EP1804920A1

EP1804920A1 - Cosmetic preparations containing copolymers of ethyl methacrylate and at least one monoethylenically unsaturated carboxylic acid

Info

Publication number: EP1804920A1
Application number: EP05801886A
Authority: EP
Inventors: Gabi Winter; Matthias Laubender; Claudia Wood
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-10-22
Filing date: 2005-10-19
Publication date: 2007-07-11
Also published as: KR20070084425A; CA2583343A1; CN101084044A; WO2006045509A1; JP2008517021A; CN101084044B; US20080274069A1; DE102004051647A1

Abstract

The invention relates to cosmetic and pharmaceutical agents containing copolymers which contain ethyl methacrylate and at least one monoethylenically unsaturated carboxylic acid which is polymerised therein. The invention also relates to said copolymers and to the use thereof.

Description

COSMETIC PREPARATIONS CONTAIN COPOLYMERS OF ETHYL METHACRYLATE AND AT LEAST ONE MONOETHYLENICALLY UNSATURATED CARBOXYLIC ACID

description

The present invention relates to cosmetic and pharmaceutical compositions comprising copolymers which comprise copolymerized ethyl methacrylate and at least one monoethylenically unsaturated carboxylic acid, the copolymers themselves and their Verwen¬ tion.

State of the art

Polymers with film-forming properties have found many applications in the field of pharmacy and cosmetics. In pharmacy, they serve, for example, as a coating agent or binder for solid dosage forms. In cosmetics, polymers with film-forming properties u. a. used for strengthening, structural improvement and shaping of the hair. They serve, for example, as conditioners to improve the dry and wet combability, the feeling of touch, the gloss and the appearance and also to give the hair antistatic properties. Requirements which are made of film-forming polymers for use as setting resins, z. B. a strong consolidation (even at high humidity), Elasti¬ capacity, leachability of the hair, compatibility in the formulation and a pleasant handle of the thus treated hair. The provision of products with a complex property profile is often difficult. Thus, there is a need for film-forming polymers for hair cosmetics which are capable of forming substantially smooth, tack-free films, have a good setting effect, and at the same time provide the hair with good sensory properties such as elasticity and a pleasant feel. If these polymers are to be used in hairspray formulations, good propellant gas compatibility, suitability for use in low-VOC formulations (VOC = volatile organic compounds), good sprayability, good solubility in water or aqueous / alcoholic solutions are also desirable ¬ medium mixtures and a good washability desired.

(Meth) acrylate-based copolymers which are water-soluble in alkaline are often used in the field of cosmetics as hair-setting agents.

For example, EP-A-379 082 describes hair setting agents which contain as film formers copolymers with a K value of from 10 to 50, which are composed of 75 to 99% by weight of t-butyl acrylate and / or t-butyl methacrylate, 1 to 25% by weight of acrylic acid and / or methacrylic acid and 0 to 10% by weight of another free-radically copolymerizable monomer. For use in cosmetics, the carboxyl groups of the copolymers are partially or completely neutralized by amines. DE-A-43 14 305 describes hair-setting compositions which contain as film formers copolymers of the type mentioned in EP-A-379 082 which are composed of 30 to 72% by weight of t-butyl acrylate and / or t-butyl methacrylate, 10 to 28 wt .-% of acrylic acid and / or methacrylic acid and 0 to 60 wt .-% of a radically copolymerizable monomer or a free-radically copolymerizable monomeric mixture, wherein at least one of these monomers provides a homopolymer having a glass transition temperature below 30 ⁰ C.

No. 3,577,517 describes hair lacquers and aerosol formulations which comprise neutralized solution polymers of from 5 to 40% by weight of a (meth) acrylic acid ester with C ₈ -C ₁₈ aliphatic alcohols, from 6 to 35% by weight of (meth) acrylic acid and 25 to 89 wt .-% ei¬ nes further vinyl monomer, a water-soluble organic solvent and propellant. By emulsion polymerization available polymers are not described.

US 5,589,157 and EP-A 590 604 describe aqueous acrylic polymer compositions containing copolymers consisting of 35 to 74 wt .-% of an alkyl acrylate, 25 to 65 wt .-% of an alkyl methacrylate and 1 to 15 wt .-% of a (Meth) acrylic acid or salts thereof and their use in hair cosmetic preparations.

JP 3056409 describes hairspray preparations containing an anionic resin which is composed of 30 to 70% by weight of C ₁ -C ₇ -alkyl or alkenyl (meth) acrylate, 10 to 50% by weight of C ₉ -C ₂₄ Alkyl or alkenyl (meth) acrylate and 10 to 40% by weight of a polymerizable carboxyl group-containing compound.

No. 3,405,084 describes terpolymer resins consisting of 25 to 75% by weight of vinylpyrrolidone, 20 to 70% by weight of (meth) acrylate and 3 to 25% by weight of olefinically unsaturated carboxylic acid for use in hair cosmetic preparations, in particular as hair sprays ,

EP-A 331 994 describes hair setting preparations comprising copolymers of a) 40-60% by weight of Ca-C 1-4 -alkyl methacrylates, b) 20 to 40% by weight of C ₄ -C ₁₀ -N-alkyl-substituted acrylamides and c ) 10 to 25% by weight of (meth) acrylic acid. Copolymers of a) isobutyl methacrylate, b) N-tert-octylacrylamide and c) acrylic acid are preferably used.

EP-A 985 401 describes hairstyling preparations comprising a resin consisting of 5-95% C ₁ -C ₁₀ alkyl (meth) acrylate, 2-16% hydroxyalkyl (meth) acrylate, 0-50% C ₃ -C ₈ monoethylenically unsaturated monocarboxylic acids and 2-10% monoethylenically unsaturated dicarboxylic acids. GB 1410012 describes aerosol hair spray preparations which contain methacrylic acid C _r C ₃ -alkyl (meth) acrylate copolymers, in particular methyl acrylate copolymers or methacrylic acid-methyl acrylate-methyl methacrylate terpolymers.

EP-A 62 002 describes hair cosmetic preparations containing terpolymers which are obtained by copolymerizing a) 40 to 60% by weight of an N-alkylacrylamide or N-alkylmethacrylamide having from 1 to 4 carbon atoms with b) 35 to 50% by weight. % of a CrCzrHydroxyalkylester or preferably C ₁ -C ₄ alkyl esters of acrylic or methacrylic acid and c) 3 to 11 wt .-% of an α, ß-unsaturated monocarboxylic acid or dicarboxylic acid are prepared.

DE 42 23 006 describes hair treatment compositions containing as film formers copolymers which by copolymerizing (a) 30 to 80 wt .-% of an acrylic or methacrylsäureesters, each having a glass transition temperature of more than 20 ° C as homopolymer or mixtures of acrylic and methacrylic esters which result from the copolymerization of copolymers having a glass transition temperature of more than 2O ⁰ C, (b) 5 to 25 wt .-% of acrylic acid, methacrylic acid or mixtures thereof and (c) 10 to 45 wt .-% N-vinylpyrrolidone, N-vinylcaprolactam or de¬ ren mixtures in the presence of radical-forming polymerization initiators are available, and in the form of the free carboxylic acid K-values (determined according to H. Fikentscher in 1 wt .-% solution in ethanol at 25 ° C) from 10 to 80, characterized in that the copolymers are prepared by the process of precipitation polymerization.

EP-A 100 890 discloses copolymers obtained by free-radical copolymerization of

a) 20 to 75 parts by weight of at least one C ₂ - to C ₂₀ -alkyl ester of

(Meth) acrylic acid, b) 5 to 50 parts by weight of at least one nitrogen-containing, neutral-reacting water-soluble monomer, c) 1 to 25 parts by weight of at least one cationic group-containing monomers and d) 1 to 25 parts by weight of at least one with a), b) and c) copolymerizable olefinically unsaturated C3- to C5-carboxylic acid, and those measured in ethanol at

25 ⁰ C have a K value according to Fikentscher of 15 to 75.

Stricter environmental regulations and increasing ecological awareness are increasingly demanding ever lower levels of volatile organic compounds (VOCs) in, for example, hairsprays. The VOC content in hair sprays is essentially given by the non-aqueous solvents and the foaming agents. Therefore, instead of non-aqueous solvents, recourse was increasingly made to water as solvent. However, this replacement of organic solvents brings some problems, especially in the field of hair spray formulations.

Thus, formulations of the aforementioned film-forming polymers from the prior art, which meet the corresponding VOC requirements, for example, not or only after further dilution sprayable and thus only conditionally suitable for use in hair sprays. This in turn leads to films that sometimes do not bring the necessary mechanical quality and thus insufficient consolidation effect and poor grip for the hair.

Requirements for hair setting resins are, for example, a strong consolidation at high humidity, elasticity, good washability from the hair, compatibility in the formulation, the lowest possible stickiness of the film formed and a pleasant handle of the treated hair. In the case of spray formulations, in particular a homogeneous distribution of small droplets to form a fine spray pattern is desired. Difficulties often arise in the provision of products with a complex property profile. Thus, there is a need for, in particular, cosmetic preparations which are capable of forming substantially smooth, tack-free films which impart to the hair and the skin good sensory properties, such as a pleasant feel, and at the same time a good conditioning effect or strength Have ¬ effect.

The object of the present invention was to provide polymers for cosmetic preparations which can be formulated in solvents or solvent mixtures with an increased water content and whose formulations when sprayed as spray good sprayability and a fine, homogeneous spray pattern with good mechanical properties of the have formed films. In addition to the good compatibility with the customary cosmetic ingredients, the polymers are said to confer good firmness and longer hold on the hair, have good leachability and have to be optically clear VOC-55 aerosols (ie with a VOC content of at most 55% by weight). -%).

Surprisingly, it has been found that the ethylmethacrylate copolymers of the invention solve this problem.

In the following, compounds which can be derived from acrylic acid and methacrylic acid are sometimes abbreviated by insertion of the syllable "(meth)" into the compound derived from the acrylic acid. The invention relates to cosmetic preparations comprising at least one copolymer which is obtainable by free-radical polymerization of

a) from more than 15 to 40% by weight of at least one monoethylenically unsaturated carboxylic acid, b) from 30 to less than 85% by weight of ethyl methacrylate, c) from 0 to 50% by weight of at least one other, from a) and b) various radi¬ calically polymerizable monomers c), wherein the amounts of Komponen¬ th a), b) and c) add up to 100 wt .-%, with the proviso that if it is in the free-radical polymerization to a Lösungspolymerisa¬ a) consists exclusively of acrylic acid and methacrylic acid and at the same time c) is selected from the group of esters of (meth) acrylic acid with aliphatic C ₈ -C ₁₈ alcohols, c) then may not be selected from 5 to 40 wt. % Esters of (meth) acrylic acid with C ₈ -C ₁₈ aliphatic alcohols and with the proviso that when c) is selected from the group consisting of N-vinylpyrrolidone, N-vinylcaprolactam and mixtures thereof, c) then in an amount of less than 10% by weight.

The invention preferably relates to cosmetic preparations comprising at least one copolymer which is obtainable by free-radical polymerization of

a) from 16 to 40% by weight of at least one monoethylenically unsaturated carboxylic acid, b) from 30 to less than 84% by weight of ethyl methacrylate, c) from 0 to 50% by weight of at least one further compound other than a) and b) radi¬ calically polymerizable monomers c), wherein the amounts of Komponen¬ a), b) and c) add up to 100 wt .-%, with the proviso that if it is in the free radical polymerization to a Lösungspolymerisati¬ on is and a) consists solely of acrylic acid and methacrylic acid and at the same time c) is selected from the group of esters of (meth) acrylic acid with aliphatic C ₈ -C ₈ alcohols, c) then must not be chosen from 5 to 40 wt % Esters of (meth) acrylic acid with C ₈ -C 12 aliphatic alcohols and with the proviso that when c) is selected from the group consisting of N-vinylpyrrolidone, N-vinylcaprolactam and mixtures thereof, c) then in in an amount of less than 10% by weight.

