50 are added to the gel formulation from the standard formulation as a hair cosmetic active ingredient. The result is clear formulations with good conditioning and setting effects. The application properties are also shown in Table 2.

Assessment: A) Clarity

Note clarity 1 clear (reference: Carbopol 940 or Carbopol Ultrez 21; polyvinylformamide with K value = 40) 1-2 almost clear (reference: LuviskoIRVA 64) 2 clear (clear when forming a thin film on the hand; reference: polyvinylformamide with K value = 110; LuviskoIRVA 73) 3 slightly cloudy (reference: polyvinylpyrrolidone K 90) 4 cloudy (reference: polyvinyl alcohol, e.g. Mowiol R4-88) 5 milky

B) viscosity

Viscosity grade 1 very firm (reference: gel made from 0.5% Carbopol 940 or Carbopol Ultrez 21 / TEA) 2 firm 3 moderately firm 4 flowing 5 low viscosity

C) stickiness

The stickiness was determined at a relative atmospheric humidity of 75% and at ambient temperature directly on dried films of the gel formulations.

Note stickiness 1 not sticky 2 slightly sticky 3 moderately sticky 4 sticky 5 very sticky Table 2

Use in hair cosmetics:

1) Hair gels with an anionic thickener: Examples No. 1-50

Phase 1: CTFA

Polymer 1-50 (30% aqueous solution) 10.0

Glycerin 0.3

Distilled water 39.2 Other additives: preservatives, soluble ethoxylated silicone, perfume q.s.

Phase 2: INCI Carbopol 940 (1% aqueous suspension) 30.0 Carbomer or Carbopol Ultrez 21 (1% aqueous suspension) 30.0 Acrylates / C 10-30 Alkyl Acrylate Crosspolymer Triethanolamine 0.5 Dest. 20.0

The components are weighed and homogenized to produce the hair gel. Phase 2 forms a clear, firm gel, into which phase 1 is slowly stirred.

2) Hair gels with another setting polymer and anionic thickener: Examples No. 51-100

Phase 1: [%] CTFA

Polymer 1-50 (30% aqueous solution) 7.0

Luviskol VA 64 1.0 vinylpyrrolidone-vinyl acetate copolymer

Univul MS 40 0.2 benzophenone-4

Glycerin 0.2

D-panthenol USP 0.1 panthenol

Ethanol 20.0

Distilled water 21, 0

Other additives: preservatives, soluble ethoxylated silicone, perfume qs Phase 2: INCI

Carbopol 940 (1% aqueous suspension) 30.0 Carbomer or Carbopol Ultrez 21 (1% aqueous suspension) 30.0 Acrylates / C 10-30 alkyl acrylate crosspolymer

Distilled water 20.0

Production: Weighing in and homogenization. Phase 2 forms a clear, firm gel. Stir phase 1 slowly into phase 2.

3) Liquid hair gels: Examples No. 101-138 CTFA

Polymer 1-38 (30% aqueous solution) 5.0

Glycerin 0.3

Natrosol 250 L (2% aqueous solution) 25.0 hydroxyethyl cellulose (Hercules)

C-Dry MD 1915 (10% aqueous solution) 25.0 degraded starch (from Cerestar)

Distilled water 44.7

Other additives: preservatives, soluble ethoxylated silicone, perfume q.s.

Preparation: Weigh in and slowly homogenize at room temperature.

4) Aqueous Hand Pump Sprays: Examples No. 139-175

[%] CTFA

Polymer 14-50 (30% aqueous solution) 10.0 LuvisetRPUR (30% water / ethanol solution) 5.0 (PU dispersion from BASF)

C-Dry MD 1915 (10% aqueous solution) 5.0 degraded starch (Cerestar)

Distilled water 45.0

Other additives: preservatives, soluble ethoxylated silicone, perfume qs Preparation: Weigh in and slowly homogenize at room temperature.

