WO2005041909A1

WO2005041909A1 - Cosmetic substance containing a copolymer with (meth)acrylic acid amide units and an ester of p-aminobenzoic acid

Info

Publication number: WO2005041909A1
Application number: PCT/EP2004/012232
Authority: WO
Inventors: Darshan Patwardhan; Claudia Wood
Original assignee: Basf Aktiengesellschaft
Priority date: 2003-10-29
Filing date: 2004-10-28
Publication date: 2005-05-12
Also published as: DE10350359A1

Abstract

The invention relates to a cosmetic substance containing at least one ester of p-aminobenzoic acid and at least one water-soluble copolymer which is obtained by radically copolymerizing acrylic acid amide and/or methacrylic acid amide and other water-soluble a,ß-ethylenically unsaturated compounds that can be copolymerized therewith, optionally in the presence of a water-soluble polymeric graft base.

Description

Cosmetic composition containing a copolymer with (meth) acrylic acid amide units and an ester of p-aminobenzoic acid

description

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

Cosmetically and pharmaceutically acceptable water-soluble polymers are widely used in cosmetics and medicine. In soaps, creams and lotions, for example, they usually serve as formulating agents, e.g. B. as a thickener, foam stabilizer or water absorbent or to mitigate the irritant effect of other ingredients or to improve the dermal application of active ingredients. Your task in hair cosmetics is to influence the properties of the hair. In pharmacy, for example, they serve as coating agents or binders for solid pharmaceutical forms. For hair cosmetics, film-forming polymers are used, for example, as setting agents and / or they serve as conditioners to improve dry and wet combability, feel, shine and appearance, and to give the hair antistatic properties.

It is often difficult to provide products with a complex property profile. There is a need for cosmetic agents which contain polymers which are capable of forming essentially smooth, tack-free films which give the hair and skin a pleasant feel and at the same time have a good conditioning effect or setting action. In addition, cosmetic and pharmaceutical products are increasingly subject to aesthetic demands from consumers. A preference for clear, opaque formulations in the form of gels is currently observed with such products. In order to present these formulations to the customer in an appealing manner, transparent packaging materials, particularly those made of plastics, are becoming increasingly important. However, since transparent, possibly also slightly colored plastics are generally transparent not only for visible light in a wavelength range from 400 to 750 nm, but also for the components of ultraviolet (UV) radiation contained in daylight, the mechanical, chemical , olfactory and / or aesthetic properties of the packaged formulations as a result of the action of UV light. In particular, a change in appearance, such as yellowing and discoloration, is noticed negatively by the consumer. In addition, the overall durability of the formulation can be greatly reduced. Because of economic and for aesthetic reasons, the packaging material is often made as thin-walled as possible, stabilizing the packaging against light is often not sufficient to adequately protect the packaged cosmetic or pharmaceutical agent. There is therefore a need for cosmetic or pharmaceutical agents stabilized against the harmful effects of light, in particular UV radiation, which can be formulated into aesthetically pleasing products, such as clear gels, and especially against a change in the appearance of light such as yellowing or discoloration are stabilized.

It is known to use polymers based on acrylic acid amide and / or methacrylic acid amide in cosmetic products.

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

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

WO 02/15854 describes the use of graft copolymers which can be obtained by radical graft copolymerization of at least one open-chain

N-vinylamide compound and optionally at least one further monomer copolymerizable therewith on a polymeric graft base, for cosmetic applications.

The unpublished international application PCT / EP03 / 04647 describes cosmetic and pharmaceutical compositions which contain at least one water-soluble polymer which can be obtained by radical copolymerization of acrylic acid amide and / or methacrylic acid amide and other water-soluble α, β-ethylenically unsaturated compounds which can be copolymerized therewith, optionally in the presence a water-soluble polymeric graft base are available. They are particularly suitable for the production of products in the form of gels.

WO 97/44422 describes laundry detergents for colored fabrics which contain a light stabilizer in order to prevent the fabrics from fading in sunlight. In addition to a large number of suitable light stabilizers, aminobenzoates are also mentioned.

US patent application 20030044365 A1 describes cosmetic compositions for tanning the skin, which may contain a light stabilizer. As suitable In addition to a large number of other classes of compounds, nete light stabilizers are also called derivatives of p-aminobenzoic acid.

The object of the present invention is to provide cosmetic and pharmaceutical compositions which are protected against the negative effects of light. They are said to be particularly suitable for the production of products in the form of clear gels which are stabilized against changes in appearance, such as yellowing and discoloration.

Surprisingly, it has now been found that this object is achieved by a cosmetic agent which contains at least one ester of p-aminobenzoic acid and at least one water-soluble copolymer which is obtained by radical copolymerization of acrylic acid amide and / or methacrylic acid amide and further water-soluble α, β-ethylenically copolymerizable therewith unsaturated compounds, optionally in the presence of a water-soluble polymeric graft base.

The invention therefore relates to a cosmetic or pharmaceutical composition containing

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

O

R1 -NR ² R ³ (I) where

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

B) at least one cosmetically acceptable carrier, and

C) at least one ester of p-aminobenzoic acid.

In the context of the present invention, the expression alkyl includes straight-chain and branched alkyl groups. Suitable short chain alkyl groups are e.g. B. straight-chain or branched CC ₇ alkyl, preferably C Cβ alkyl and particularly preferably CC ₄ alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec.-butyl, tert.-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl , 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2 , 3-dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethylbutyl,

2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl etc. Suitable longer-chain C ₈ -C ₃₀ alkyl or C ₈ -C ₃₀ alkenyl groups are straight-chain and branched alkyl or alkenyl groups. These are preferably predominantly linear alkyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols, which may optionally also be mono-, di- or poly-unsaturated. These include e.g. B. n-hexyl (en), n-heptyl (en), n-octyl (en), n-nonyl (en), n-decyΙ (en), n-undecyl (en), n-dodecyl (en) , n-tridecyl (en), n-tetradecyl (en), n-pentadecyl (en), n-hexadecyl (en), n-heptadecyl (en), n-octadecyl (en), n-nonadecyl (en) etc ,

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

The term heterocycloalkyl in the sense of the present invention encompasses saturated, cycloaliphatic groups with generally 4 to 7, preferably 5 or 6 ring atoms, in which 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from the elements oxygen, nitrogen and sulfur and which may optionally be substituted, where in the case of a substitution, these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1, selected from alkyl, aryl, COOR ^a , COO ^" M ⁺ and NE ¹ E ² , preferably alkyl, are examples of such heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, Tetrahydrothiophenyl, Tetrahydrofuranyl, Tetrahydropyranyl, Dioxanyl called.

Aryl includes unsubstituted and substituted aryl groups and is preferably phenyl, tolyl, xylyl, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl, tolyl, xylyl or mesityl.

Substituted aryl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, -SO ₃ H, sulfonate, NE ¹ E ² , alkylene-NE ¹ E ² , nitro, cyano or halogen.

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

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

The agents according to the invention can advantageously be formulated as gels under normal conditions (20 ° C.). "Gel-shaped consistency" means agents which have a higher viscosity than a liquid and which are self-supporting, ie which retain their shape without a shape-stabilizing coating. In contrast to solid formulations, gel formulations are easy to use deform by shear forces. The viscosity of the gel-like agents are preferably in a range from greater than 600 to about 60,000 mPas. The gels are preferably hair gels, these having a viscosity of preferably 6,000 to 30,000 mPas.