Accordingly, the invention also relates to polymers obtainable by radical polymerization of a) from 16 to 40% by weight of at least one monoethylenic compound b) from 30 to 84% by weight of ethyl methacrylate, c) from 0 to 50% by weight of at least one further radically polymerizable monomer c) different from a) and b), the amounts of components a), b and c) add up to 100% by weight, with the proviso that if the free radical polymerization is a solution polymerization and a) consists exclusively of acrylic acid and methacrylic acid and at the same time c) is selected from the group of Esters of (meth) acrylic acid with aliphatic C ₈ -C ₁₈ -alcohols, c) then may not be selected from 5 to 40 wt .-% esters of (meth) acrylic acid with aliphatic C ₈ -C ₁₈ alcohols and with with the proviso that, when c) is selected from the group consisting of N-vinylpyrrolidone, N-vinylcaprolactam and mixtures thereof, c) then present in an amount of less than 10 wt .-%.

The object is further achieved by the provision of cosmetic preparations comprising at least one copolymer obtainable by free-radical polymerization of a) from 16 to 40% by weight of at least one monoethylenically unsaturated carboxylic acid, b) from 30 to 84% by weight % Of ethyl methacrylate, c) 0 to 50% by weight of at least one further radically polymerizable monomer c) which differs from a) and b), the amounts of components a), b) and c) being too 100 wt .-% add and wherein the polymerization is an emulsion polymerization.

The invention accordingly also provides polymers obtainable by free-radical polymerization of a) from 16 to 40% by weight of at least one monoethylenically unsaturated carboxylic acid, b) from 30 to 84% by weight of ethyl methacrylate, c) from 0 to 50% by weight At least one further, of a) and b) different radically polymerizable Mo¬ nomeren c), wherein the amounts of the compo nents a), b) and c) add up to 100 wt .-% and wherein the polymerization is an emulsion polymerization ,

The invention further provides polymers obtainable by free-radical polymerization of a) from 5 to 40% by weight, preferably from 10 to 35% by weight, more preferably from 12 to 30% by weight, of at least one monoethylenically unsaturated carboxylic acid, b) 30 to 95 wt .-%, preferably 40 to 80 wt .-%, particularly preferably 45 to 75 wt .-% ethyl methacrylate, c) 0 to 50 wt .-% of at least one further, of a) and b) free-radically polymerizable monomers c), the amounts of a), b) and c) adding up to 100% by weight, with the proviso that when the free-radical polymerization is a solution polymerization and a) exclusively from Acrylic acid and methacrylic acid and at the same time c) is selected from the group of the esters of (meth) acrylic acid with α-aliphatic C ₈ -C ₈ -alcohols, c) then may not be selected from 5 to 40% by weight Esters of (meth) acrylic acid with aliphatic C ₈ -C ₁₈ -alcohols and with the proviso that when c) is selected from the group consisting of N-vinylpyrrolidone, N-vinylcaprolactam and mixtures thereof, c) then in one Less than 10% by weight, and provided that less than 35% by weight of the monomers are selected from C 1 -C 5 -alkyl acrylate.

Component a) The monomers a) include monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms, which can also be used in the form of their salts or anhydrides. Examples thereof are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid. The monomers a) furthermore include the half-esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, eg. B. of maleic acid such as monomethyl maleate. The monomers a) also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts. The monomers a) can be used as such or as mixtures with one another. The stated proportions by weight are all based on the Säu¬ reform.

Preferably, monomer a) is selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof, particularly preferably Acrylic acid, methacrylic acid and mixtures thereof and in particular methacrylic acid.

In a preferred embodiment of the invention, a) consists of a1) methacrylic acid and optionally a2) other monoethylenically unsaturated monocarboxylic acids other than methacrylic acid.

In a preferred embodiment of the invention, a) consists of a1) methacrylic acid and optionally a2), where a2) is selected from the group consisting of acrylic acid, ethacrylic acid, .alpha.-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, Citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.

In a further preferred embodiment of the invention, a) consists of a1) acrylic acid and optionally a2), where a2) is selected from the group consisting of methacrylic acid, ethacrylic acid, .alpha.-chloroacrylic acid, crotonic acid, maleic acid, maleic acid, Acid anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.

In a further preferred embodiment, component a) contains no monoethylenically unsaturated dicarboxylic acids.

In a further preferred embodiment, component a) comprises a mixture of methacrylic acid and itaconic acid or component a) consists of a mixture of methacrylic acid and itaconic acid.

In a further preferred embodiment, component a) comprises a mixture of methacrylic acid and acrylic acid or component a) consists of a mixture of methacrylic acid and acrylic acid.

If component a) is a mixture of methacrylic acid and further monoethylenically unsaturated carboxylic acids, it is advantageous if the weight ratio of methacrylic acid to further acids is greater than 1, preferably greater than 2, more preferably at least 3 and in particular at least 4.

According to the invention, the amount of a) is at least 16, preferably at least 18, more preferably at least 20 and at most 40, preferably at most 38, more preferably at most 35 and most preferably at most 30 wt .-%.

In a preferred embodiment, the polymers according to the invention consist exclusively of ethyl methacrylate and component a).

Component c)

For the preparation of the polymers according to the invention optionally 0 to 50 wt .-% of a monomer c) are used.

Esters of α, ß-ethylenically unsaturated mono- and dicarboxylic acids

Suitable monomers c) are, for example, selected from C 1 -C ₈ -alkyl acrylates and

CrCie methacrylates. Suitable monomers c) are the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids other than ethyl methacrylate, such as, for example, methyl (meth) acrylate, ethyl acrylate, methyl methacrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-propylethacrylate, ethylethacrylate, i-propylethacrylate, n-butyl (meth) acrylate, n-butylethacrylate, tert-butyl (meth) acrylate, tert-butylethacrylate, i-butyl (meth) acrylate, i-butyl ethacrylate, sec-butyl (meth) acrylate, butlyethacrylate, 2-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, isopentyl acrylate, neopentyl acrylate, hexyl (meth) acrylate, 1-methylpentyl (meth) acrylate, 2- Methylpentyl (meth) acrylate, 3-methylpentyl (meth) acrylate, 4-methyl pentyl (meth) acrylate, 1, 1-dimethylbutyl (meth) acrylate, 1, 2-dimethylbutyl (meth) acrylate, 1, 3-dimethylbutyl (meth) acrylate, 2,2-dimethylbutyl (meth) acrylate, 2,3- Dimethylbutyl (meth) acrylate, 3,3-dimethylbutyl (meth) acrylate, 1-ethylbutyl (meth) acrylate, 1,1,2-trimethylpropyl (meth) acrylate, 1,2,2-trimethylpropyl (meth) acrylate, 1-ethyl-1-methylpropyl (meth) acrylate, 1-ethyl-2-methylpropyl, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth acryloate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, arrachinyl (meth) acrylate, behenyl (meth) acrylate, lignocerenyl (meth) acrylate, cerotinyl (meth) acrylate, melissinyl (meth) acrylate , Palmitoleyl (meth) acrylate, oleyl (meth) acrylate, linolyl (meth) acrylate, linolenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, phenoxyethyl acrylate, tB ethylcyclohexyl acrylate, cyclohexyl (meth) acrylate, ureido (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ureido methacrylate and mixtures thereof.

Preferred monomers c) are the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids other than ethyl methacrylate with C ₁ -C ₄ -alkanols.

Hydroxyalkyl (meth) acrylates Suitable monomers c) are furthermore esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with polyhydric alcohols, such as, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- Hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate, 3 Hydroxy-2-ethylhexyl methacrylate and mixtures thereof.

When a) is composed exclusively of acrylic acid and methacrylic acid, and is selected at a time component c) from the group of esters of (meth) acrylic acid with aliphatic C ₈ -C ₈ alcohols, then c) will not be chosen from 5 to 40 wt .-% Esters of (meth) acrylic acid with aliphatic C ₈ -C ₁₈ -alcohols.

Suitable monomers c) are also vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ester of the Versatiesäure (VeoVa ^® monomers), 4-tert-butylbenzoate and their mixtures.

Suitable monomers c) are furthermore ethylene, propylene, isobutylene, butadiene, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.

N-vinylamides of saturated C 1 -C ₈ monocarboxylic acids Suitable monomers c) are N-vinylamides of saturated C _r C ₈ mono-carboxylic acids such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N- methylacetamide, N-vinyl-N-ethylacetamide , N-vinylpropionamide, N-vinyl-N-methyl-propionamide, N-vinylbutyramide and mixtures thereof.

Amides of α, ß-ethylenically unsaturated mono- and dicarboxylic acids

Suitable monomers c) are also NC _r C ₁₈ -alkylacrylamides and N-Ci-Ci ₈ -alkyl methacrylamides.

Further suitable monomers c) are, in particular, primary amides of α, β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives which, in addition to the carbonyl carbon atom of the amide group, have at most 8 further carbon atoms, for example acrylic acid amide , Methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) methacrylamide, N- (sec-butyl) methacrylamide, N- (tert Butyl) methacrylamide, N- (n-pentyl) (meth) acrylamide, N- (n-hexyl) (meth) acrylamide, N- (n-heptyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (tert-octyl) (meth) acrylamide N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide, N-myristyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (meth) acrylamide, N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-ar- rachinyl (meth) ac rylamide, N-behenyl (meth) acrylamide, N-lignocerenyl (meth) acrylamide, N-cerotinyl (meth) acrylamide, N-melissinyl (meth) acrylamide, N-palmitoleinyl (meth) acrylamide, N-oleyl (meth) acrylamide , N-linolyl (meth) acrylamide, N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-lauryl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide piperidinyl (meth) acrylamide and morpholinyl (meth) acrylamide and mixtures thereof.

In a preferred embodiment of the invention, c) comprises methacrylamide and / or N- (tert-butyl) acrylamide or consists of one of these components or of a mixture of methacrylamide and N- (tert-butyl) acrylamide.

Suitable monomers c) are also amides of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols having a primary or secondary amino group, such as 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, 2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide, 2-hydroxypropylmethacrylamide , 3-hydroxypropylacrylamide, 3-hydroxypropylmethacrylamide, 3-hydroxybutylacrylamide, 3-hydroxybutylmethacrylamide, 4-hydroxybutylacrylamide, 4-hydroxybutylmethacrylamide, 6-hydroxyhexylacrylamide, 6-hydroxyhexylmethacrylamide, 3-hydroxy-2-ethylhexylacrylamide, 3-hydroxy-2-ethylhexylmethacrylamide and mixtures thereof. The copolymers of the invention may additionally contain at least one compound having a free-radically polymerizable, .alpha.,. Beta.-ethylenically unsaturated double bond and at least one cationogenic and / or cationic group per molecule.

The cationogenic or cationic groups of component c) are preferably nitrogen-containing groups, such as primary, secondary and tertiary amino groups, and quaternary ammonium groups. Preferably, the nitrogen-containing groups are tertiary amino groups. The compounds c) are preferably used in an uncharged form for the polymerization. However, use in charged form is also suitable. Charged cationic groups can be z. B. from the amine nitrogens by protonation, z. B. with monohydric or polyhydric carboxylic acids such as lactic acid or tartaric acid, or mineral acids such as Phos¬ phosphoric acid, sulfuric acid and hydrochloric acid.

Component c) can be selected from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, which may be mono- or dialkylated on the amine nitrogen, amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines, which at least one primary or secondary amino group, N, N-diallylamine, N, N-diallyl-N-alkylamines and their derivatives, vinyl- and aliyl-substituted nitrogen heterocycles, vinyl- and allyl-substituted heteroaromatic compounds and mixtures thereof.

As the acid component of these esters are z. Acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Preference is given to using acrylic acid, methacrylic acid and mixtures thereof. Examples of such compounds c) are N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N- (n-propyl) aminoethyl (meth) acrylate, N- (n-butyl) aminoethyl (meth) acrylate, N N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth ) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate.

In particular, as compound c) N- (tert-butyl) aminoethyl acrylate and N- (tert-butyl) aminoethyl methacrylate are used.

Suitable monomers c) are furthermore the amides of the abovementioned α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group. Preference is given to diamines which have a tertiary and a primary or secondary amino group. Preference is given as monomers c) to 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 and N- [4- (dimethylamino) cyclohexyl] methacrylamide used. Particular preference is given to using N- [3- (dimethylamino) propyl] acrylamide and / or N- [3- (dimethylamino) propyl] methacrylamide.

These cationogenic monomers c) can also be present in quaternized form. The quaternization is carried out in the case of the abovementioned monomers, if appropriate using methyl chloride, methyl sulfate or diethyl sulfate.