5) VOC 55 hand pump spray: Examples No. 176-194

CTFA

Polymer 4-10, 11, 12, 15-18, 21-25, 27 (30% aqueous solution) 10.0 distilled water. 35.0 ethanol 55.0

Other additives: preservatives, soluble ethoxylated silicone, perfume q.s.

6) VOC 55 aerosol hairspray: Examples No. 195-213

[%] CTFA

Polymer 4-10, 11, 12, 15-18, 21-25, 27 (30% aqueous solution) 5.0

LuvisetRPUR (30% water / ethanol solution) 5.0 (PU dispersion from BASF)

Distilled water 35.5

Dimethyl ether 30.0

Ethanol 24.5

Other additives: preservatives, soluble ethoxylated silicone, perfume q.s.

7) Foam setting agent: Examples No. 214-232

CTFA polymer 4-10, 11, 12, 15-18, 21-25, 27 (30% aqueous solution) 5.0 CremophorA 25 (Ceteareth 25 / BASF) 0.2 Comperlan KD (Coamide DEA / Henkel) 0. 1 distilled water 74.7 dimethyl ether 10.0

Other additives: preservatives, soluble ethoxylated silicone, perfume q.s.

Preparation: Weigh in and dissolve with stirring. Fill and add propellant. 8) Sha poo: Examples No. 233-272

Conditioner shampoo: CTFA

A) Texapon NSO 28% (sodium lauryl sulfate / Henkel) 50.0

Comperlan KD (Coamide DEA / Henkel) 1.0

Polymer 1-38, 46, 48 (30% aqueous solution) 3.0 distilled water. 17.0 q.s. perfume oil

B) water 27.5 sodium chloride 1.5 q.s. preservative

Preparation: Weigh in and separate phases A) and B) with stirring and mix. Stir phase B) slowly into phase A).

Use in skin cosmetics:

9) Standard O / W Cream: Examples No. 273-290

Oil phase: [%] CTFA

CremophorAδ 3.5 ceteareth-6 and stearyl alcohol

Cremophor A25 3.5 ceteareth-25 glycerol monostearate s.e. 2.5 glyceryl stearate

Paraffin Oil 7.5 Paraffin Oil Cetyl Alcohol 2.5 Cetyl Alcohol Luvitol EHO 3.2 Cetearyl Octanoate Vitamin E Acetate 1.0 Tocopheryl Acetate Nip-Nip 0.1 Methyl- and Propyl-4-hydroxybenzoate (7: 3) Water phase:

Polymer No. 3, 14, 16, 20-23, 30-38, 45, 46

(30% aqueous solution) 3.0

Water 74.6

1, 2-propylene glycol 1, 5

Germall II 0.1 imidazolidinyl urea

Production: Weigh in and homogenize the oil phase and the water phase separately at a temperature of 80 ° C. Slowly stir the water phase into the oil phase. Cool slowly to room temperature while stirring.

10) Day Lotion: Examples No. 291-308

Oil phase: [%] CTFA

CremophorAδ 1.5 ceteareth-6 and stearyl alcohol

CremophorA25 1, 5 ceteareth-25 glycerol monostearate s.e. 5.0 Glyceryl Stearate Uvinul MS 40 0.5 Benzophenone-4 Paraffin Oil 3.5 Paraffin Oil Cetyl Alcohol 0.5 Cetyl Alcohol Luvitol EHO 10.0 Cetearyl Octanoate D-Panthenol 50P 3.0 Panthenol and Propylene Glycol

Vitamin-E-acetate 1.0 Tocopheryl Acetate Tegiloxan 100 0.3 Dimethicone Nip-Nip 0.1 Methyl- and Propyl- 4-hydro-ybenzoate (7: 3)

Water phase:

Polymer No. 4, 12, 17, 18, 20, 24-28, 33-34, 38-48, 55-56, (30% aqueous solution) 1.5

Water 70.0

1, 2-propylene glycol 1.5

Germall II 0.1 imidazolidinyl urea Production: Weigh in and homogenize the oil phase and the water phase separately at a temperature of 80 ° C. Slowly stir the water phase into the oil phase. Cool slowly to room temperature while stirring.