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

Surprisingly, it has been found that derivatives of p-aminobenzoic acid (PABA) are advantageously suitable for stabilizing cosmetic and pharmaceutical compositions based on copolymers which contain copolymerized acrylic acid amide and / or methacrylic acid amide. In this way, they can be formulated into remedies with a very low intrinsic color or imperceptible to the human eye. In addition, they are notable for high compatibility both with the copolymers used according to the invention and with the otherwise customary ingredients of cosmetic and pharmaceutical compositions. This is particularly necessary for the manufacture of clear products, such as clear gels, since even minor incompatibilities, which can be seen in the fact that the product becomes cloudy or even segregated, impair the aesthetic properties. The derivatives of p-aminobenzoic acid used according to the invention are also very well suited for negative changes in the agents protected with them, for example a change in appearance such as yellowing and discoloration, a change in odor and / or a breakdown of ingredients over a long period of time to avoid. In this way, the durability of these agents can be ensured over a long period of time with attractive aesthetic properties. The means protected in this way are also suitable for packaging in transparent packaging materials, for example made of plastics, which enable a good view of the packaged product. The derivatives of p-aminobenzoic acid according to the invention are particularly well compatible with gel formers, as are usually used in the production of gels.

The esters of p-aminobenzoic acid used as component C) in the agents according to the invention are preferably selected from compounds of the general formula IV

wherein

R ¹² , R ¹³ and R ¹⁴ independently of one another are alkyl, hydroxyalkyl or a group of the formula - (CH ₂ CH ₂ O) _d (CH ₂ CH (CH ₃ ) O) _e -R ¹⁵ in which the order of the Al-- kylene oxide units is arbitrary, d and e independently of one another are an integer from 0 to 100, the sum of d and e being at least 2, and R ^{15 being} hydrogen or alkyl.

The compounds of the formula IV are preferably selected from ethyl 4-bis (hydroxypropyl) aminobenzoate (Amerscheen® P), 4-dimethylaminobenzoic acid (2-ethylhexyl) ester (Escalol® 507), amyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate , Butyl 4-dimethylaminobenzoate, octyl 4-dimethylaminobenzoate, lauryl 4-dimethylaminobenzoate, oleyl 4-dimethylaminobenzoate,

4-bis- (polyethoxy) -4-aminobenzoic acid polyethoxyethyl ester (Uvinul® P 25), and mixtures thereof.

The aforementioned compound of the general formula IV is particularly preferably a compound of the formula IV.1

(IV.1)

is in which the sum of d ¹ , d ² and d ³ is from 20 to 30, in particular about 25.

Particularly preferred are stabilizer compositions which contain 4-bis (polyethoxy) -4-aminobenzoic acid polyethoxyethyl ester (Uvinul® P 25) or consist of this as the only component.

The agents according to the invention generally contain component C) in an amount of 0.001 to 10% by weight, particularly preferably 0.01 to 5% by weight and in particular 0.05 to 1% by weight, based on the Total weight of the product. The copolymers A) are described in more detail below. The copolymers A) used according to the invention preferably do not contain any copolymerized acid-containing monomers.

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

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

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

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

Preferred monomers b) are N-vinyl lactams and their derivatives, which, for. B. may have one or more -CC ₆ alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. These include e.g. B. 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. N-vinylpyrrolidone and N-vinylcaprolactam are preferably used.

N-vinylamides suitable as monomers b) are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl- N-methyl propionamide, N-vinyl butyramide and mixtures thereof. N-vinylformamide is preferably used. Suitable monomers b) N-alkyl- and N, N-dialkylamides, β-ethylenically unsaturated monocarboxylic acids are, for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-tert .-Butyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, etc.

The aforementioned monomers b) can be used individually and in the form of mixtures.

According to a preferred embodiment, the copolymer A) contains 3 to 30% by weight, particularly preferably 5 to 25% by weight, of at least one compound of component c) polymerized.

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

The cationogenic and / or cationic groups of component c) are preferably nitrogen-containing groups, such as primary, secondary and tertiary amino groups as well as quaternary ammonium groups. The nitrogen-containing groups are preferably tertiary amino groups or quaternary ammonium groups. Charged cationic groups can be derived from the amine nitrogen either by protonation, e.g. B. with carboxylic acids, such as lactic acid, or mineral acids, such as phosphoric acid, sulfuric acid and hydrochloric acid, or by quaternization, for. B. with alkylating agents such as CC ₄ alkyl halides or sulfates. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Protonation or quaternization can generally take place both before and after the polymerization.

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

Suitable monomers c) of esters of vinyl alcohol with monocarboxylic acids are, for example, vinyl formate, vinyl acetate and vinyl propionate. Suitable vinyl and allyl-substituted heteroaromatic compounds as monomers c) are, for example, N-vinylimidazole and derivatives thereof, such as N-vinyl-2-methylimidazole etc.

Suitable monomers c) are also allylamines and aliylammonium salts, such as dialylamine, diallylmethylamine and diallyldimethylammonium chloride.

Suitable monomers c) are furthermore the amides of the abovementioned, ß-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have a tertiary and a primary or secondary amino group. These include e.g. B.

N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide, N- [4 - (Dimethylamino) cyclohexyl] methacrylamide etc. N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide are preferably used.

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

R ⁵ O

CH ₂ = CCY (CH ₂ CH ₂ O) _k (CH ₂ CH (CH ₃ ) O), RB (||)

wherein

the order of the alkylene oxide units is arbitrary,

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

R ^{5 represents} hydrogen or CC ₈ alkyl, and R ^{6 represents} hydrogen or d-Ciβ-alkyl,

Y represents O or NR ⁷ , where R ^{7 represents} hydrogen, CC ₈ alkyl or C ₅ -C ₈ cycloalkyl.

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

R ⁵ preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, seα-butyl, tert-butyl, n-pentyl or n-hexyl, in particular hydrogen, methyl or ethyl.

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

Y in formula II is preferably O or NH.

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

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

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

Crosslinking monomers which can be used are compounds having at least two ethylenically unsaturated double bonds, such as, for example, esters of ethylenically unsaturated carboxylic acids, such as acrylic acid or methacrylic acid and polyhydric alcohols, ethers of at least dihydric alcohols, such as, for example, vinyl ether or allyl ether. Examples of the underlying alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol , But-2-en-1, 4-diol, 1, 2-pentanediol, 1,5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1 , 12-dodecanediol, neopentyl glycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1st , 4-cyclohexanediol,

1,4-bis (hydroxymethyl) cyclohexane, hydroxypivalic acid neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane, diethylene glycol, triethylene glycol, tetraethylene glycol , Dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thio-pentane-1, 5-diol, and also polyethylene glycols, polypropylene glycols and polytetrahydrofurans with molecular weights of 200 to 10,000 each. In addition to the homopolymers of ethylene oxide or propylene oxide, block copolymers or propylene oxides from ethylene can also be used or copolymers which contain ethylene oxide and propylene oxide groups incorporated. Examples of underlying alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, triethoxycyanoic acid, sorbitan, sugars such as sucrose, glucose, mannose. Of course, the polyhydric alcohols can also be used as the corresponding ethoxylates or propoxylates after reaction with ethylene oxide or propylene oxide. The polyhydric alcohols can also first be converted into the corresponding glycidyl ethers by reaction with epichlorohydrin.

Other 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, cinnamon alcohol , Citronellol, crotyl alcohol or cis-9-octadecen-1-ol. However, the monohydric, unsaturated alcohols can also be esterified with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.