Suitable monomers c) are also NN-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts. Alkyl is preferably C _r C ₂₄ -alkyl. Preferably, for example, N, N-diallyl-N-methylamine.

These cationogenic monomers c) can also be present in quaternized form. The quaternization is carried out with conventional quaternizing agents such as methyl chloride, methyl sulfate or diethyl sulfate.

Suitable monomers c) are also vinyl- and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinylimidazole derivatives, eg. N-vinyl-2-methylimidazole, vinyl- and allyl-substituted heteroaromatic compounds such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.

Suitable monomers c) are also N-vinylimidazoles of the general formula (I) in which R ¹ to R ^{3 are} hydrogen, C 1-4 -alkyl or phenyl

Examples of compounds of the general formula (I) are given in Table 1 below:

Table 1

Me = methyl Ph = phenyl

In a preferred embodiment of the invention, component c) is selected from N- (tert-butylamino) ethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- [3- (dimethylamino) propyl] (meth) acrylamide , Vinylimidazole and mixtures thereof.

polyether

Suitable components c) are also polyether acrylates. In the context of this invention, polyether acrylates are generally understood to mean esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with polyetherols. Suitable polyetherols are linear or branched, terminal hydroxyl-containing substances containing ether bonds. In general, 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 preparation of alkylene oxide copolymers are e.g. Ethylene oxide, propylene oxide, epichlorohydrin, 1, 2, and 2,3-butylene oxide. The alkylene oxide copolymers may randomly distribute the alkylene oxide units or contain them in copolymerized form in the form of blocks. Preferred are ethylene oxide / propylene oxide copolymers.

Preferred as. Component c) are polyether acrylates of the general formula V

wherein

the order of the alkylene oxide units is arbitrary,

k and I independently of one another represent an integer from 0 to 1000, the sum of k and I being at least 5,

R ^{4 is} hydrogen, C ₁ -C ₃₀ -alkyl or C ₅ -C ₈ -cycloalkyl,

R ⁵ is hydrogen or C ₈ alkyl _R C,

Y ^{2 is} O or NR ⁶ , where R ^{6 is} hydrogen, C 1 -C ₁₀ -alkyl or C ₅ -C ₈ -cycloalkyl,

Preferably, k is an integer from 1 to 500, in particular 3 to 250. Preferably, I is an integer from 0 to 100.

R ⁵ 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.

In the formula V, R ⁴ is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl.

Preferably, Y ² in the formula V is 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 epi-chlorohydrin with a starter molecule, such as water or a short-chain alcohol R ⁴ -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 for the preparation of the polymers used according to the invention. Suitable components c) are also allyl alcohol propoxylates or allyl alcohol ethoxylates.

Suitable monomers c) are also N-vinyllactams are unsubstituted N-vinyllactams and N-vinyllactam derivatives, the z. B. one or more C 1 -C ₆ -alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc., have kön¬ NEN. These include z. 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.

The copolymers according to the invention preferably comprise less than 10% by weight, preferably less than 5% by weight, particularly preferably less than 3% by weight, of copolymerized N-vinyllactams. With very particular preference the copolymers according to the invention contain less than 1% by weight and in particular no N-vinyllactams.

In the event that monomer c) is selected from the group consisting of N-vinylpyrrolidone, N-vinylcaprolactam and mixtures thereof, the amount of c) is less than 10, preferably less than 5,% by weight, especially preferably less than 3 and in particular less than 1 wt .-%.

In preferred cosmetic preparations, the at least one monomer c) is selected from the group consisting of C 1 -C 4 -alkyl acrylates, C 1 -C 4 -alkyl methacrylates, acrylamide, methacrylamide, N-C 1 -C 6 -alkyl acrylamides and N-C 1 -C ₁₈ - Alkyl methacrylamides, with n-butyl acrylate, tert-butyl acrylate, hydroxyethyl methacrylate, ethyl acrylate and mixtures thereof are particularly preferred.

The abovementioned monomers c) can each be used individually or in the form of any desired mixtures.

A preferred cosmetic formulation comprises a copolymer obtainable by free radical polymerization of

a) from 18 to 35% by weight of a monoethylenically unsaturated carboxylic acid, b) from 40 to 80% by weight of ethyl methacrylate, c) from 0 to 50% by weight of monomer c), the amounts of components a), b) and c) add to 100 wt .-%.

A particularly preferred cosmetic formulation comprises a copolymer obtainable by radical polymerization of a) from 20 to 35% by weight of a monoethylenically unsaturated carboxylic acid, b) from 45 to 80% by weight of ethyl methacrylate, c) from 0 to 50% by weight of monomer c), the amounts of components a), b) and c) add to 100 wt .-%.

The monomers c) are used in amounts of from 0 to 50% by weight, preferably in amounts of from 0 to 30, more preferably in amounts of from 0 to 20% by weight, most preferably in amounts of from 0 to 15% by weight. -% and in particular in amounts of less than 10 wt .-% used.

crosslinkers

If desired, the copolymers according to the invention may contain at least one crosslinker, ie. H. in copolymerized form contain a compound having two or more than two ethylenically unsaturated, non-conjugated double bonds.

Crosslinkers are preferably used in an amount of 0.01 to 7 wt .-%, particularly preferably 0.1 to 5 wt .-%, based on the total weight of the monomers used for the polymerization.

Suitable crosslinkers are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the underlying alcohols can be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.

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-ene-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-methylpentane-1, 5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1 , 4-Cyclohexanediol, 1,4-bis (hydroxymethyl) cyclohexane, hydroxypivalic neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane, Diethy - 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 having molecular weights of 200 to 10,000. Except the homopolymers of ethylene oxide or propylene oxide also block copolymers of ethylene oxide or propylene oxide or copolymers containing incorporated incorporated ethylene oxide and propylene oxide groups. Examples of underlying alcohols having 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, NEN the polyhydric alcohols are also used after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates. The polyhydric alcohols can also be first converted by reaction with epichlorohydrin in the corresponding glycidyl ether.

Further suitable crosslinkers are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C ₃ -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, cinnamyl alcohol Citronellol,

Crotyl alcohol or cis-9-octadecen-1-ol. However, it is also possible to esterify the monohydric, unsaturated alcohols with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.

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

Also suitable as crosslinking agents are straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated in aliphatic hydrocarbons, eg. B. divinylbenzene, divinyltoluene, 1, 7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights of 200 to 20,000.

Other suitable crosslinking agents are the acrylic acid amides, methacrylic acid amides and N-allylamines of at least divalent amines. Examples of such amines are 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine. Also suitable are the amides of allylamine and unsaturated Carbonsäu¬ ren, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least bivalent carboxylic acids, as described above.

Further, triallylamine and Triallylmonoalkylammoniumsalze, z. As triallylmethylammonium chloride or methyl sulfate, suitable as a crosslinker.

Also suitable are N-vinyl compounds of urea derivatives, at least bivalent amides, cyanurates or urethanes, for example of urea, ethylene urea, propylene urea or tartaramide, for. N, N'-divinylethyleneurea or N, N'-divinylpropyleneurea. Further suitable crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane.

Of course, it is also possible to use mixtures of the abovementioned compounds. Preferably, water-soluble crosslinkers are used.

Crosslinkers used with particular preference are, for example, methylenebisacrylamide, triallylamine and triallylalkylammonium salts, divinylimidazole, pentaerythritol triallyl ether, N, N'-divinylethyleneurea, reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic acid esters and acrylic esters of polyalkylene oxides or polyhydric alcohols which react with ethylene oxide and / or Propylene oxide and / or epichlorohydrin have been implemented.

Very particularly preferred crosslinkers are pentaerythritol triallyl ether, Methylenbis¬, N, N ^J divinylethyleneurea, triallylamine and salts and Triallylmonoalkylammonium- acrylate of glycol, butanediol, trimethylolpropane or glycerol or of acrylate with ethylene oxide and / or epichlorohydrin unreacted glycol, Bu¬ tandiol, Trimethylolpropane or glycerin.

Preparation of the Copolymers The copolymers are prepared by customary methods known to the person skilled in the art, e.g. by solution, precipitation, suspension or emulsion polymerization.

The preparation is preferably by solution or emulsion polymerization.

Preferred solvents for the solution polymerization are aqueous solvents such as 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-butyl Hexanol and cyclohexanol and glycols such as ethylene glycol, propylene glycol and butylene glycol and the methyl or ethyl ethers of dihydric alcohols, diethylene glycol, triethylene glycol, polyethylene glycols with number average molecular weights up to about 3000, glycerol and dioxane.

The polymerization in water or a water / alcohol mixture, for example in a water / ethanol mixture, is particularly preferred. When using water as a solvent component desalted water is preferably used.

The copolymers are particularly preferably prepared in a known manner by free-radically initiated aqueous emulsion polymerization of the monomers a), b) and optionally c).

emulsion The method of free-radically initiated aqueous emulsion polymerization has been described in detail and is therefore sufficiently known to the person skilled in the art [cf. for example, Encyclopedia of Polymer Science and Engineering, Vol. 8, pp. 659-677, John Wiley & Sons, Inc., 1987; DC Blackley, Emulsion Polymerization, pp. 155-465, Applied Sciences Publishers, Ltd., Essex, 1975; . DC Blackley, polymer latices, 2 ^nd Edition, Vol 1, pages 33 to 415, Chapman & Hall, 1997; H. Warson, The Applications of Synthetic Resin Emulsions, pages 49 to 244, Ernest Benn, Ltd., London, 1972; D. Diederich, Chemistry in our Time 1990, 24, pages 135 to 142, Verlag Chemie, Weinheim; J. Piirma, Emulsion Polymerization, pages 1 to 287, Academic Press, 1982; F. Hölscher, dispersions of synthetic high polymers, pages 1 to 160, Springer-Verlag, Berlin, 1969 and DE-A 40 03 422]. The free-radically initiated aqueous emulsion polymerization is usually carried out by dispersing the monomers, generally with co-use of dispersants, in aqueous medium and polymerizing them by means of at least one free radical polymerization initiator.

initiators

Suitable free-radical polymerization initiators for the inventive radical aqueous emulsion polymerization are all those which are capable of initiating a free-radical aqueous emulsion polymerization.

In principle, it may be both peroxides and azo compounds. Of course, redox initiator systems come into consideration.

In principle, inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric acid, such as, for example, their mono- and di-sodium, potassium or ammonium salts or organic peroxides, can be used as peroxides. such as alkyl hydroperoxides, for example tert-butyl, p-menthyl or cumyl hydroperoxide, tert-butyl perpivalate and dialkyl or diaryl peroxides, such as di-tert-butyl or di-cumyl peroxide, 2,5-dimethyl-2, 5-di (t) butyl peroxy (hexane) or dibenzoyl peroxide are used.

The azo compounds are essentially 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (amidinopropyl) dihydrochloride (AIBA, corresponding to V-50 ™ from Wako Chemicals ), 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2-amidinopropane) salts, 4,4'-azobis (4-cyanovaleric acid) or 2- (carbamoylazo) isobutyronitrile ,

Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides. Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium bisulfite, alkali metal metisulfites, for example potassium and / or sodium metabisulfite. sulfite, formaldehyde sulfoxylates, for example potassium and / or sodium formaldehyde sulfoxylate, alkali metal salts, especially potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrogensulfides, for example potassium and / or sodium hydrogensulfide, salts of polyvalent metals, such as iron (II ) sulfate, iron (II) ammonium sulfate, iron (II) phosphate, endiols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid, and reducing saccharides, such as sorbose, glucose, fructose and / or dihydroxyacetone ,

The initiators are usually used in amounts of up to 10, preferably 0.02 to 5 wt .-%, based on the monomers to be polymerized.

Surfactants and protective colloids

The emulsion polymerization is usually carried out in the presence of surfactants and / or

Protective colloids performed. In the preparation of the polymers used in the preparations according to the invention, at least one dispersing assistant is used which can hold both the monomer droplets and polymer particles dispersed in the aqueous phase and thus ensures the stability of the aqueous polymer dispersion produced. As such, both the protective colloids commonly used for carrying out free-radical aqueous emulsion polymerizations and emulsifiers are suitable.

Suitable protective colloids are, for example, polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing copolymers. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, pages 411 to 420, Georg Thieme Verlag, Stuttgart, 1961.