Recipes for use in hair styling (parts by weight are given)

Recipe 1: hair styling gel

A 0.50 carbomer 87.60 aqua dem.

B 0.70 triethanolamine

C 6.00 polymer 1-50 5.00 PVP (Luviskol K30 or Luviskol K90; BASF) q.s. Perfume oil q.s. PEG-40 Hydrogenated Castor Oil q.s. Preservative 0.10 Tocopheryl Acetate

Preparation: Let phase A swell and neutralize with phase B. Dissolve phase C and stir into phase A + B.

Recipe 2: hair styling gel

A 0.50 carbomer 87.60 aqua dem.

B 0.90 tetrahydroxypropyl ethylenediamine

C 2.00 polymer according to the invention 1-50 9.00 VPA A copolymer (Luviskol VA64W; BASF) q.s. Perfume oil q.s. PEG-40 Hydrogenated Castor Oil q.s. Preservative 0.10 propylene glycol

Preparation: Let phase A swell and neutralize with phase B. Dissolve phase C and stir into phase A + B. Recipe 3: Hair styling gel 2.00 polymer 1-50 6.00 Com Starch Modified (Amaze, National Starch) 0.50 Chitosan qs perfume oil qs PEG-40 Hydrogenated Castor Oil 0.10 PEG-14 Dimethicone 0.10 preservative

91.40 Aqua dem.

production:

Mix all components until they are homogeneous.

Formulation 4: hair styling gel 8.00 polymer according to the invention 1-50 5.00 VP / DMAPA acrylates copolymer (ISP: Styleze CC-10) 0.05 aminomethyl propanol

84.85 Aqua dem. q.s. Perfume oil q.s. PEG-40 Hydrogenated Castor Oil 0.10 Dimethicone Copolyol 0.10 Preservative 2.00 hydroxypropyl cellulose

production:

Mix all components until they are homogeneous.

Formulation 5: hair styling gel 6.00 polymer according to the invention 1-50 1.00 VP / acrylates / lauryl methacrylate copolymer (ISP: Styleze 2000) 0.26 aminomethyl propanol

90.64 Aqua the q.s. Perfume oil q.s. PEG-40 Hydrogenated Castor Oil 0.10 Sorbitol 0.10 Preservative 2.00 Hydroxypropyl Guar (Rhodia Inc., N-Hance Hydroxypropylguar)

Production: Mix all components until they are homogeneous. Recipe 6: hair gel A 0.50 carbomer 90.01 aqua dem. B 0.70 triethanolamine C 6.00 polymer according to the invention 1-50 2.00 acrylates / C1-2 succinates / hydroxyacrylates copolymer (Rohm & Haas, Allianz LT-120) 0.19 aminomethyl propanol qs perfume oil qs PEG-40 hydrogenated castor oil 0. 10 PEG-8 0.10 preservative 0.50 hydroxyethyl cellulose

Preparation: Let phase A swell and neutralize with phase B. Dissolve phase C and stir into phase A + B.

^• Formulation 7: hair gel 7.00 polymer 1-50 7.00 according to the invention methacrylic acid / sodium acrylamidomethyl propane sulfonate copolymer (Ondeo Nalco, Fixomer A30) 0.70 triethanolamine qs perfume oil qs PEG-40 hydrogenated castor 0.10 panthenol 0.10 Preservative 84.90 Aqua dem. 1, 00 polyacrylamide / C13-14 isoparaffin / Laureth-7 (Seppic, Sepigel 305)

Production: Mix all components until they are homogeneous. Recipe 8: Hair gel A 0.50 Acrylates / C 10-30 Alkyl Acrylate Crosspolymer 90.50 Aqua dem. B 0.70 triethanolamine C 7.00 polymer according to the invention 1-50 1.00 polyvinylformamide qs perfume oil qs PEG-40 hydrogenated castor oil 0.10 preservative 0.10 ethylhexyl methoxycinnamate 0.10 PEG-14 dimethicone

Preparation: Let phase A swell and neutralize with phase B. Dissolve phase C and stir into phase A + B.