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

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

Amides of unsaturated carboxylic acids, such as, for. B., acrylic and methacrylic acid, itaconic acid, maleic acid, and N-allylamines of at least two valuable amines, such as 1, 2-diaminomethane, 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, 1, 12-dodecanediamine, pipazin, diethylenetriamine or isophoronediamine. The amides of allylamine and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above, are also suitable.

Furthermore, triallylamine or corresponding ammonium salts, e.g. B. Triallylmethylam- moniu chloride or methyl sulfate, suitable as a crosslinker.

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

Other suitable crosslinkers are divinyl dioxane, tetraallylsilane or tetravinylsilane.

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

Particularly preferred crosslinkers are pentaerythritol triallyl ether, allyl ethers of sugars such as sucrose, glucose, mannose, divinylbenzene, N, N'-methylenebisacrylamide, N, N'-divinylethylene urea, and (meth) acrylic acid esters of glycol, butanediol, trimethylolpropane or glycerol or (Meth) acrylic acid esters of glycol, butanediol, trimethylolpropane or glycerol reacted with ethylene oxide and / or epichlorohydrin. N, N'-methylenebisacrylamide, diallyl tartaric acid diamide, dialyl phthalate, diallyl urea, glycol di (meth) acrylate, allyl (meth) acrylate and polyallyl ether are very particularly preferred.

According to a suitable embodiment, the copolymerization for the preparation of the copolymers A) takes place in the presence of at least one compound of component d).

According to a preferred embodiment, the amount of component d) used is 1 to 25% by weight, particularly preferably 3 to 20% by weight, based on the total weight of components a) to d). The compounds of component d) used according to the invention essentially contain no carbon-carbon double bonds. According to a suitable embodiment, the compounds of component d) contain no groups containing silicon atoms.

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

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

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

R ^{8 is} dC ₂₄ alkyl, preferably CC ₄ alkyl.

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

-C (= O) -O-, -OC (= O) -O-, -C (= O) -NR ^a -, -OC (= O) -NR ^a -, -NR ^b - (C = O ) -NR ^a -

wherein R ^a and R ^b independently of one another are hydrogen, d-do-alkyl, preferably dd-alkyl or cycloalkyl.

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

R ¹⁰ -H CH ₂ CH (CH ₃ ) - OH

-Af (CH ₂ ) ₂ -ö - CH ₂ CH (CH ₃ ) - Off (CH ₂ ) ₄ - θ

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

R ^{10 is} hydrogen, dC ₂₄ alkyl, R ⁸ -C (= O) -, R ⁸ -NH-C (= O) -, polyalcohol radical;

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

R ⁸ dC ₂₄ alkyl;

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

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

n 1 to 200, preferably 1 to 100;

s 0 to 1000, preferably 0 to 100;

t 2 to 12, preferably 2 to 6;

u 1 to 1000, preferably 1 to 500;

v 0 to 1000, preferably 1 to 500;

w 0 to 1000, preferably 1 to 500;

x 0 to 1000, preferably 1 to 500;

y 0 to 1000, preferably 1 to 500;

z 0 to 1000, preferably 1 to 500.

The terminal primary hydroxyl groups of the polyethers produced on the basis of polyalkylene oxides and the secondary OH groups of polyglycerol can both be freely available in unprotected form and can be etherified or esterified with alcohols with a chain length dC ₂ or with carboxylic acids with a chain length dC ₂₄ or with Isocyanates are converted to urethanes. Polyether urethanes are preferably used.

Preferred representatives of the above-mentioned alkyl radicals are branched or unbranched CτC ₁₂ -, particularly preferably CrC ₆ -alkyl chains.

The molecular weight of the polyethers is in the range greater than 300 (by number average), preferably in the range from 300 to 100,000, particularly preferably in the range from 500 to 50,000, very particularly preferably in the range from 800 to 40,000. Homopolymers of ethylene oxide or copolymers with an ethylene oxide content of 40 to 99% by weight are advantageously used. The proportion of ethylene oxide polymerized in is therefore 40 to 100 mol% for the ethylene oxide polymers to be used with preference. Propylene oxide, butylene oxide and / or isobutylene oxide are suitable as comonomers for these copolymers. For example, copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide are suitable. The ethylene oxide content of the copolymers is preferably 40 to 99 mol%, the propylene oxide content 1 to 60 mol% and the butylene oxide content in the copolymers 1 to 30 mol%. In addition to straight-chain, branched homopolymers or copolymers can also be used as polyether-containing compounds d1).

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

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

According to a preferred embodiment, a component d1) which comprises at least one polyether urethane is used to prepare the copolymers A).

Suitable polyether urethanes are the condensation products of polyether polyols, such as polyether diols, with polyisocyanates, such as diisocyanates. Suitable polyether polyols are the aforementioned polyalkylene glycols, which are obtainable, for example, from the polymerization of cyclic ethers, such as tetrahydrofuran, or from the reaction of one or more alkylene oxides with a starter molecule which has two or more active hydrogen atoms.

Suitable polyisocyanates are selected from compounds with 2 to 5 isocyanate groups, isocyanate prepolymers with an average number of 2 to 5 isocyanate groups, and mixtures thereof. These include e.g. B. aliphatic, cycloaliphatic and aromatic di-, tri- and polyisocyanates. Suitable diisocyanates are e.g. B. tetramethylene diisocyanate, hexamethylene diisocyanate, 2,3,3-trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate, 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and their mixtures of isomers (e.g. 80% 2,4- and 20 % 2,6-isomer), 1,5-naphthylene diisocyanate, 2,4- and 4,4'-diphenylmethane diisocyanate. A suitable triisocyanate is e.g. B. triphenylmethane-4,4 ', 4 "triisocyanate. Also suitable are isocyanate prepolymers and

Polyisocyanates which can be obtained by adding the aforementioned isocyanates to polyfunctional compounds containing hydroxyl or amine groups. Polyisocyanates which are formed by the formation of biurets or isocyanurates are also suitable. Hexamethylene diisocyanate, trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate and mixtures thereof are preferably used.

Also suitable as a graft base are polymers d2) which have at least 50% by weight of vinyl alcohol units. These polymers preferably contain at least 70% by weight, very particularly preferably 80% by weight, of polyvinyl alcohol units. Such polymers are usually prepared by polymerizing a vinyl ester and then at least partially alcoholysis, aminolysis or hydrolysis. Vinyl esters of linear and branched dC ₁₂ carboxylic acids are preferred; vinyl acetate is very particularly preferred. The vinyl esters can of course also be used in a mixture.

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

Other suitable comonomers for the preparation of the graft base d2) are, for example, monoethylenically unsaturated C ₃ -C ₆ -carboxylic acids such as, for. As acrylic acid, methacrylic acid, crotonic acid, fumaric acid, and their esters, amides and nitriles such as. B. acrylic acid methyl ester, acrylic acid ethyl ester, methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid stearyl ester, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, methyl maleate malate, hydroxyl maleate methylate

2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, maleic anhydride and its half esters, alkylene glycol (meth) acrylates, acrylamide, methacrylamide, N-dimethylacrylamide, N-tert-butylacrylamide, acrylonitrile, methacrylonitrile, vinyl ethers such as, for. B. methyl, ethyl, butyl or dodecyl vinyl ether, cationic monomers such as dialkylaminoalkyl (meth) acrylates and dialkylaminoalkyl (meth) acrylamides such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the salts of the latter monomers with carboxylic acids or mineral acids and the quartered products. Preferred graft bases d2) are polymers which are produced by homopolymerization of vinyl acetate and subsequent at least partial hydrolysis, alcoholysis or aminolysis.