Of course, mixtures of emulsifiers and / or protective colloids can be used. The dispersants used are preferably exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They may be anionic, cationic or nonionic in nature. Of course, in the case of the use of mixtures of surface-active substances, the individual components must be compatible with one another, which in case of doubt can be checked by hand on the basis of a few preliminary tests. In general, anionic emulsifiers are compatible with each other and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually incompatible with one another.

Common emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ to C ₁₂ ), ethoxylated fatty alcohols (EO degree: 3 to 50; Alkyl: ₈ to C ₃₆₎ and alkali metal and ammonium salts (of alkyl sulfates alkyl radical C: ethoxylated C ₁₂ to C ₁₈₎ and C ₈ to C _12), ethoxylated sulfuric acid monoesters of alkanols (EO units: 4 to 30, alkyl radical alkylphenols (EO units: 3 to 50, alkyl radical: C ₄ to C _I2), of alkylsulfonic acids (alkyl radical: C ₁₂ to C ₈₎ and of alkylarylsulfonic acids (alkyl radical: C ₉ to C _18). Further suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, pages 192 to 208, Georg-Thieme-Verlag, Stuttgart, 1961.

As surface-active substances are also compounds of the general formula II

wherein R ⁹ and R ^{10 are} C ₄ - to C ₂₄ -alkyl and one of R ⁹ or R ^{10 may} also be hydrogen, and A and B may be alkali metal ions and / or ammonium ions proved. In the general formula II, R ⁹ and R ^{10 are} preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or H atoms, where R ⁹ and R ^{10 are} not both simultaneously H and Atoms are. A and B are preferably sodium, potassium or ammonium ions, with sodium ions being particularly preferred. Particularly advantageous are compounds II in which A and B are sodium ions, R ^{9 is} a branched alkyl radical having 12 C atoms and R ^{10 is} an H atom or R ⁹ . Industrial mixtures are used which have a share of 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ^® 2A1 (trademark of Dow Chemical Company). The compounds II are well known, for example from US-A 4,269,749, and commercially available.

Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali and alkaline earth metal salts, e.g. Sodium, potassium, magnesium, calcium, as well as ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates, alkyl glycol alkoxylates and diglycol alkoxylates and alkyl ether carboxylates can have between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.

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

Suitable surfactants are, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium laurylsuccinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.

In general, the amount of dispersant used is 0.1 to 5 wt .-%, preferably 1 to 3 wt .-%, each based on the total amount of the monomers to be radically polymerized. It is often favorable if a partial or total amount of the dispersing assistant is supplied to the fluid reaction medium before the initiation of the free-radical polymerization. In addition, a partial or total amount of the dispersing assistant may advantageously also be added to the reaction medium together with the monomers to be polymerized, in particular in the form of an aqueous monomer emulsion during the polymerization. Preference is given to a combination of ionic and nonionic dispersion auxiliaries.

regulator

The regulators used are preferably alkanethiols. Mixtures of several controllers can also be used.

The alkanethiols linear and branched alkanethiols with a carbon chain length of C io to C are used _22nd Particular preference is given to linear alkanethiols, furthermore preference is given to alkanethiols having a chain length of from C ₁₂ to C ₂₂ , in particular from C ₁₂ to C ₁₈ . Preferred alkanethiols which may be mentioned are n-decanethiol, n-dodecanethiol, tert-dodecanethiol, n-tetradecanethiol, n-pentadecanethiol, n-hexadecanethiol, n-heptanecanethiol, n-octadecanethiol, n-nonadecanethiol, n-eicosanthiol, n- Docosanthiol. Particularly preferred are linear, even alkane thiols. The alkanethiols can also be used in mixtures.

The alkanethiols are usually used in amounts of 0.1 to 5 wt .-%, in particular 0.25 to 2 wt .-% based on the monomers to be polymerized. Usually the alkanethiols are added to the polymerization together with the monomers. Particularly preferred for use as a regulator is n-dodecanethiol.

hydrogen peroxide treatment If alkanethiols with a C chain length of C ₁₀ to C ₁₃ are used in the polymerization, subsequent hydrogen peroxide treatment may be required in order to obtain odorless neutral polymers. For this hydrogen peroxide treatment subsequent to the polymerization, usually 0.01 to 2.0% by weight, in particular 0.02 to 1.0% by weight, preferably 0.3 to 0.8% by weight, furthermore preferably 0.03 to 0.15% by weight of hydrogen peroxide, based on the monomers to be polymerized. It has proved advantageous that Was¬ serstoffperoxidbehandlung at a temperature of 20 to 100 ^c C, in particular from 30 to 80 ⁰ C to carry out. The hydrogen peroxide treatment is usually carried out for a period of 30 minutes to 240 minutes, in particular from 45 minutes to 90 minutes.

If alkanethiols with a C chain length of C ₁₄ to C ₂₂ are used, the hydrogen peroxide treatment can be omitted. In a further embodiment of the invention, however, a hydrogen peroxide treatment can also be used in the use of alkanethiols having a chain length of C ₄ to C ₂₂ .

K value

In a preferred embodiment, the K value of the polymers according to the invention is in the range from 20 to 70, particularly preferably in the range from 20 to 55 and very particularly preferably in the range from 25 to 45. The respectively desired K value can be selected the polymerization conditions, for example, the Polymerisa¬ tion temperature and the initiator concentration set.

In a preferred embodiment, regulators are used to set the K value, in particular when the emulsion and suspension polymerization are used.

The K value can be adjusted by selecting the type and / or the amount of the regulator. In a preferred embodiment, lower K values are set by larger amounts of regulator based on the total amount of monomer.

Carrying out the emulsion polymerization

The emulsion polymerization is usually carried out with exclusion of oxygen, spielsweise under nitrogen or argon atmosphere, at temperatures ranging from 20 to 200 ⁰ C. Advantageously, polymerization temperatures are in the range of 50 to 130, especially 70 to 95 ° C.

In the case of the free-radically initiated emulsion polymerization, it is important to ensure that the polymerisation mixture does not boil, especially at relatively high temperatures in order to avoid coagulum formation. This can be avoided, for example, by carrying out the polymerization reaction at an inert gas pressure which is higher than the vapor pressure of the polymerization mixture, for example 1, 2 bar, 1, 5 bar, 2 bar, 3 bar, 5 bar, 10 bar or even higher (absolute values in each case). The polymerization can be carried out batchwise, semicontinuously or continuously. Often, the polymerization or the monomer and the regulator dosage semikontinu¬ ierlich after the feed process.

The amounts of monomers and dispersants are conveniently chosen so as to contain a 30 to 80 wt .-% dispersion of the copolymers. Preferably, at least some of the monomers, initiators and, if appropriate, regulators are metered uniformly into the reaction vessel during the polymerization (feed run). However, the monomers and the initiator can also be initially charged in the reactor and polymerized, it being necessary to cool.

According to a preferred embodiment, the polymerization is carried out using a seed latex. Conveniently, the seed latex is usually prepared from the polymers to be polymerized in the first polymerization. Subsequently, the remaining portion of the monomer mixture is added, preferably by the feed process.

The polymerization reaction is advantageously carried out to a monomer conversion> 95 wt .-%, preferably> 98 wt .-% or> 99 wt .-%.

It is often useful if the resulting aqueous polymer dispersion is subjected to a postpolymerization step to further lower the unreacted amount of monomer. This measure is known to the person skilled in the art (for example EP-B 3957, EP-B 28348, EP-B 563726, EP-A 764699, EP-A 767180, DE-A 3718 520, DE-A 3834734, DE-A 4232194, DE -A 19529599, DE-A 19741187, DE-A 19839199, DE-A 19840586, WO 95/33775 or US 4529753).

Preparation of the Dispersions The aqueous polymer dispersions obtainable according to the invention can be converted in a simple manner into redispersible polymer powders.

When the polymer is prepared by emulsion polymerization, the resulting dispersion may either be incorporated directly into the aqueous, aqueous-alcoholic or alcoholic hair cosmetic preparation or the dispersion may be dried, e.g. Spray drying, fluidized spray drying, drum drying or Ge freeze drying, so that the polymer can be used as a powder and processed.

Preferably, the spray drying is used. The resulting polymer dry powders can advantageously be converted again into an aqueous solution or dispersion by dissolving or redispersing in water. Powdery copolymers have the advantage of a better shelf life, a ein¬ easier transport and usually show a lower propensity for microbial attack. These include, in general, anionic, cationic, amphoteric and neutral polymers.

Of course, it is also possible to subject the aqueous polymer dispersion obtained before or after the postpolymerization step to an inert gas and / or water vapor stripping which is likewise known to the person skilled in the art. This stripping process preferably takes place after the postpolymerization step. As described in EP-A 805169, a partial neutralization of the dispersion to a pH in the range of 5 to 7, preferably to a pH in the range of 5.5 to 6.5 before the physical De¬ sodorierung of Advantage.

For neutralization, aqueous buffer solutions, such as, for example, buffers based on alkali metal or ammonium carbonate or bicarbonate, are suitable.

The neutralizing agents are preferably added as a dilute aqueous solution for polymer dispersion.

Optionally, the pH can also be adjusted by adding a buffer solution, with buffers based on alkali metal or ammonium carbonate or bicarbonate being preferred.

Neutralization

In addition, the polymers present in the aqueous dispersion prior to or after the aftertreatment can be partly or completely neutralized.

In particular for the use of the polymers in hair cosmetic preparations, a partial or complete neutralization of the polymer dispersions is advantageous.

In preferred embodiments, the polymers are for example at least 10, preferably at least 30, more preferably at least 40, more preferably at least 50, most preferably at least 70 and in particular at least 95% neutralized.

In a particularly preferred embodiment, the polymers are at least 99% neutralized. Most preferably, the neutralization is at least 100%. It is also advantageous if the neutralizing agent is added in more than equivalent amount, wherein the equivalent amount is understood to mean the amount needed to neutralize all neutralizable groups of the polymers.

The neutralization can also be done with

a mono-, di- or trialkanolamine having 2 to 5 carbon atoms in the alkanol radical, which is optionally present in etherified form, for example mono-, di- and triethanolamine, mono-, di- and tri-n-propanolamine, mono-, di and triisopropanolamine, 2-amino-2-methylpropanol and di (2-methoxyethyl) amine, an alkanediolamine having 2 to 5 carbon atoms, for example 2-amino-2-methylpropane-1,3-diol and 2-amino-2 -ethylpropane-1,3-diol, or a primary, secondary or tertiary alkylamine having a total of 5 to 10 carbon atoms, for example N, N-diethylpropylamine or 3-diethylamino-1-propylamine.

Suitable alkali metal hydroxides for neutralization are, in particular, sodium hydroxide or potassium hydroxide and also ammonium hydroxide.

Often, good neutralization results are obtained with 2-amino-2-methylpropanol, triisopropanolamine, 2-amino-2-ethylpropane-1,3-diol, N, N-dimethylaminoethanol or 3-diethylamino-1-propylamine.

To neutralize the polymers in the preparations and compositions according to the invention, in particular, amino-containing silicone polymers are also suitable. Geeigne¬ te silicone polymers comprising amino groups, for example, the silicone amino oxide block copolymers of WO 97/32917, the products Silsoft ^® A-843 (di- methicone bisamino hydroxypropyl copolyol) and Silsoft ^® A-858 (trimethylsilyl Amodi- methicone copolymer) (both company Witco). Furthermore, the neutralization polymers of EP-A 1035144 and in particular the silicone-containing neutralization polymers of claim 12 of EP-A 1035144 are also suitable.

Preservation of the dispersions

For stabilizing and preserving the dispersion polymers, conventional preservatives are used. Hydrogen peroxide is preferably used.

Cosmetic and pharmaceutical preparations

The invention relates to cosmetic and pharmaceutical preparations ent¬ holding the copolymers of the invention.

The copolymers described above contained in the preparations according to the invention are outstandingly suitable for the preparation of cosmetic and pharmaceutical preparations. shear means. They serve z. As a polymeric film former in preparations for personal care, which includes the application in cosmetic preparations for keratinous Ober¬ surfaces such as skin, hair, nails and oral care preparations.

They can be used universally in a wide variety of cosmetic preparations and formulated and compatible with the usual components. In particular, the copolymers according to the invention are suitable for the preparation of hair cosmetic compositions.