Recipe 9: Aquawax

10.00 copolymer according to the invention 1-50 q.s. Perfume oil q.s. PEG-40 Hydrogenated Castor Oil 0.10 Diethyl Phtalate 0.10 Cetearyl Ethylhexanoate 0.10 PEG-7 Glyceryl Cocoate 0.10 Preservative

87.70 aqua dem. 2.00 Caprylic / Capric Triglyceride, Acrylates Copolymer (Luvigel EM)

Production: Mix and homogenize everything. Stir for 15 minutes.

Recipe 10: Hair Wax Cream 5.00 inventive copolymer 1-50 6.00 Caprylic / Capric Triglyceride 3.00 Glyceryl Stearate 2.00 Cetyl Alcohol 2.00 CremophoerAδ 2.00 CremophorA25 0.50 Dimethicone 0.50 Vitamin E Acetate 2 , 00 Caprylic / Capric Triglyceride and Sodium Acrylates Copolymer (Luvigel EM) 1.00 D-Panthenol USP 0.10 EDTA 7.50 Luviskol Plus qs preservative ad 100 water

production:

Mix and homogenize everything. Stir for 15 minutes.

Recipe 11: Conditioning Hairgel, superstrong

Phase A 0.50 Acrylates / C10-30 Alkyl Acrylate Crosspolymer

Phase B 0.70 triethanolamine

Phase C 0.50 Luviquat Hold (Polymquatemium-46) 33, 0000 Luviskol VA 64 (VPA / A copolymer) 0.50 panthenol 3.00 copolymer according to the invention 1-50 0.50 dimethiconol (DC-193, Dow Corning) 0 , 10 EDTA qq..ss .. Allow the preservative to swell with water 100 phase A and neutralize with phase B. Dissolve phase C and stir into phase A + B.

Recipe 12: gel fluid

3.00 Kollicoat IR (BASF) q.s. Preservative 3.00 copolymer according to the invention 1-50 1.00 hydroxypropyl guar 5.00 alcohol 0.20 niacinamide 0.50 panthenol 0.50 dimethocone copolyol 0.20 amodimethocone

production:

Mix everything until homogeneous. Stir for 15 minutes.

Recipe 13: hair pudding 3.00 Kollicoat IR qs preservative 2.00 inventive copolymer 4.00 acrylates / beheneth-25, methacrylate copolymer (Aculyn 28 polymer, R&H) 0.50 dimethicone copolyol 0.10 EDTA 0.20 Beπzophenone-4 ad 100 water

production:

Mix everything until homogeneous. Stir for 15 minutes.

Claims

claims

1. Cosmetic or pharmaceutical composition containing

A) at least one water-soluble or water-dispersible copolymer which can be obtained by radical copolymerization of a) 5 to 90% by weight, based on the total weight of components a) to d), acrylic acid amide and / or methacrylic acid amide, 10 b) 0 to 85 % By weight, based on the total weight of components a) to d), of at least one α, β-ethylenically unsaturated amide group-containing compound of the general formula I

O 15 R ¹ - C - NR ² R ³ where

R ^{1 represents} a group of the formula CH ₂ = CR ⁴ - with R ⁴ = H or CC ₄ alkyl and R ² and R ³ independently of one another represent H, alkyl, cycloalkyl, 20 heterocycloalkyl, aryl or hetaryl, with the proviso , one of the radicals R ² and R ^{3 is} different from H, or R ² and R ³ together with the nitrogen atom to which they are attached represent a five- to eight-membered heterocycle,

25 or R ^{2 represents} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ³ independently of one another represent H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ¹ and R ³ together with the amide group to which they are bound are a lactam with 5 to 8 ring atoms, 30 c) 0 to 40% by weight, based on the total weight of components a) to d), of at least one different from components a) and b) , thus copolymerizable unsaturated water-soluble compound, 35 where the proportion by weight of the sum of components b) and c) is at least 5% by weight, optionally in the presence of up to 25% by weight, based on the total weight of components a ) to d), at least one water-soluble component d), which is selected from d1) polyether-containing compounds,

lA d2) polymers which have at least 50% by weight repeating units derived from vinyl alcohol, d3) starch and starch derivatives, and mixtures thereof, and

B) at least one cosmetically acceptable carrier.