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

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

Particularly preferred graft bases d2) are polymers which are prepared by homopolymerizing vinyl acetate and then at least partially saponifying. Such polymers containing polyvinyl alcohol units are available under the name Mowiol®.

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

If desired, mixtures of compounds of component d) can be used. Are advantageous for. B. Mixtures containing at least one compound d2) and at least one compound d3).

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

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

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

c) 0 to 25% by weight, based on the total weight of components a) to d) of at least one of a) and b) different and thus copolymerizable unsaturated water-soluble compound,

optionally in the presence of up to 20% by weight, based on the total weight of components a) to d), polymers d2) and / or starch and starch derivatives d3).

The agents according to the invention particularly preferably contain a copolymer A) which can be obtained by radical polymerization of

a) 20 to 40% by weight of methacrylic acid amide,

b) 40 to 70% by weight of vinyl pyrrolidone,

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

Furthermore, the agents according to the invention particularly preferably contain a copolymer A) which can be obtained by radical polymerization of

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

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

Furthermore, the agents according to the invention preferably contain a copolymer A) which can be obtained by radical polymerization of a) 20 to 40% by weight of methacrylic acid amide,

b) 40 to 70 wt .-% vinyl pyrrolidone and

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

In a second embodiment, the copolymer A) used in the agents according to the invention is preferably obtainable by radical copolymerization of

a) 5 to 50% by weight, based on the total weight of components a) to d), of methacrylic acid amide,

b) 40 to 85% by weight, based on the total weight of components a) to d), of at least one compound selected from vinylpyrrolidone, vinylcaprolactam, N, N-dimethylacrylamide and mixtures thereof,

c) 0.2 to 20% by weight, based on the total weight of components a) to d), of at least one unsaturated, water-soluble compound which is different from a) and b) and is copolymerizable therewith and is selected from vinylimidazole and derivatives thereof, Polyether acrylates and mixtures thereof,

optionally in the presence of up to 10% by weight, based on the total weight of components a) to d), of polymers d2) which are derived from vinyl alcohol, and optionally in the presence of up to 1% by weight on the total weight of components a) to d), at least one crosslinker.

Furthermore, the agents according to the invention preferably contain a copolymer A) which can be obtained by radical polymerization of

a) 7 to 45% by weight of methacrylic acid amide,

b) 50 to 80% by weight of at least one compound selected from vinylpyrrolidone, vinylcaprolactam, N, N-dimethylacrylamide and mixtures thereof,

c) 0.3 to 10% by weight of at least one compound selected from vinylimidazole and derivatives thereof, polyether acrylates and mixtures thereof,

in the presence of 0.1 to 10% by weight of polymers d2) which are derived from vinyl alcohol.

The agents according to the invention particularly preferably contain a copolymer A) which can be obtained by radical polymerization of a) 10 to 45% by weight, preferably 10 to 43% by weight, methacrylic acid amide,

b) 50 to 80 wt .-% vinyl pyrrolidone and vinyl caprolactam and

c) 0.3 to 10 wt .-% vinylimidazole and / or a derivative thereof.

a) 10 to 45% by weight, preferably 20 to 45% by weight, particularly preferably 20 to 43% by weight, and in particular 30 to 40% by weight, methacrylic acid amide,

b) 50 to 80 wt .-%, preferably 55 to 70 wt .-%, vinyl pyrrolidone and

c) 0.5 to 5% by weight, preferably 1 to 4% by weight, vinylimidazole.

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

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

To prepare the polymers, the monomers can optionally be polymerized in the presence of component d) both with the aid of initiators which form free radicals and by the action of high-energy radiation, which should also be understood to mean the action of high-energy electrons.

The peroxo and / or azo compounds customary for this purpose can be used as initiators for the radical polymerization, for example alkali or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate , tert-butyl peroxy-2-ethylhexanoate, tert-butyl permaleinate, cumene hydroperoxide, diisopropyl peroxidicarbamate, bis- (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl peris-butyl peracetate, tert .-Amyl peroxide, tert-butyl hydroperoxide, azo-bis-isobutyronitrile,

Azo-bis- (2-amidinopropane) dihydrochloride or 2-2'-azo-bis- (2-methyl-butyronitrile). Initiator mixtures or redox initiator systems, such as. B. ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate.

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

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

The polymerization can take place, for example, in bulk. In bulk polymerization using a graft base d), this can be dissolved in at least one monomer and possibly other comonomers and, after the addition of a polymerization initiator, the mixture can be polymerized out. The polymerization can also be carried out semi-continuously by first of all part, for. B. 10% of the mixture to be polymerized from the graft base d), at least one monomer from group a), possibly further comonomers and initiator, the mixture is heated to the polymerization temperature and after the polymerization has started, the rest of the mixture to be polymerized after the polymerization has progressed admits. The polymers can also be obtained by placing the graft base d) in a reactor, heating to the polymerization temperature and adding and polymerizing at least one monomer from group a), possibly further comonomers and polymerization initiator either all at once, batchwise or, preferably, continuously ,

Polymerization in a solvent is preferred. Suitable solvents are 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-Hexanol and cyclohexanol as well as glycols such as ethylene glycol, propylene glycol and butylene glycol and the methyl or ethyl ether of the dihydric alcohols, diethylene glycol, triethylene glycol, glycerin and dioxane. Polymerization in water or a water / alcohol mixture, for example in a water / ethanol mixture, is particularly preferred. The ratio of alcohol to water in such mixtures is preferably in a range from 1: 1 to 1: 7% by volume.

To adjust the molecular weight, the polymerization can be carried out in the presence of at least one regulator. As a regulator, the usual compounds known to those skilled in the art, such as, for. B. sulfur compounds, e.g. B. mercaptoethanol, 2-ethylhexylthioglycolate, thioglycolic acid or dodecyl mercaptan, and tribromochloromethane or other compounds which regulate the molecular weight of the NEN polymers act, are used. Silicon-free controllers are preferably used.

To achieve the purest possible polymers with a low residual monomer content, the polymerization (main polymerization) can be followed by a post-polymerization step. The post-polymerization can be carried out in the presence of the same or a different initiator system as the main polymerization. The postpolymerization preferably takes place at least at the same temperature, preferably at a higher temperature than the main polymerization. The temperature in the main and postpolymerization is preferably at most 90 ° C.

Furthermore, in order to achieve the purest possible polymers with a low residual monomer content, the polymerization is preferably carried out at a pH in the range from 6 to 8, particularly preferably from 6.4 to 7.4, in order to reduce the ammonia which may arise under the polymerization conditions can optionally react with monomers to form unwanted by-products. The pH is adjusted by adding a suitable acid, such as lactic acid.

Products with particularly high purity and correspondingly advantageous properties for use in cosmetics can be achieved if the reaction product is subjected to steam distillation or steam stripping after the polymerization, if appropriate before and / or after postpolymerization. This treatment with water vapor also essentially serves to remove ammonia and other undesirable by-products which can be removed with water vapor from the reaction mixture. The steam treatment is preferably carried out at least between main and post-polymerization. The pH of the polymerization product is preferably adjusted to a value of at most 6 before the steam treatment. The temperature of the water vapor used and the treated polymer solution is preferably at least 90 ° C.

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

If an organic solvent is used in the preparation of the polymers, this can be done by customary methods known to those skilled in the art, e.g. B. can be removed by distillation under reduced pressure. The polymer solutions can by various drying processes, such as. B. spray drying, fluidized spray drying, roller drying or freeze drying can be transferred in powder form. Spray drying is preferably used. The polymer dry powders obtained in this way can advantageously be converted again into an aqueous solution or dispersion by dissolving or redispersing them in water. Powdery copolymers have the advantage of better storage stability, easier transportation and generally have a lower tendency to infest germs.