Compared with customary polymers known from the prior art, they are advantageously suitable for producing elastic hairstyles while at the same time having strong strength even at high atmospheric humidity.

The copolymers according to the invention are also distinguished by good propellant gas compatibility, good solubility in water or aqueous / alcoholic solvent mixtures, the suitability for use in low-VOC formulations and good washability. In addition, they usually also have good conditioning properties, d. H. They improve treated hair in terms of its sensory properties such as grip, volume, handling, etc.

Hairspray formulations based on the copolymers according to the invention are distinguished by good rheological properties such as flexural strength and elasticity and good sprayability. Furthermore, the films which can be prepared from the polymers according to the invention are not tacky.

The cosmetic preparations according to the invention can be used as aqueous or aqueous-alcoholic solutions, O / W and W / O emulsions in the form of shampoos, creams, foams, sprays (pump spray or aerosol), gels, gel sprays, lotions or mousses be present and accordingly formulated with conventional further excipients.

The polymers are preferably formulated in hair cosmetic preparations as sprays (pump spray or aerosol). Most preferably, they are provided as VOC-55 formulations.

Cosmetically or pharmaceutically acceptable carrier B) The preparations according to the invention additionally have at least one cosme¬ tically or pharmaceutically acceptable carrier B which is selected from

i) water, ii) water-miscible organic solvents, preferably C ₂ -C ₄ -alkanols, especially ethanol, iii) oils, fats, waxes, iv) of iii) various esters of Ce-Cso monocarboxylic acids with mono-, di- or trihydric alcohols, v) saturated acyclic and cyclic hydrocarbons, vi) fatty acids, vii) fatty alcohols, viii) propellants, and mixtures thereof.

Additives The preparations according to the invention have, for. An oil or fat component B) selected from: low polarity hydrocarbons such as mineral oils; linear saturated hydrocarbons, preferably having more than 8 C atoms, such as tetradecane, hexadecane, octadecane, etc .; cyclic hydrocarbons, such as deca- hydronaphthalene; branched hydrocarbons; animal and vegetable oils; To grow; Wax esters; Petroleum jelly; Esters, preferably esters of fatty acids, such as. As the esters of C _r C ₂₄ -Monoalkbholen with such as isopropylisostearate, n-propyl myristate, isopropyl myristate, n-propyl palmitate, isopropyl palmitate, hexacosanyl palmitate, octacosanyl palmitate, triacontanyl palmitate, dotriacontanyl palmitate, tetratriacontanyl palmitate, hexane cosanyl stearate, octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, tetratriacontanyl stearate; Salicylates such as C ₁ -C ₁₀ salicylates, e.g. Octyl salicylate; Benzoates, such as C ₁₀ -C ₁₅ alkyl benzoates, benzyl benzoate; other cosmetic esters, such as fatty acid triglycerides, propylene glycol monolaurate, polyethylene glycol monolaurate, C ₁₀ -C ₁₅ -alkyl lactates, etc., and mixtures thereof.

Suitable silicone oils B) are z. As 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, for. B. under the term cyclomethicone commercially available.

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, lard, spermaceti, sperm oil, sperm oil, wheat germ oil, macadamia nut oil, evening primrose oil, jojoba 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 beeswax, carnauba wax, candililla wax, spermaceti and mixtures of the aforementioned oil or fat components. Suitable cosmetically and pharmaceutically acceptable oil or fat components B) are described in Karl-Heinz Schrader, Grundlagen und Rezepturen der Kosmetika, 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 Mehrwerti¬ conditions alcohols having preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, iso-propanol, propylene glycol, glycerol, sorbitol, etc.

The cosmetic agents according to the invention may be skin-cosmetic, hair-cosmetic, pharmaceutical, hygienic or pharmaceutical agents. Because of their film-forming properties, the copolymers described above are particularly suitable as additives for hair and skin cosmetics.

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

In a preferred embodiment of the invention, the compositions have a proportion of volatile organic components of at most 80% by weight, preferably at most 55% by weight and in particular at most 30% by weight. A preferred article are thus means that comply with the Iow VOC standard, ie VOC 80 and VOC 55 standard.

The cosmetically or pharmaceutically active agents according to the invention may additionally contain cosmetically and / or pharmaceutically active agents as well as excipients.

The cosmetic or pharmaceutical compositions according to the invention preferably contain at least one copolymer as defined above (= component A), at least one carrier B as defined above and at least one different component thereof, which is selected from cosmetically care agents and active ingredients such as AHA Acids, fruit acids, ceramides, phytantriol, collagen, vitamins and pro-vitamins, for example vitamin A, E and C, retinol, bisabolol, panthenol, emulsifiers and co-emulsifiers, surfactants, preservatives, perfume oils, thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, silicone compounds, natural and synthetic light stabilizers, bleaching agents, gelling agents, care compositions, colorants, opacifiers, tinting agents, tanning agents, dyes, pigments, micro-pigments such as titanium oxide or zinc oxide, consistency regulators, moisturizers fats, collagen, protein hydrolysates, lipids, antioxidants, defoamers, antistati- ka, emulsifiers, solubilizers, repellents, superfatting agents, pearlescent waxes, bodying agents, thickeners, solubilizers, complexing agents, pH regulators, reflectors, proteins and protein hydrolysates (eg wheat, almond or pea proteins) and plasticizers.

The auxiliaries may be present in the preparation of the polymers according to the invention and / or added after the polymerization.

Examples of the respective classes of excipients are mentioned below, without limiting the possible auxiliaries to those exemplified.

Another object of the invention accordingly relates to the use of the inventive acrylate polymers in cosmetic, especially hair cosmetic preparations.

emulsifiers

Examples of suitable emulsifiers are nonionic surfactants from at least one of the following groups:

(1) addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group;

(2) C12 / 18 fatty acid mono- and diesters of addition products of 1 to 30 moles of ethylene oxide with glycerol;

(3) glycerol mono- and diesters and sorbitan mono- and diesters of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and their ethylene oxide addition products;

(4) alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogs;

(5) addition products of 15 to 60 moles of ethylene oxide with castor oil and / or hydrogenated castor oil;

(6) polyol and especially polyglycerol esters, e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate. Also suitable are mixtures of compounds of several of these substance classes;

(7) addition products of 2 to 15 moles of ethylene oxide with castor oil and / or hydrogenated castor oil; (8) partial esters based on linear, branched, unsaturated or saturated Ce / ∞ fatty acids, ricinoleic acid and 12-hydroxystearic acid and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (eg sorbitol), alkyl glucosides (eg methyl glucoside, butyl glucoside, lauryl glucoside ) as well as polyglucosides (eg

Cellulose);

(9) mono-, di- and trialkyl phosphates and mono-, di- and / or tri-PEG-alkyl phosphates and their salts;

(10) wool wax alcohols;

(11) polysiloxane-polyalkyl-polyether copolymers or corresponding derivatives;

(12) mixed esters of pentaerythritol, fatty acids, citric acid and fatty alcohol according to DE-PS 1165574 and / or mixed esters of fatty acids having 6 to 22 carbon atoms, methylglycose and polyols, preferably glycerol or polyglycerol, and

(13) Polyalkylene glycols.

The addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are homolog mixtures, whose average degree of alkoxylation corresponds to the ratio of the molar amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out. C ₁₂ to C 18 -fatty acid mono- and diesters of addition products of ethylene oxide with glycerine are known from DE-PS 2024051 as refatting agents for cosmetic preparations. C ₈ to C ₈ alkyl mono- and oligoglycosides, their preparation and their dung Verwen¬ are known from the prior art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With respect to the glycoside ester, both monoglycosides in which a cyclic sugar residue is glycosidically bound to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably about 8 are suitable. The degree of oligomerization is a statistical mean value based on a homolog distribution which is customary for such technical products.

Furthermore, zwitterionic surfactants can be used as emulsifiers. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and / or one sulfonate group in the molecule. Particularly suitable zwitterionic Surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example the cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3- Hydroxyethylimidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacyl- aminoethylhydroxyethylcarboxy methylglycinat.

Particularly preferred is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine. Also suitable emulsifiers are ampholytic surfactants. Ampholytic surfactants are understood as meaning those surface-active compounds which contain, in addition to a C ₈ to C ₁₈ -alkyl or -acyl group, at least one free amino group and at least one -COOH and / or -SO ₃ H group in the molecule, and capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C ₁₂ to C ₁₈ acylsarcosine.

In addition to the ampholytic, quaternary emulsifiers are also suitable, with those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.

oil body

Examples of oil bodies are Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C ₆ -C ₂₂ fatty acids with linear C ₆ -C ₂₂ fatty alcohols, esters of branched C ₆ -C ₁₃ Carboxylic acids with linear C ₆ -C ₂₂ -fatty alcohols, esters of linear C ₆ -C ₂₂ -fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C ₆ -C ₂₂ -fatty alcohols, in particular 2-hydroxy-succinic acid dioctyl esters, esters of linear and / or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimer triol) and / or guarentextholes, triglycerides based on C ₆ -C ₁₀ -fatty acids, liquid mono- / Di- / triglyceride mixtures based on C ₆ -C ₁₈ fatty acids, esters of C ₆ -C ₂₂ fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, vegetable oils, branched primary Al alcohols, substituted cyclohexanes, linear and branched C ₆ -C ₂₂ fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and / or branched C ₆ -C ₂₂ -alcohols (eg Finsolvä TN), linear or branched, symmetrical or unsymmetrical dialkyl ethers with 6 to 22 Kohlenstoffato¬ men per alkyl group, ring-opening products of epoxidized fatty acid esters with Po lyols, silicone oils and / or aliphatic or naphthenic hydrocarbons in Be¬ costume.

Preservatives Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the further classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Regulation.

Perfume oils Optionally, the cosmetic preparations may contain perfume oils. Examples of perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, lemon, Orange), roots (macis, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme ), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore, animal raw materials come into question, such as civet and castorum. Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, 4-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, methylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallopropionate and benzylsalicylate. The ethers include, for example, benzyl ether ethers, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonate, to the ketones such as the ionones, cc-lsomethylionen and methyl cedryl ketone , among the alcohols anethof, citronellol, eugenol, isoeugenol, geraniol, linoleol, phenylethyl alcohol and terioneol, the hydrocarbons mainly include the terpenes and balsams. However, preference is given to using mixtures of different fragrances which together produce an attractive fragrance. Essential oils of lower volatility, which are most commonly used as aroma components, are suitable as perfume oils, for example sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil. Bergamot oil, dihydro myrcenol, lilial, lyral, citronellol, phenylethyl alcohol, a-hexyl cinnamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedones, sandelice, lemon oil, tangerine oil, orange oil, allylamyl glycolate, cyclovertal are preferably used , Lavandin oil, muscat sage oil, b-damascone, geranium oil bourbon, cyclohexyl salicylate, vertofix coeur, iso-e-super, fixolide NP, evernyl, iraldeine gamma, phenylacetic acid acid, geranyl acetate, benzyl acetate, rose oxide, romillate, irotyl and floramate used alone or in mixtures.

Superfatting Agents Superfatting agents may be substances such as lanolin and lecithin, as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter ones also serving as foam stabilizers.

pearlescent

Suitable pearlescent waxes are, for example: alkylene glycol esters, special ethylene glycol disterate; Fatty acid alkanolamides, especially coconut fatty acid diethanoamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms, especially laurone and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols containing 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

bodying

Suitable consistency factors are primarily fatty alcohols or hydroxy fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, partial glycerides, fatty acids or hydroxyfatty acids. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates. Suitable thickening agents are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates (eg Carbopol ™ from Goodrich or Synthalen Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated Fettsäu- reglyceride, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or Alkyloligoglucoside and electrolytes such as sodium chloride and ammonium chloride.

thickener

Typical thickeners in such formulations are crosslinked polyacrylic acids and their derivatives, polysaccharides such as xanthan gum, agar-agar, alginates or tylo acids, cellulose derivatives, eg. Carboxymethyl cellulose or hydroxycarboxymethyl cellulose, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinylpyrrole. idon. Suitable thickeners are also Aculyn ^® brands säureethoxilaten of Messrs. Rohm and Haas as Aculyn ^® 22 (copolymer of acrylates and methacrylic acid with stearyl rest (20 EO units)) and Aculyn ^® 28 (copolymer of acrylates and methacrylic with Behenyl residue (25 EO units)).

hydrotropes

Hydrotropes, such as, for example, ethanol, isopropyl alcohol, or polyols can also be used to improve the flow behavior. Polyols contemplated herein preferably have from 2 to 15 carbon atoms and at least two hydroxyl groups.