Composition according to claim 1, wherein component b) comprises at least one compound which is selected from N-vinyl lactams, N-vinyl amides of saturated monocarboxylic acids, N-alkyl and N, N-dialkyl amides of α, β-ethylenically unsaturated monocarboxylic acids and mixtures thereof.

3. Composition according to one of the preceding claims, wherein component c) comprises at least one compound which is selected from esters α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, their N-alkyl and N, N-dialkyl derivatives; Esters of vinyl alcohol with monocarboxylic acids; vinyl and allyl substituted heteroaromatic compounds; Amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have a tertiary and a primary or secondary amino group; Polyether acrylates and mixtures thereof.

4. Agent according to one of the preceding claims, wherein component B) is selected from i) water, ii) water-miscible organic solvents, preferably CrC ₄ alkanols, iii) oils, fats, waxes, iv) from iii) esters of C ₆ -C ₃₀ monocarboxylic acids with mono-, di- or trihydric alcohols, v) saturated acyclic and cyclic hydrocarbons, vi) fatty acids, vif) fatty alcohols and mixtures thereof.

5. Composition according to one of the preceding claims in the form of a gel, foam, spray, ointment, cream, emulsion, suspension, lotion, milk or paste.

6. Copolymer A) as defined in any one of claims 1 to 4.

7. A) copolymer according to claim 6, obtainable by radical copolymerization of a) 10 to 45 wt .-%, based on the total weight of components a) to d), methacrylic acid amide, b) 60 to 90 wt .-%, based on the total weight of components a) to d), vinylpyrrolidone and / or vinylcaprolactam, c) 0 to 25% by weight, based on the total weight of components a) to d) of at least one copolymer, which is different from a) and b) and is copolymerized therewith baren unsaturated water-soluble compound, optionally in the presence of up to 20 wt .-%, based on the total weight of components a) to d), polymers d2) and / or starch and starch derivatives d3).

8. Copolymer A) according to claim 7, obtainable by radical polymerization of a) 30 to 40 wt .-% methacrylic acid amide, b) 30 to 60 wt .-% vinyl pyrrolidone, in the presence of 1 to 20 wt .-% polymers d2) and / or starch and starch derivatives d3).

9. A) copolymer according to claim 7, obtainable by radical polymerization of a) 30 to 40 wt .-% methacrylic acid amide, b) 20 to 60 wt .-% vinyl pyrrolidone and 1 to 20 wt .-% vinyl caprolactam.

10. Copolymer A) according to claim 7, obtainable by radical polymerization of a) 30 to 40% by weight methacrylic acid amide, b) 20 to 60% by weight vinylpyrrolidone and c) 1 to 20% by weight at least one of a) and b) various water-soluble compounds copolymerizable therewith.

11. Use of a copolymer A), as defined in any one of claims 1 to 4, in skin cleansing agents, agents for the care and protection of the skin, nail care agents, preparations for decorative cosmetics and hair treatment agents.

12. Use according to claim 11 in hair treatment compositions as a setting agent and / or as a conditioner.

13. Use according to claim 12, wherein the agent is in the form of a hair gel, shampoo, foaming agent, hair tonic, hair sprays or hair foam.

14. Use of a copolymer A), as defined in one of claims 1 to 4, as an auxiliary in pharmacy, preferably as or in coating agent (s) for solid dosage forms and as or in coating agent (s) for textile, paper , Printing and leather industries.