The cosmetically acceptable carrier B) is preferably selected from

i) water,

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

iii) oiling, greasing, waxing,

iv) esters of C ₆ -C ₃₀ monocarboxylic acids with mono-, di- or trihydric alcohols which are different from iii),

v) saturated acyclic and cyclic hydrocarbons,

vi) fatty acids,

vii) fatty alcohols

and mixtures thereof.

The agents according to the invention have z. B. an oil or fat component B), which is selected from: hydrocarbons of low polarity, such as mineral oils; linear saturated hydrocarbons, preferably with more than 8 carbon atoms, such as tetra-decane, hexadecane, octadecane, etc .; cyclic hydrocarbons such as decahydronaphthalene; branched hydrocarbons; animal and vegetable oils; To grow; Wax esters; Petroleum jelly; Esters, preferably esters of fatty acids, such as. B. the esters of dC ₂₄ monoalcohols with CC ₂₂ monocarboxylic acids, such as isopropyl isostearate, n-propyl myristate, iso-propyl myristate, n-propyl palmitate, iso-propyl palmitate, hexaconasyl palmitate, octacosanyl palmitate, triacontanyl palmitate, tiacontanyl palmitate, Hexacosanyl stearate, octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, tetratriacontanyl stearate; Salicylates such as dd.-salicylates, e.g. B. octyl salicylate; Benzoate testers, 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 e.g. B. 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 e.g. B. commercially available under the name Cyclomethicone.

Preferred oil or fat components B) are selected from paraffin and paraffin oils; Petroleum jelly; natural fats and oils, such as castor oil, soybean oil, peanut oil, olive oil, sunflower oil, sesame oil, avocado oil, cocoa butter, almond oil, peach kernel oil, castor oil, cod liver oil, pork lard, walnut, spermacet oil, sperm oil, wheat germ oil, macadamia nut oil, evening primrose 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, walrus and mixtures of the oil or fat components mentioned above.

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

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

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

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

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

The cosmetic compositions according to the invention preferably contain at least one copolymer A as defined above, at least one carrier B as defined above, a light stabilizer C and at least one further constituent different therefrom, which is selected from cosmetically active ingredients, emulsifiers, Surfactants, preservatives, perfume oils, thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, bleaching agents, gelling agents, care agents, colorants, tinting agents, browning agents, dyes, pigments, consistency enhancers, moisturizing agents, moisturizing agents, moisturizing agents , Lipids, antioxidants, defoamers, antistatic agents, emoilizers, plasticizers.

In a preferred embodiment, the agents according to the invention contain at least one gel former (thickener). In principle, all gel formers customary in cosmetics can be used as gel formers. These include slightly cross-linked polyacrylic acid, for example carbomer (INCI), cellulose derivatives, e.g. B. hydroxypropyl cellulose, hydroxyethyl cellulose, cationically modified celluloses, polysaccharides, e.g. , B. Xanthan gum, capryl / caprin triglyceride, sodium acrylate copolymers, polyquaternium-32 (and) Paraffinum Liquidum (INCI), sodium acrylate copolymers (and) Paraffinum Liquidum (and) PPG-1 trideceth-6, acrylamidopropylthmonium chloride / acrylamide copolymers, Steareth-10 allyl ether, acrylate copolymers, Polyquatemium-37 (and) Paraffinum Liquidum (and) PPG-1 Trideceth-6, Polyquaternium 37 (and) Propylene Glycol Dicaprate Dicaprylate (and) PPG-1 Trideceth-6, Polyquaternium-7, Polyquaternium -44.

Anionic polymers preferred as thickeners, especially for the formulation of gels, are, for example, homopolymers and copolymers of acrylic acid and methacrylic acid and their salts. This also includes cross-linked polymers of acrylic acid, as are available under the INCI name Carbomer. Crosslinked homopolymers of acrylic acid of this type are commercially available, for example, under the name Carbopol® from the company BF GOODRICH. A preferred product is Carbopol® 940. Hydrophobically modified crosslinked polyacrylate polymers, such as Carbopol® Ultrez 21 from Noveon, are also preferred. Further examples of preferred anionic polymers as thickeners are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes and polyureas. Polymers are particularly suitable

Copolymers of (meth) acrylic acid and polyether acrylates, the polyether chain being terminated with a C ₈ -C ₃₀ alkyl radical. These include e.g. B. Acrylate / Beheneth-25 methacrylate copolymers, which are available under the name Aculyn® from Rohm and Haas. Particularly suitable thickeners are e.g. B Aculyn® 22 (copolymer made from acrylates and methacrylic acid ethoxylates with stearyl residue (20 EO units)) and Aculyn® 28 (copolymer made from acrylates and methacrylic acid ethoxylates with behenyl residue (25 EO units)).

Suitable cosmetically and / or dermatologically active ingredients are e.g. B. coloring agents, skin and hair pigmentation agents, tinting agents, tanning agents, bleaching agents, keratin-curing substances, antimicrobial agents, light filter agents, repellent agents, hyperemising agents, keratolytic and keratoplastic agents, antidandruff agents, anti-inflammatory agents, or keratinizing agents, as antioxidant agents Radical scavenger active ingredients, skin moisturizing or -Humidifying substances, lipid-replenishing active substances, anti-inflammatory or anti-allergic active substances and mixtures thereof.

Artificially tanning agents that are suitable for tanning the skin without natural or artificial radiation with UV rays are, for. B. dihydroxyacetone, alloxane and walnut shell extract. Suitable keratin-curing substances are usually active substances, such as those used in antiperspirants, such as. As potassium aluminum sulfate, Alu.miniumhydroxychlorid, aluminum lactate, etc. Antimicrobial agents are used to destroy microorganisms or 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 e.g. B. conventional preservatives known to those skilled in the art, such as p-hydroxybenzoic acid ester, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are e.g. B. Zincricinoate, triciosan, undecylenic acid alkylolamides, citric acid triethyl ester, chlorhexidine etc. Suitable light filter substances are substances that absorb UV rays in the UV-B and / or UV-A range. Suitable UV filters are e.g. B. 2,4,6-triaryl-1, 3,5-triazines, in which the aryl groups can each carry at least one substituent, which is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and mixtures thereof ,

Also suitable are cinnamic acid esters, benzophenones, camphor derivatives and pigments that block UV rays, such as titanium dioxide, talc and zinc oxide. Suitable repellent agents are compounds which are able to deter or drive away certain animals, in particular insects, from humans. This includes e.g. B.

2-ethyl-1, 3-hexanediol, N, N-diethyl-m-toluamide etc. Suitable hyperemising substances which stimulate blood circulation to the skin are e.g. B. 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. B. salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc. Suitable anti-dandruff agents are, for. B. sulfur, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate, zinc pyrithione, aluminum pyrithione, etc. Suitable anti-inflammatory drugs that counteract skin irritation are, for. B. allantoin, bisabolol, dragosantol, chamomile extract, panthenol, etc.

The cosmetic agents according to the invention can contain at least one cosmetically or pharmaceutically acceptable polymer different from compounds of component A) as a cosmetic and / or pharmaceutical active ingredient (as well as optionally as an auxiliary). These generally include anionic, cationic, amphoteric and neutral polymers.