Typical examples are

glycerol;

Alkylene glycols such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols having an average molecular weight of from 100 to 1000 daltons; technical oligoglycerine mixtures having an intrinsic degree of condensation of from 1.5 to 10, such as technical grade diglycerine blends having a diglycerol content of from 40 to 50% by weight; Methylol compounds, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;

Niedrigalkylglucoside, in particular those having 1 to 8 carbons in the alkyl radical, such as methyl and Butylglucosid;

Sugar alcohols with 5 to 12 carbon atoms, such as sorbitol or

mannitol; Sugars having 5 to 12 carbon atoms, such as, for example, glucose or sucrose; Amino sugars, such as glucamine.

UV-light protection The sunscreen filters used in cosmetic preparations have the task of preventing damaging effects of sunlight on human skin and human hair or at least reducing their effects. In addition, these light protection filters also serve to protect other ingredients against destruction or degradation by UV radiation. In hair cosmetic formulations damage to the keratin fibers is to be reduced by UV rays.

Sunlight reaching the earth's surface has UV-B (280 to 320 nm) and UV-A (320 to 400 nm) radiation directly adjacent to the visible light. The influence on human skin is particularly noticeable in UVB radiation from sunburn.

As a maximum of the erythema efficiency of sunlight, the narrower range around 308 nm is given.

For protection against UV-B radiation, numerous compounds are known in which it u.a. derivatives of 3-benzylidene camphor, 4-aminobenzoic acid, cinnamic acid, salicylic acid, benzophenone and 2-phenylbenzimidazole.

Also for the range between about 320 nm and about 400 nm, the so-called UV-A range, it is important to have available filter substances, since its rays can cause reactions in photosensitive skin. It has been proven that UVA Radiation leads to damage to the elastic and collagen fibers of the Bindege¬ webes, which causes the skin to age prematurely, and that it can be seen as the cause of numerous phototoxic and photoallergic reactions. The harmful influence of UV-B radiation can be enhanced by UV-A radiation.

Oil-soluble organic UV-A filters and / or UV-B filters and / or water-soluble organic UV-A filters and / or UV-B filters can be used as UV light protection filters. The total amount of UV photoprotective filters is generally from 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 15 wt .-%, in particular 1 to 10 wt .-%, based on the total weight of preparations.

Advantageously, the UV photoprotective filters are chosen so that the preparations protect the skin from the entire range of ultraviolet radiation.

For example, UV protection filters are:

Other combinable sunscreens are u.a. following connections:

OCH3

H 3 Co

(H3C) COO-isooctyl COOCH2CH (OH) CH2OH

[H3CCH (OH) CH2] 2NCOOC2H5

COO-isooctyl

Also suitable are UV-blocking pigments, such as titanium dioxide, talc and zinc oxide.

Light stabilizers suitable for use in the preparations according to the invention are furthermore the compounds mentioned in EP-A 1 084696 in paragraphs [0036] to [0053], to which reference is made in its entirety.

The enumeration of said UV light protection filters which can be used in the preparations according to the invention should of course not be limiting.

Germ-inhibiting agents Furthermore, germ-inhibiting agents can also be used in the preparations according to the invention. These generally include all suitable preservatives having specific activity against Gram-positive bacteria, e.g. Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether), chlorhexidine (1,1'-hexamethylenebis [5- (4-chlorophenyl) biguanide), and TTC (3,4,4'-trichlorocarbanilide).

Quaternary ammonium compounds are also suitable in principle, but are preferably used for disinfecting soaps and washing lotions.

Also numerous fragrances have antimicrobial properties. Special combinations with particular efficacy against Gram-positive bacteria are used for the composition of so-called Deopfarums.

A large number of essential oils or their characteristic ingredients such as clove oil (eugenol), mint oil (menthol) or thyme oil (thymol), show a pronounced antimicrobial activity. The antibacterial substances are usually used in concentrations of about 0.1 to 0.3 wt .-%.

Because of their film-forming properties, the copolymers described above are particularly suitable as additives for hair and skin cosmetics.

Cosmetically and / or pharmaceutically active agents

Other suitable cosmetically and / or pharmaceutically active agents are, for. Coloring agents, skin and hair pigmenting agents, tinting agents, tanning agents, bleaching agents, keratin-hardening substances, repellent active ingredients, hyperemic substances, keratolytic and keratoplastic substances, antidandruff active ingredients, antiphlogistics, keratinizing substances, antioxidant or active substances which are active as free radical scavengers, skin-moisturizing or moisturizing substances, moisturizing active substances, anti-erythematous or anti-allergic active substances and mixtures thereof.

Artificial skin tanning agents that are suitable for tanning the skin without natural or artificial irradiation with UV rays, z. Dihydroxyacetone, alloxan and walnut shell extract.

Suitable keratin-hardening substances are as a rule active ingredients, as are also used in antiperspirants, such as, for example, Potassium aluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc.

Antimicrobial agents 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 formation or intensity of body odor. These include z. For example, conventional, known in the art Konservie¬ rungsmittel, such as p-hydroxybenzoic acid, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are, for. Zinc ricinoleate, triclosan, undecylenic acid alkylolamides, citric acid triethyl ester, chlorhexidine etc. Suitable repellent active ingredients are compounds which are able to prevent or expel certain animals, in particular insects, from humans. This includes z. B. 2-ethyl-1,3-hexanediol, N, N-diethyl-m-toluamide, etc.

Suitable hyperemic substances which stimulate the perfusion of the skin are, for. For example, essential oils such as mountain pine, lavender, rosemary, juniper berry, horse chestnut extract, birch leaf extract, hay flower extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil, etc.

Suitable keratolytic and keratoplastic substances are for. Salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc.

Suitable anti-uppen active ingredients are, for. Sulfur, Schwefelpolyethylenglykolsor- bitanmonooleat, Schwefelricinolpolyethoxylat, Zinkpyrithion, Aluminiumpyrithion, etc. Suitable antiphlogistics, which counteract skin irritation, z. Allantoin, bisabolol, dragosantol, chamomile extract, panthenol, etc.

The cosmetic agents according to the invention may contain as cosmetic and / or pharmaceutical active ingredient (as well as optionally as excipient) at least one cosmetically or pharmaceutically acceptable polymer.

Hair cosmetic preparations

Possible forms of hair cosmetic preparations are hair treatments, hair lotions, hair rinses, hair emulsions, top fluids, perming agent for permanent waving, hot oil treatment preparations, conditioners, curl relaxers, styling wrap alloys, setting lotions, shampoos, hair waxes, pomades, hair foams, Hair dyes or hair sprays.

Particularly preferred are hair cosmetic preparations for strengthening hairstyles, which are in the form of spray preparations and / or hair foams.

The polymers contained in the hair cosmetic preparations according to the invention are distinguished by their high compatibility with the nonpolar propellants in spray preparations, in particular with hydrocarbons such as n-propane, isopropane, n-butane, isobutane, n-pentane and mixtures thereof and especially due to the excellent sprayability as a pump spray or aerosol.

The polymers are furthermore very well tolerated with other additives customary in hair cosmetics, have a good hair-firming action, form films with very good mechanical properties, are easy to wash out and are characterized by the fact that they practically do not stick to the hair. In addition to odorlessness, the polymers display excellent results in the performance properties in hair cosmetic preparations. They are clearly soluble in alcohols such as ethanol or isopropanol and in mixtures of these alcohols with water. The clarity of the solutions is retained even when the solutions in standard spray formulations are used together with blowing agents such as dimethyl ether. In particular, they are clearly formu lable in aqueous low-VOC preparations with at most 55% by weight of volatile organic constituents (VOC-55).

The hair cosmetic preparations according to the invention are perfectly washable out of the hair. Treated hair has increased suppleness and a pleasant natural feel. The strengthening effect is at the same time high, so that in principle a reduction of the required amount of film former in the hair spray formulation is possible. Due to the odorlessness of the polymers can be dispensed with if necessary to add odor masking perfume oils.

The hair cosmetic preparations usually comprise from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, in particular from 2 to 10% by weight, of the partially or completely neutralized polymers, based on the preparation.

Hair spray formulations

A preferred embodiment of the invention are hairspray preparations containing the following ingredients:

0.1 to 20 wt .-%, preferably 0.5 to 15 wt .-%, in particular 1 to 10 wt .-% of the partially or completely neutralized polymer 0 to 99.9 wt .-%, preferably 1 to 50 wt %, in particular 10 to 20 wt .-% water - 0 to 95 wt .-%, preferably 20 to 60 wt .-%, in particular 25 to

50 wt .-% of a conventional organic solvent such as especially ethanol, isopropanol and dimethoxymethane and also acetone, n-propanol, n-butanol, 2-methoxypropan-1-ol, n-pentane, n-hexane, cyclohexane, n- Heptane, n-octane or dichloromethane or mixtures thereof - 0 to 90 wt .-%, preferably 30 to 80 wt .-%, in particular 45 to

60% by weight of a customary propellant, such as n-propane, isopropane, n-butane, isobutane, 2,2-dimethylbutane, n-pentane, isopentane, dimethyl ether, difluoroethane, fluorotrichloromethane, dichlorodifluoromethane or dichlorotetrafluoroethane, HFC 152A or their mixtures.

Alkanolamines are used to neutralize various types of acids and to adjust the pH of cosmetic products. Examples (designations according to INCI) are aminomethyl propanol, diethanolamines, diisopropanolamines, ethanolamines, methylethanolamines, N-lauryl diethanolamines, triethanolamines, triisopropanolamines, etc. In addition, alkali metal hydroxides (eg NaOH, KOH) and other bases can be used for neutralization (eg histidine, Arginine, lysine or Ethylenediami- ne, diethylenetriamine, melamine, benzoguanamine). All stated bases can be used alone or as a mixture with other bases for the neutralization of acid-containing cosmetic products.

Propellants (Propellant Gases) The propellants (propellants) used are in particular the hydrocarbons, in particular propane, n-butane, n-pentane and mixtures thereof, as well as dimethyl ether and difluoroethane, of the compounds mentioned. Optionally, one or more of said chlorinated hydrocarbons are used in propellant mixtures, but only in small amounts, for example up to 20 wt .-%, based on the propellant mixture.

The hair cosmetic preparations according to the invention are also particularly suitable for pump spray formulations without the addition of propellants or else for aerosol sprays with customary compressed gases such as nitrogen, compressed air or carbon dioxide as propellant.

The copolymers according to the invention are particularly suitable as setting agents in hairstyling preparations, in particular hairsprays (aerosol sprays and pump sprays without propellant gas) and hair foams (aerosol foams and pump foams without propellant gas).

In a preferred embodiment, spray formulations contain

a) from 0.1 to 10% by weight of at least one copolymer according to the invention, b) from 20 to 99.9% by weight of water and / or alcohol, c) from 0 to 70% by weight of at least one blowing agent, 20% by weight of other ingredients.

Blowing agents are the blowing agents commonly used for hairsprays or aerosol foams. Preference is given to mixtures of propane / butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152a), carbon dioxide, nitrogen or compressed air.

A preferred formulation for aerosol hair foams according to the invention

a) from 0.1 to 10% by weight of at least one copolymer according to the invention, b) from 55 to 99.8% by weight of water and / or alcohol, c) from 5 to 20% by weight of a blowing agent, d) O ₁ 1 to 5 wt .-% of an emulsifier, e) 0 to 10 wt .-% further ingredients.

As emulsifiers all emulsifiers commonly used in hair foams can be used. Suitable emulsifiers may be nonionic, cationic or anionic or amphoteric.

Propellants particularly suitable for aerosol foams are mixtures of dimethyl ether and, optionally halogenated, hydrocarbons, such as propane, butane, pentane or HFC-152a.

Examples of nonionic emulsifiers (INCI nomenclature) are Laurethe, z. B. Laureth-4; Cetethe, z. Cetheth-1, polyethylene glycol cetyl ether; Cetearethe, z. Cethethreeth-25, polyglycol fatty acid glycerides, hydroxylated lecithin, lactyl esters of fatty acids, alkylpolyglycosides.