Examples of anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and ren salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes, e.g. B. Luviset PUR® from BASF, and polyureas. Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (eg Luvimer® 100P), copolymers of ethyl acrylate and methacrylic acid (eg Luviflex® Soft and Luvimer® MAE), copolymers of

N-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold® 8, strong), copolymers of vinyl acetate, crotonic acid and optionally further vinyl esters (eg Luviset® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, e.g. B. carboxy-functional, t-butyl acrylate, methacrylic acid (z. B. Luviskol® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as. B. C -C ₃₀ alkyl esters of meth (acrylic acid), C -C ₃₀ alkyl vinyl esters, C ₄ -C ₃₀ alkyl vinyl ether and hyaluronic acid. Examples of anionic polymers are also vinyl acetate / crotonic acid copolymers, such as are commercially available, for example, under the names Resyn® (National Starch) and Gafset® (GAF), and vinyl pyrrolidone / inylacrylate copolymers, available, for example, under the trademark Luviflex® ( BASF). Other suitable polymers are the vinyl pyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF) and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyester.

Other suitable polymers are cationic polymers with the name Polyquaternium according to INCI, z. B. Copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ N-N-caprolate copolymers) / N-vinyl pyrrolidone / N-vinyl imidazolium salts (Luviquat® Hold); cationic cellulose derivatives (polyquaternium-4 and -10), acrylamido copolymers (polyquaternium-7) and chitosan. Suitable cationic (quaternized) polymers are also Merquat® (polymer based on dimethyldiallylammonium chloride), Gafquat® (quaternary polymers which are formed by the reaction of polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR (hydroxyethyl cellulose with cationic groups) and cationic polymers on vegetable Base, e.g. B. guar polymers, such as the Jaguar® brands from Rhodia.

Other suitable polymers are also neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose Polyaspartic acid salts and derivatives. These include, for example, Luviflex® Swing (partially saponified copolymer of polyvinyl acetate and polyethylene glycol, from BASF).

Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinylcaprolactam, eg. B. Luviskol® Plus (BASF), or polyvinylpyrrolidone and their copolymers, in particular with vinyl esters, such as vinyl acetate, for. B. Luviskol® VA 37 (BASF); Polyamides, e.g. B. based on itaconic acid and aliphatic diamines, such as z. B. are described in DE-A-43 33 238. Suitable polymers are also amphoteric or zwitterionic polymers, such as the octylacrylamide / methyl methacrylate / tert.-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® (National Starch), as well as zwitterionic polymers, as described, for example, in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 are disclosed. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers. Other suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon®).

Suitable polymers are also nonionic, siloxane-containing, water-soluble or

-Dispersible polymers, e.g. B. polyether siloxanes, such as Tegopren® (from Goldschmidt) or Belsil® (from Wacker).

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

Suitable auxiliaries can be: lubricants, wetting agents, emulsifying and suspending agents, preserving agents, antioxidants, anti-irritants, chelating agents, emulsion stabilizers, film-forming agents, gelling agents, odor masking agents, resins, hydrocolloids, solvents, solubilizers, neutralizing agents, permeation compounds, accelerators, ammonium, pigment, Refatting and overfatting agents, ointment, cream or oil base materials, silicone derivatives, stabilizers, sterilants, blowing agents, drying agents, opacifiers, thickeners, waxes, plasticizers, white oils. A design in this regard is based on professional knowledge, as is shown, for example, in Fiedler, H. P. Lexikon der Hilfsmittel für Pharmazie, Kosmetik und neighboring areas, 4th ed., Aulendorf: ECV-Editio-Kantor-Verlag, 1996.

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

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

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

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

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

Skin cosmetic and dermatological agents based on the previously described polymers A) have advantageous effects. The polymers can be used, among other things

Keeping and moisturizing the skin and improving the feeling on the skin. The polymers can also act as thickeners in the formulations. By adding the polymers according to the invention, a considerable improvement in skin tolerance can be achieved in certain formulations.

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

Due to the component C) contained, the agents according to the invention are well suited for use as light stabilizers.

Depending on the field of application, the agents according to the invention can be used in a form suitable for skin care, such as. B. as a cream, foam, gel, stick, mousse, milk, spray (pump spray or spray containing blowing agent) or lotion. Use in the form of a gel, in particular in the form of a clear gel, is particularly preferred. In addition to the polymers A) and suitable carriers, the skin cosmetic preparations can also contain other active ingredients and auxiliaries customary in skin cosmetics, as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisaboiol, panthenol, light stabilizers, bleaches, colorants, tinting agents, tanning agents, collagen, protein hydrolyzates, stabilizers, pH Value regulators, dyes, salts, thickeners, gelling agents, consistency enhancers, silicones, humectants, moisturizers and other common additives.

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

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

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

The cosmetic or dermatological preparations are produced by customary methods known to the person skilled in the art.

The cosmetic and dermatological agents are preferably in the form of emulsions, in particular in the form of water-in-oil (W / O) or oil-in-water (O / W) emulsions. However, it is also possible to choose other types of formulation, for example hydrodispersions, gels, oils, oleogels, multiple emulsions, for example in the form of W / O / W or O / W / O emulsions, anhydrous ointments or ointment bases, etc.

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

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

The proportion of the emulsifier system in this type of emulsion is preferably about 4 and 35% by weight, based on the total weight of the emulsion. The proportion of the fat phase is preferably about 20 to 60% by weight. The proportion of the aqueous phase is preferably about 20 and 70%, in each case based on the total weight of the emulsion. The emulsifiers are those which are usually used in this type of emulsion. They are selected, for example, from: C ₁₂ -C ₁₈ sorbitan fatty acid esters; Esters of hydroxystearic acid and C ₁₂ -C ₃₀ fatty alcohols; Mono- and diesters of C ₁₂ -C ₁₈ fatty acids and glycerin or polyglycerin; Condensates of ethylene oxide and propylene glycols; oxypropylenated / oxyethylated C ₁₂ -C ₁₈ fatty alcohols; polycyclic alcohols such as sterols; high molecular weight aliphatic alcohols such as lanolin; Mixtures of oxypropylene / polyglycerolated alcohols and magnesium isostearate; Succinic esters of polyoxyethylenated or polyoxypropylenated fatty alcohols; and mixtures of magnesium, calcium, lithium, zinc or aluminum lanolate and hydrogenated lanolin or lanolin alcohol.

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

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

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

In general, the water-in-oil emulsions are prepared by placing the fat phase and the emulsifier in a batch container. You heat it up at a temperature of about 50 to 75 ° C, then adds the oil-soluble active ingredients and / or auxiliaries and adds, with stirring, water which has previously been heated to about the same temperature and in which the water-soluble ingredients have optionally been dissolved beforehand. The mixture is stirred until an emulsion of the desired fineness is obtained and then allowed to cool to room temperature, stirring less if necessary.

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

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

These formulations preferably contain 2 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight, of surfactants, based on the total weight of the formulation.

All anionic, neutral, amphoteric or cationic surfactants commonly used in personal cleansing agents can be used in the washing, showering and bathing preparations.

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

These include e.g. B. sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.

Suitable amphoteric surfactants are e.g. B. alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or propionates, alkyl amphodiacetates or dipropionates. For example, cocodimethylsulfopropylbetaine, laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate can be used.

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

In addition, the washing, showering and bathing preparations can contain conventional cationic surfactants, such as. B. quaternary ammonium compounds, for example cetyltrimethylammonium chloride. In addition, other conventional cationic polymers can be used, such as. B. copolymers of acrylamide and dimethyldiallylammonium chloride (Polyquaternium-7), cationic cellulose derivatives (Polyquaternium-4, -10), guar hydroxypropyltrimethylammonium chloride (INCI: hydroxylpropyl guar hydroxypropyltrimonium chloride), copolymers of N-vinylpyrrolidol (16-quaternized) and quaternized poly (quaternized) , -44, -46), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Polyquaternium-11) and others.

Furthermore, the shower gel / shampoo formulations thickeners such. B. table salt, PEG-55, propylene glycol oleates, PEG-120 methyl glucose dioleates and others, and preservatives, other active ingredients and auxiliaries and water.

According to a further preferred embodiment, the agents according to the invention are a hair treatment agent. Hair treatment compositions according to the invention preferably contain at least one copolymer A) in an amount in the range from about 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the composition.

The hair treatment compositions according to the invention are preferably in the form of a foaming agent, hair mousse, hair gel, shampoo, hair spray or hair foam. Hair sprays include both aerosol sprays and pump sprays without propellant. Hair foams include both aerosol foams and pump foams without propellant. Particularly preferred hair treatment agents are in the form of a gel. Such a hair treatment composition contains, for example: a) 0.1 to 20% by weight, preferably 1 to 10% by weight, of at least one polymer A), as previously defined,

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

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

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

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

f) 0 to 1% by weight of at least one refatting agent, preferably selected from glycerol and glycerol derivatives,

g) 0 to 30% by weight of further active substances and / or auxiliaries, for. B. at least one silicone compound,

h), 0.001 to 10% by weight, preferably 0.01 to 5% by weight, in particular 0.05 to 1% by weight, of at least one ester of p-aminobenzoic acid,

i) water ad 100 wt .-%.

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

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

Furthermore, the hair treatment compositions according to the invention can generally contain customary cosmetic auxiliaries, for example plasticizers, such as glycerol and glycol; emollients; perfumes; surfactants; UV component different from component C); dyes; antistatic agents; Combing agents; Preservatives; and defoamers. If the compositions according to the invention are formulated as a hairspray, they contain a sufficient amount of a blowing agent, for example a low-boiling hydrocarbon or ether, such as propane, butane, isobutane or dimethyl ether. Compressed gases such as nitrogen, air or carbon dioxide can also be used as blowing agents. The amount of blowing agent can be kept low so as not to unnecessarily increase the VOC content. It is then generally not more than 55% by weight, based on the total weight of the composition. If desired, however, higher VOC contents of 85% by weight and above are also possible.

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

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

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

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

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

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

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

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

f) 0.001 to 10% by weight, preferably 0.01 to 5% by weight, in particular 0.05 to 1% by weight, of at least one ester of p-aminobenzoic acid,

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

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

Another object of the present invention is a method for protecting a cosmetic composition containing

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

OR ¹ C NR ² R ³ (0 where

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

B) at least one cosmetically acceptable carrier,

against the action of light, the agent being mixed with a stabilizing amount of at least one ester of p-aminobenzoic acid, as previously defined.

The above statements regarding suitable and preferred configurations of the polymers A), the carrier B) and the esters of p-aminobenzoic acid C) apply accordingly.

Another object of the present invention is the use of a stabilizer composition consisting of or containing at least one ester of p-aminobenzoic acid, as previously defined, for protecting a cosmetic composition

A) at least one water-soluble or water-dispersible copolymer which can be obtained by radical copolymerization of a) 5 to 90% by weight, based on the total weight of components a) to d), acrylic acid amide and / or methacrylic acid amide, b) 0 to 85% by weight, based on the total weight of components a) to d), of at least one α, β-ethylenically unsaturated amide group-containing compound of the general formula I. ORC NR ² R ³ 0) where R ^{1 is} a group of the formula CH ₂ = CR ⁴ - with R ⁴ = H or CC ₄ alkyl and R ² and R ³ independently of one another are H, alkyl, cycloalkyl, heterocycloalkyl , Aryl or hetaryl, with the proviso that one of the radicals R ² and R ^{3 is} different from H, or R ² and R ³ together with the nitrogen atom to which they are attached represent a five- to eight-membered heterocycle stand, or R ^{2 represents} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ³ independently of one another represent H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ¹ and R ³ together with the amide group, to which they are bound are a lactam with 5 to 8 ring atoms, c) 0 to 40% by weight, based on the total weight of components a) to d), of at least one of components a) and b), so that copolymerizable unsaturated water-soluble compound, the proportion by weight of the sum of components b) and c) being at least 5 % By weight, optionally in the presence of up to 25% by weight, based on the total weight of components a) to d), of at least one water-soluble component d) which is selected from d1) polyether-containing compounds, d2) Polymers which have at least 50% by weight of repeating units derived from vinyl alcohol, d3) starch and starch derivatives, and mixtures thereof, and

B) at least one cosmetically acceptable carrier,

against the influence of light. The above statements regarding suitable preferred configurations of the polymers A), the carrier B) and the esters of p-aminobenzoic acid C) apply accordingly.

The invention is explained in more detail on the basis of the following non-limiting examples.

Examples

General Preparation Instructions for Examples 1 to 50 and Comparative Examples A to D: Solution Polymerization (Example 10)

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

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

Feed 3: initiator solution from: 4 g of Wako V 50 [2,2'-azobis (2-amidinopropane) - dihydrochloride] and 180 g of water

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

Feed 5: 1 g of 90% lactic acid in 9 g of water

10% of feed 1, 20% of feed 2 and 10% of feed 3 were placed in 490 g of water in a stirring apparatus with reflux condenser, internal thermometer and four separate feed devices and the mixture was heated to approx. 60 ° C. with stirring. After the polymerization, recognizable by the beginning of an increase in viscosity, the rest of feed 1 was added at 65 ° C. within three hours, the rest of feed 2 within 1.5 hours and the rest of feed 3 within four hours. In an alternative embodiment, the pH of the reaction solution was adjusted to 6.4 to 7.4 using feed 5. After the end of the addition, polymerization was continued for a further two hours at this temperature. Feed 4 was then added to the postpolymerization within 30 minutes at 65.degree. C. and after the end of the addition, postpolymerization was continued for about two hours at this temperature and for a further two hours at a temperature of 80 to 90.degree. In an alternative embodiment, the reaction mixture was then 1 h treated with water vapor at a pH of about 6. An approximately 30% aqueous microdispersion is obtained. To stabilize the solution with 100 ppm of Euxyl®K 100 from Schülke & Mayr (5-chloro-2-methyl-3- (2H) -isothiazolone / 2-methyl-3- (2H) -isothiazolone / benzyl alcohol) added. When using water / ethanol mixtures, there is no need to use a stabilizer.