A standard aqueous spray formulation has, for example, the following composition:

^From 2% to 10% by weight of the 100% 2-amino-2-methylpropanol neutralized polymer

^■ 10 to 76% by weight of ethanol

^■ 2 to 20% by weight of water

^From 10 to 60% by weight of dimethyl ether and / or propane / n-butane and / or propane / isobutane.

The hair cosmetic formulations of the invention comprise in a preferred embodiment

a) 0.05 to 20 wt .-% of at least one copolymer of the invention, b) 20 to 99.95 wt .-% of water and / or alcohol, c) 0 to 50 wt .-% of at least one propellant gas, d) 0 to 5% by weight of at least one emulsifier, e) 0 to 3% by weight of at least one thickener, and f) up to 25% by weight of further constituents.

By alcohol, all alcohols customary in cosmetics are to be understood, for. For example, ethanol, isopropanol, n-propanol. Other polymers

For the targeted adjustment of the properties of the hair cosmetic preparations, it may be advantageous to use the setting polymers as a mixture with other polymers.

Suitable conventional polymers include, for example, anionic, cationic, amphoteric and neutral polymers.

Preferred examples of such further polymers are

Copolymers of ethyl acrylate and methacrylic acid

Copolymers of N-tert-butylacrylamide, ethyl acrylate and acrylic acid

polyvinylpyrrolidones

Polyvinylcaprolactams - polyurethanes

Copolymers of acrylic acid, methyl methacrylate, octylacrylamide, butylaminoethylmethyl acrylate and hydroxypropyl methacrylate,

Copolymers of vinyl acetate and crotonic acid and / or (vinyl) -nodecanoate, copolymers of vinyl acetate and / or vinyl propionate and N-vinylpyrrolidone, - carboxy-functional copolymers of vinylpyrrolidone, t-butyl acrylate, methacrylic acid, copolymers of tert-butyl acrylate, methacrylic acid and dimethicones copolyol.

Surprisingly, it has been found that preparations containing the polymers in combination with these other polymers have unexpected properties. The preparations according to the invention are superior to the preparations of the prior art, in particular with regard to their hair cosmetic properties. Furthermore, they have very good film-forming and firming properties.

Copolymers of ethyl acrylate and methacrylic acid (INCI name: Acrylates Copo- lymer), are available, for example, as commercial products Luviflex Soft ^® (BASF).

Copolymers of N-tert-butylacrylamide, ethyl acrylate and acrylic acid (INCI Bezeich¬ voltage: Acrylates / Acrylamide Copolymer) are available, for example, as commercial products UIT rahold ^® Strong, Ultrahold ^® 8 (BASF).

Polyvinylpyrrolidones (INCI name: PVP) for example, are among the Handels¬ Luviskol ^® K, Luviskol ^® K 30 ™ (BASF) and PVP K (ISP) name available.

Polyvinylcaprolactams (INCI: Polyvinylcaprolactams) are for example available under the trade name Luviskol ^® Plus ™ (BASF). Polyurethanes (INCI: Polyurethane-1) are for example available under the trade name Luviset ^® PUR.

Copolymers of acrylic acid, methyl methacrylate, octyl acrylamide, methyl acrylate butylaminoethyl methacrylate, hydroxypropyl methacrylate (INCI: Octylacrylami- de / Acrylates / Butylaminoethyl Methacrylate Copolymer) are known for example under the trade name Amphomer ^® 28-4910 and Amphomer ^® LV-71 (National Starch).

Copolymers of vinyl acetate and crotonic acid (INCI: VA / crotonates / copolymer) are available for example under the trade name Luviset CA 66 ^® (BASF), Resyn ^® 28-1310 (Na¬ tional Starch) and Aristoflex ^® A (Celanese).

Copolymers of vinyl acetate, crotonic acid and (vinyl) neodecanoate (INCI: VA / Crotonates / Neodecanoate Copolymer) are available for example under the trade names Resyn ^® 28-2930 (National Starch) and Luviset ^® CAN (BASF).

Copolymers of vinyl acetate and N-vinylpyrrolidone (INCI: PVP / VA) are available for example under the trade name Luviskol VA ^® (BASF), and PVP / VA (ISP).

Carboxy-functional copolymers of vinylpyrrolidone, t-butyl acrylate, methacrylic acid are available for example, under the trade name Luviskol ^® VBM (BASF).

Copolymers of tert-butyl acrylate, methacrylic acid and dimethicone copolyol are bei¬ pielsweise under the trade name Luviflex Silk ^® (BASF).

Suitable further polymers are, for example, anionic polymers. Such anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or salts thereof, copolymers of acrylic acid and acrylamide and salts thereof, sodium salts of polyhydroxycarboxylic acids, copolymers of acrylic acid and methacrylic acid with, for example, the novel (meth) acrylate polymers hydrophobic monomers, such as C ₄ -C ₃₀ -alkyl esters of (meth) acrylic acid, C ₄ - C ₃₀ -Alkylvinylester, C ₄ -C ₃₀ -alkyl and hyaluronic acid and further under the trade names Amerhold DR-25, Ultrahold ^®, Luviset ^® PUR, Acronal ^®, ^® Acudyne, Lovocryl ^®, ^® Versatyl, Amphomer ^® (28-4910, LV-71), Placise ^® L53, Gantrez ^® ES 425, Advantage Plus ^®, Omnirez ^® 2000, Resyn ^® 28-1310, Resyn ^® 28-2930, Balance ^® (0/55), Acudyne ^® 255, Aristoflex ^® A or Eastman AQ ^® known polymers.

Also suitable as additional polymers are water-soluble or water-dispersible polyesters, polyureas, co-polyurethane ureas, maleic anhydride copolymers optionally reacted with alcohols or anionic polysiloxanes. Other suitable polymers which are furthermore suitable include, for example, cationic polymers with the INCI name Polyquaternium, for example

- copolymers of N-vinylpyrrolidone / N-vinylimidazolium salts (available spielsweise under the trade names Luviquat ^® FC, Luviquat ^® HM, Luviquat ^® MS, Luviquat Care ^® (BASF),

Copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (for example, available under the trade name Luviquat ^® Hold), - copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (available, for example under the trade name Luviquat ^® PQ 11), cationic cellulose derivatives ( Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7), - Styleeze ^® CC-10, Aquaflex ^® SF-40,

Guar hydroxypropyltrimethylammonium chloride (INCI: hydroxypropyl guar hydroxypropyltrimonium chlorides), polyethyleneimines and their salts, polyvinylamines and their salts.

Other hair cosmetic polymers which are also suitable are neutral polymers, such as polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinylpropionate, polysiloxanes, polyvinylcaprolactam and copolymers with N-vinylpyrrolidone, cellulosic derivatives, polyaspartic acid salts and derivatives. These include those known under the trade name Luviskol ^® (K, VA, Plus), PVP K, PVP / VA, Advantage ^® HC and _H2 OLD EP * -1.

Also suitable are biopolymers, i. Polymers obtained from naturally renewable raw materials and constructed from natural monomer building blocks, e.g. Cellulose derivatives, chitin, chitosan, DNA, hyaluronic acid and RNA derivatives.

Other suitable polymers include betaine polymers such as Yukaformer (R205, SM) and diaformer.

Of course, the hair cosmetic preparations, if necessary, all previously mentioned cosmetic ingredients may be added.

In a further preferred embodiment of the invention, the cosmetic preparation is a product for styling. SO

A preparation suitable for styling gels according to the invention can be composed, for example, as follows:

a) 0.1 to 10 wt .-% of at least one copolymer of the invention, b) 80 to 99.85 wt .-% of water and / or alcohol, c) 0 to 3 wt .-%, preferably 0.05 to 2 wt .-%, of a gelling agent, d) 0 to 20 wt .-% further constituents.

However, the use of gelling agents may be advantageous to adjust for specific theological or other performance properties of the gels. As Gelbild¬ ner all customary in cosmetics gelling agents can be used. These include slightly crosslinked polyacrylic acid, for example carbomer (INCI), cellulose derivatives, eg. Hydroxypropyl cellulose, hydroxyethyl cellulose, cationic modified celluloses, polysaccharides, e.g. Xanthan gum, caprylic / capric triglyceride, sodium acrylate copolymers, Polyquaternium-32 (and) Paraffinum Liquidum (INCI), sodium acrylate copolymers (and) Paraffinum Liquidum (and) PPG-1 trideceth-6, acrylamidopropyltrimonium chloride / acrylamide Copolymers, Steareth-10 Allyl Ether Acrylate Copolymers, Polyquaternium-37 (and) Paraffinum Liquidum (and) PPG-1 Trideceth-6, Polyquaternium 37 (and) Propylene Glycol Dicaprate Dicaprylate (and) PPG-1 Trideceth-6, Polyquaternium-7, Polyquaternium-44th

A further preferred embodiment of the invention are products for the hair, which are selected from hair shampoo and hair products, which are rinsed or not rinsed off and applied before or after shampooing, dyeing, decolorization, perming or wrinkling.

In a further preferred embodiment of the invention, the cosmetic preparation is packaged in an atomizer, pump bottle or aerosol container in order to obtain a spray, a lacquer or a foam.

Another object of the invention is a method for the treatment of hair, characterized in that the hair is brought into contact with the cosmetic preparation according to the invention and optionally rinsed with water.

The copolymers according to the invention, as defined above, can preferably be used in shampoo formulations as setting and / or conditioning agents. Be¬ preferred Shampooformulierungen included

a) 0.05 to 10 wt .-% of at least one copolymer of the invention, b) 25 to 94.95 wt .-% water, c) 5 to 50 wt .-% of surfactants, c) 0 to 5 wt .-% of a further conditioning agent, d) 0 to 10 wt .-% further cosmetic ingredients.

In the shampoo formulations all anionic, neutral, amphoteric or cationic surfactants commonly used in shampoos can be used.

Another object of the invention is the use of the copolymer of the invention in cosmetic preparations.

Another object of the invention is the use of the copolymer of the invention as auxiliaries in pharmacy, preferably as or in coating agent (s) for solid dosage forms, for the modification of theological properties, as surface-active compound, as or in adhesives (n ) as well as in or in coating agent (s) for the textile, paper, printing and leather industries.

The following examples are intended to exemplify the invention without limiting it in any way.

Examples

The polymers can be prepared by conventional methods known to those skilled in the art. Preference is given to the solution polymerization in alcohol and / or water, and particularly preferably the emulsion polymerization.

Abbreviations:

MAS methacrylic acid

AS acrylic acid

ITS itaconic acid

UMA ureidomethacrylate

MMA methylmethacrylate

EMA ethyl methacrylate n-BMA n-butyl methacrylate t-BMA t-butyimethacrylate t-BA t-butyl acrylate

EA ethyl acrylate

EHA ethylhexyl acrylate n-BA n-butyl acrylate

HEMA hydroxyethyl methacrylate

HEA hydroxyethyl acrylate

HPA hydroxypropyl acrylate w / w in weight ratio

WS active ingredient

DME dimethyl ether Preparation of the polymers by emulsion polymerization

Example 1: Ethyl Methacrylate / Methacrylic Acid 75/25 w / w

In a 2 l polymerization vessel with a stirrer and heating and cooling devices wur¬ at a temperature of 20 to 25 ⁰ C.

250 g of deionized water 0.6 g of a 15% strength by weight aqueous solution of sodium lauryl sulfate in deionized water

35g of feed Il (see below)

submitted and heated to 45 ° C with stirring and nitrogen atmosphere. After reaching the temperature, feed I (see below) was added within 5 minutes. The mixture was then heated to 80 ⁰ C and over 2.5 hours with gleichbleiben¬ the metered feed streams while stirring and maintaining the reaction temperature Re¬ the remainder of feed Il.

After the feeds, the reaction mixture was stirred for a further hour at 80 ⁰ C and then cooled to 60 °.

While maintaining the temperature of 60 °, feed III (see below) was added. It was then cooled to 35 ° C and while maintaining the Reaktionstempe¬ temperature feed IV (see below) was added.

Feed I:

5 g of 7% strength by weight aqueous solution of sodium persulfate in deionized water

Feed Il is an aqueous monomer emulsion prepared from:

For example, Tween ™ 80 can be used as the nonionic emulsifier. Production Feed Il

The total amount of the 15% strength by weight aqueous solution of sodium lauryl sulfate and then the total amount of the nonionic emulsifier are added to the initially introduced deionized water with stirring. The corresponding amounts of ethyl methacrylate, methacrylic acid and n-dodecylmercaptan are added in the order given to the homogeneous solution which is stirred further.

Feed III: 2 g 30% strength by weight solution of hydrogen peroxide in deionized water

Feed IV:

40 g of a 10% by weight solution of ammonium bicarbonate in deionized water

The polymers of the following Examples 2 to 20 were synthesized analogously to Example 1, wherein Feed II for each example was chosen as indicated below. Emulsifier / asser / batch size / emulsion preparation / controller analogous to example 1.

Example 2: Ethyl methacrylate / t-butyl acrylate / methacrylic acid 50/25/25 w / w / w

Example 3: n-butyl methacrylate / methacrylic acid 75/25 w / w (comparative example)

Example 4: t-butyl methacrylate / methacrylic acid 75/25 w / w (comparative example)

Example 5: Methyl Methacrylate / Methacrylic Acid 75/25 w / w (Comparative Example)

The polymers of the following Examples 6 to 20 were synthesized analogously to Example 1, wherein feed Il was chosen as appropriate for each example as indicated below. Emulsifiers / water / batch size / emulsion preparation / controller analogous to example 1.

Example 21: Ethyl methacrylate / acrylic acid / methacrylic acid 75/5/2 w / w / w

250 gped water

0.6 g of a 15% by weight aqueous solution of sodium lauryl sulfate in deionized

water

35 g of feed Il (see below) and heated to 45 ° C. with stirring and nitrogen atmosphere. After reaching the temperature, feed I (see below) was added within 5 minutes. The mixture was then heated to 80 ⁰ C and over 2.5 hours with gleichbleiben¬ the metered feed streams while stirring and maintaining the reaction temperature Re¬ the remainder of feed Il.

While maintaining the temperature of 60 °, feed III (see below) was added. The mixture was then cooled to 35 ⁰ C and temperature while maintaining the Reaktionstempe¬ feed IV (see below) was added.

Feed I:

Feed Il is an aqueous monomer emulsion prepared from:

* as a non-ionic emulsifier, for example, TweenTM 80 can be used.

Production Zulauf Il

Feed Nl:

2 g 30 wt% solution of hydrogen peroxide in deionized water

Feed IV:

40 g of a 10% by weight solution of ammonium bicarbonate in deionized water

The polymers of Examples 22 to 25 were synthesized analogously to Example 21, wherein feed Il for each example was chosen as indicated below. Emulsifiers / water / batch size / production of emulsion / controller analogous to example 21.

measurement methods

1) Determination of the K value

The K values are measured according to Fikentscher, Cellulose Chemistry, Vol. 13, pp. 58 to 64 (1932) at 25 ° C. in aqueous / ethanolic or ethanolic solution and represent a measure of the molecular weight. The aqueous / ethanolic or ethanolic solution The polymer contains 1 g of polymer in 100 ml of solution. In the case where the polyesters are present in the form of aqueous dispersions, depending on the polymer content of the dispersion, appropriate amounts of the dispersion are made up to 100 ml with ethanol, so that the concentration of 1 g of polymer in 100 ml of solution arises ,

The K value is measured in a Micro Ubbelohde capillary type M Ic from Schott.

Determine droplet size distribution (TGV) using Malvem ^® scattered light analysis

The droplet size distribution was determined using Particle Size Measurement System for Detecting Liquid Aerosols " ^Malvern® Master Sizer X" (Malvern Instruments Inc., Southborough MA, USA).

Measuring principle:

The measuring system is based on the method of laser light diffraction on the particle, which is used not only for spray analysis (aerosols, pump sprays) but also for sizing

Solids, suspensions and emulsions in the size range of 0.1 microns to 2000 microns is suitable.

A particle collective (= droplet) is illuminated by a laser. At each droplet part of the incident laser light is scattered. This light is received at a multi-element detector and the associated light energy distribution is determined. From these data, the associated particle distribution is calculated via the evaluation software.

Execution: The aerosols were sprayed at a distance of 29.5 cm to the laser beam. The spray cone entered at right angles to the laser beam.

The aerosol cans were fixed to a fixed holding device before each measurement, thus ensuring that all the aerosols to be tested were measured at exactly the same distance.

Before the actual particle measurement, a "background measurement" was performed, eliminating the effects of dust and other contaminants in the measurement area.

Subsequently, the aerosol was sprayed into the test room. The entire particle volume was recorded and evaluated over a test period of 2 s.

Evaluation:

The evaluation contains a tabular representation over 32 class widths from 0.5 .mu.m to 2000 .mu.m and in addition a graphic representation of the Teilchengrößen¬ distribution.

Since the spraying tests show an approximately uniform distribution, the average diameter "mean diameter" D (v, 0.5) is given, which indicates that 50% of the total measured particle volume is below this value.

In the case of sprayable aerosol systems in the cosmetic sector, this value is between 30 μm and 80 μm, depending on the polymer content, valve, spray head geometry, solvent ratio and propellant charge.

Consolidation (flexural strength): The consolidation of polymeric film formers was measured physically as well as objectively by physical judgment as flexural stiffness of thin strands of hair which were treated with the polymer solution and dried again. In this case, a force transducer determines the force required for bending, while the entire measurement runs under standardized conditions in a climatic room at 65% relative humidity.

To measure the bending stiffness, 3.0% strength by weight solutions of the novel polymers were prepared. The flexural strength was measured on 5 to 10 hair strands (a about 3 g and 24 cm in length) at 2O ⁰ C and 65% relative humidity. The weighed, dry strands of hair were immersed in the 3.0% by weight polymer solution, whereby a uniform distribution was ensured by immersing and removing three times. The excess film former solution was then stripped between the thumb and forefinger and the hair tresses closing by expressions between filter paper carefully expressed. The tresses were manually shaped so that they th round in cross section erhiel¬. At 20 ⁰ C and 65% relative humidity was dried over night in a conditioned room.

The tests were mit¬ in a climatic chamber at 20 ⁰ C and 65% relative humidity means of a train / pressure tester performed. The lock of hair was placed symmetrically on two cylindrical rollers of the sample holder. Exactly in the middle of the strand was now bent from above with a rounded punch 40 mm (Bre¬ chen of the polymer film). The required force was measured with a load cell (50 N) and reported in Newton. The values determined were set to those of a commercially available comparative polymer (Amphomer ^® LV 71 as standard 100% as given an¬) in relation.

Washed Out:

The hair tress was in an approximately 37 ° C warm Texapon ^® NSO - solution (6ml of Texapon ^® NSO (28%) in 11 hot water) for about 15 seconds by δmaliges immersing and squeezing washed. The hair strand was then rinsed and treated again in the same way. Thereafter, the lock of hair was well squeezed out on filter paper and allowed to dry overnight. The dry strand of hair was screwed in and examined for residues.

Performance properties of some polymers of Examples 1 to 20:

* Comparative experiments

** as surfactant Texapon NSO (Cognis) was used

*** 5% WS means that the characterized preparation contained 5% by weight of polymer

⁴ * the valve Seaquist Perfect 1 Ariane M was used as the standard valve (Seaquist Perfect Dispensing GmbH)

^{5 *} sample was 60% neutralized, all other samples were 100% neutralized.

Claims

claims

1. Cosmetic preparation containing at least one copolymer which is obtainable by free-radical polymerization of

a) from more than 15 to 40% by weight of at least one monoethylenically unsaturated carboxylic acid, b) from 30 to less than 85% by weight of ethyl methacrylate, c) from 0 to 50% by weight of at least one further, from a) and b) various radically polymerizable monomers c), wherein the amounts of the

Components a), b) and c) add to 100 wt .-%, with the proviso that when it is in the radical polymerization is a Lösungspoly¬ merization and a) consists exclusively of acrylic acid and methacrylic acid and c ) is selected from the group of esters of (meth) acrylic acid with aliphatic C ₈ -C ₁₈ alcohols, c) then may not be selected from 5 to 40 wt .-% esters of (meth) acrylic acid with aliphatic C ₈ C ₁₈ alcohols and with the proviso that when c) is selected from the group consisting of N-vinylpyrrolidone,

N-vinylcaprolactam and mixtures thereof, c) is then present in an amount of less than 10 wt .-%.

2. Cosmetic preparation according to claim 1, with the proviso that when c) is selected from the group consisting of N-vinylpyrrolidone, N-vinyl caprolactam and mixtures thereof, c) then in an amount of less than 5 wt .-% is present.

3. Cosmetic preparation according to one of claims 1 or 2, wherein the copolymer is obtainable by free-radical polymerization of

a) from 18 to 35% by weight of at least one monoethylenically unsaturated carboxylic acid, b) from 40 to 82% by weight of ethyl methacrylate, c) from 0 to 50% by weight of monomer c), where the amounts of components a), b) and c) to ad 100% by weight.

4. Cosmetic preparation according to one of claims 1 to 3, wherein the copolymer is obtainable by free-radical polymerization of polymer a) from 20 to 35% by weight of at least one monoethylenically unsaturated carboxylic acid, b) from 45 to 80% by weight of ethyl methacrylate, c) from 0 to 50% by weight of monomer c), where the amounts of components a), b) and c) add to 100 wt .-%.

5. Cosmetic preparation according to one of claims 1 to 4, wherein a) consists of

a1) methacrylic acid and optionally a2) where a2) is selected from the group consisting of acrylic acid, ethacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.

6. Cosmetic preparation according to one of claims 1 to 4, wherein a) consists of

a1) methacrylic acid and, if appropriate, a2) other monoethylenically unsaturated monocarboxylic acids other than methacrylic acid.

7. Cosmetic preparation according to one of claims 5 or 6, wherein the weight ratio a1) to a2) is greater than 2.

8. Cosmetic preparation according to one of claims 1 to 7, wherein the mindes¬ least one monomer c) is selected from the group consisting of acrylamide, methacrylamide, Ci-Ci ₈ alkyl acrylates, Crdβ-alkyl methacrylates, NC ₁ -C ₁₈ -AIKyI - acrylamides and N-CrC ^ -Alkyimethacrylamiden.

9. Cosmetic preparation according to one of claims 1 to 8, wherein the at least one monomer c) is selected from the group consisting of n-butyl acrylate, tert-butyl acrylate, hydroxyethyl methacrylate, ethyl acrylate and mixtures thereof.

10. The cosmetic preparation according to claim 9, wherein the at least one monomer c) is tert-butyl acrylate.

11. Cosmetic preparation according to one of claims 1 to 10 containing

A) at least one copolymer according to any one of claims 1 to 10 and

B) at least one cosmetically or pharmaceutically acceptable carrier.

12. The preparation of claim 11 wherein component B) is selected from the group consisting of

i) water, ii) water-miscible organic solvents, preferably C ₂ -C ₄ -

Alkanols, in particular ethanol, iii) oils, fats, waxes, iv) of iii) various esters of C ₆ -C ₃₀ monocarboxylic acids with mono-, di- or trihydric alcohols, v) saturated acyclic and cyclic hydrocarbons, vi) fatty acids, vii) fatty alcohols, viii) propellants

and mixtures thereof.

13. Cosmetic preparation according to one of claims 1 to 12, characterized gekenn¬ characterized in that it is a product for styling.

14. A cosmetic preparation according to any one of claims 1 to 13, wherein the preparation is a product for the hair, which is selected from the hair washing agents and products for the hair, which are rinsed or not rinsed out and before or after a hair wash, dyeing, Entfär¬ exercise, perm or Entkräuselung be applied.

15. A cosmetic preparation according to any one of claims 1 to 14, wherein the kosme¬ tables preparation is kon¬ in an atomizer, pump bottle or aerosol container kon¬ to obtain a spray, a paint or a foam.

16. A method for the treatment of hair, characterized in that the hair with the cosmetic preparation according to one of claims 1 to 15 are brought into contact Kon¬ and optionally rinsed with water.

17. A copolymer as defined in any one of claims 1 to 10.

18. Use of a copolymer according to claim 17 in cosmetic preparations.

19. Use of a copolymer according to claim 17 as auxiliaries in the pharmaceutical industry, preferably as or in coating agent (s) for solid dosage forms, for modifying rheological properties, as a surface-active compound, as or in adhesive (s) and as or in Coating material (s) for the textile, paper, printing and leather industries.