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

Table 1 :

AM acrylamide MAM methacrylamide VP N-vinylpyrrolidone VCap N-vinylcaprolactam VFA N-vinylformamide DMAA dimethylacrylamide 350-MA polyethylene glycol methacrylate (Mn = 350) Q-DMAEMA dimethylaminoethyl methacrylate-dimethyl sulfate C-Dry MD1934 degraded starch (dextrose equivalents) = 38 PVOH partially saponified polyvinyl alcohol (Mowiol © 4-88, Clariant) General preparation instructions for Examples 51 to 65: solution polymerization with post-polymerization and steam treatment (Example 63)

Feed 1: Monomer mixture of: 120 g vinyl pyrrolidone and 2 g vinyl imidazole

Feed 2: 466.7 g of a 15% aqueous solution of methacrylamide (= 70 g methacrylamide)

Feed 3: initiator solution from: 2 g of Wako V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] and 18 g of water

Feed 4: initiator solution from: 2 g of Wako V 50 [2,2'-azobis (2-amidinopropane) dihydrochloride] and 18 g of water

Feed 5: 3 g of 25% lactic acid solution

Initial charge: 26.7 g of a 50% aqueous polyvinyl alcohol solution (= 8 g Mowiol® 4-88)

30.5 g of feed 1, 117 g of feed 2 and 4 g of feed 3 were placed in 150 g of water in a stirring apparatus with reflux condenser, internal thermometer and 4 separate feed devices and the mixture was heated to approx. 65 ° C. with stirring. After the polymerisation, recognizable by the beginning of an increase in viscosity, the rest of feed 1 was added at 65 ° C within 3 hours, the rest of feed 2 in 5 hours and the rest of feed 3 within 6 hours, the internal temperature rising to approx 67 ° C was increased. After the end of the addition, the reaction mixture was left at this temperature for about 2 hours. The polymer solution was treated with steam for 30 minutes. Then feed 4 was added within 30 minutes and feed 5 within 5 minutes, and the polymer solution was polymerized for a further approx. Three hours at a temperature of approx. 70 ° C. About 800 g of an about 22% polymer solution were obtained. The solution was treated with steam for about 1 hour and stirred at a temperature of about 100 ° C for 2 hours.

To stabilize the solution, 100 ppm Euxyl® K100 from Schülke & Mayr (5-chloro-2-methyl-3- (2) -isothiazolone / 2-methyl-3- (2H) -isothiazolone / benzyl alcohol) was added. Powdery products were obtained by spray drying or freeze drying.

Analogously, all of the products listed in Table 2 below were polymerized.

Table 2:

VI: vinyl imidazole

VCap: N-vinyl caprolactam

DMAA: dimethylacrylamide

350-MA: polyethylene glycol methacrylate (M _n 350)

PVOH: partially saponified polyvinyl alcohol (Mowiol® 4-88, Clariant)

Application properties

Standard formulation:

A gel is formulated from 0.5% by weight of a commercially available polyacrylic acid thickener (Carbopol 940, BF Goodrich), neutralized with triethanolamine (TEA), which shows essentially no conditioning or setting effect when used on the hair. The performance properties are shown in Table 3, Comparative Example A. Comparative Examples B - D:

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

According to the invention:

3% by weight of copolymers 1 to 65 are added to the gel formulation from the standard formulation as a hair cosmetic active ingredient. The result is clear formulations with good conditioning and setting effects. The application properties are also shown in Table 3.

Rating:

A) Clarity

A touch of clarity

1 clear (reference: Carbopol 940; polyvinylformamide with K value = 40)

1-2 almost clear (reference: Luviskol® VA 64) 2 clear (clear when forming a thin film on the hand; reference: polyvinylformamide with K value = 110; Luviskol® VA 73)

3 slightly cloudy (reference: polyvinylpyrrolidone K 90) 4 cloudy (reference: polyvinyl alcohol, e.g. Mowiol® 4-88) 5 milky

B) viscosity

Grade viscosity

1 very firm (reference: gel made from 0.5% Carbopol 940 / TEA)

2 firm

3 moderately firm

4 fluent

5 low viscosity

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

Note stickiness

1 not sticky

2 slightly sticky

3 moderately sticky

4 sticky

5 very sticky

Table 3:

The clarity of the gels can be improved by adding up to 20% by weight of ethanol.

Use in hair cosmetics 1. "Ultra Hold" hair gel

To produce the hair gel, component A is placed in a flask, component B is stirred in and dispersed until the particles sink to the bottom. Then component C is added and the mixture is stirred until a homogeneous gel forms. Component D is mixed and stirred until dissolved. Then component D is added to the gel. pH value: 7.2, viscosity (Brookfield): 30500 mPas, transmission: 97% (600 nm) 2. "Hard Hold" gel:

To produce the hair gel, component A is placed in a flask, component B is stirred in and dispersed until the particles sink to the bottom. Then component C is added and the mixture is stirred until a homogeneous gel forms. Component D is mixed and stirred until dissolved. Then component D is added to the gel. pH: 6.9, viscosity (Brookfield): 33850 mPas, transmission: 98.1% (600 nm) 3. "Strand hold" gel:

To produce the hair gel, component A is placed in a flask, component B is stirred in and dispersed until the particles sink to the bottom. Then component C is added and the mixture is stirred until a homogeneous gel forms. Component D is mixed and stirred until dissolved. Then component D is added to the gel. pH value: 7.3, viscosity (Brookfield): 24300 mPas, transmission: 97.9% (600 nm)

4. "Hard Hold" gel:

To prepare component A, the thickener is allowed to swell in water and stirred until the solution is homogeneous. Then neutralized with component B. To produce component C, the Cremophor® is dissolved in water, then component D is weighed in and stirred until a clear solution is obtained. With stirring, the combined components C and D are added to the combined components A and B. pH: 7.2, viscosity (Brookfield): 13000 mPas, transmission: 96.9% (600 nm) 5. "Wet Look" -Gel:

To produce the hair gel, component A is placed in a flask, component B is stirred in and dispersed until the particles sink to the bottom. Then component C is added and the mixture is stirred until a homogeneous gel has formed forms. Component D is mixed and stirred until dissolved. Then component D is added to the gel. pH: 6.9, viscosity (Brookfield): 47600 mPas, transmission: 97.5% (600 nm)

6. "Hold and Feel" Gel:

To produce the hair gel, component A was stirred and component B added. Due to the large number of air bubbles in the formulation, centrifugation is required. pH value: 7.0, viscosity (Brookfield): 90200 mPas, transmission: 97.0% (600 nm)

7. "Fantasy" hair gel:

To produce the hair gel, component A is placed in a flask, component B is stirred in and dispersed until the particles sink to the bottom. Then component C is added and the mixture is stirred until a homogeneous gel forms. Component D is mixed and stirred until dissolved. Then component D is added to the gel. pH value: 7.25, viscosity (Brookfield): 44000 mPas, transmission: 95.0% (600 nm)

Claims

claims

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

O

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

B) at least one cosmetically acceptable carrier, and

C) at least one ester of p-aminobenzoic acid.

2. Composition according to claim 2, wherein component C) is selected from compounds of general formula IV

wherein

R ¹² , R ¹³ and R ¹⁴ independently of one another represent alkyl, hydroxyalkyl or a group of the formula - (CH ₂ CH ₂ O) d (CH ₂ CH (CH ₃ ) O) _e -R ¹⁵ , in which the order of the alkylene oxide units is arbitrary is, d and e are independently an integer from 0 to 100, the sum of d and e being at least 2, and R ^{15 is} hydrogen or alkyl.

3. Composition according to claim 2, wherein the compound of general formula IV is a compound of formula IV.1

(IV.1), in which the sum of d ¹ , d ² and d ³ is from 20 to 30, in particular about 25.

Agent according to one of the preceding claims, wherein component b) comprises at least one compound which is selected from N-vinyl lactams, N-vinyl amides saturated monocarboxylic acids, N-alkyl and N, N-dialkyl amides α, β-ethylenically unsaturated monocarboxylic acids and mixtures from that.

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

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

7. Composition according to one of the preceding claims, further comprising at least one component different from components A), B) and C), which is selected from cosmetically active ingredients, emulsifiers, surfactants, preservatives, perfume oils, thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-konhaltigen polymers, bleaches, gel formers, care agents, colorants, tinting agents, tanning agents, dyes, pigments, bodying agents, humectants, refatting agents, collagen, protein hydrolysates, lipids, antioxidants such, defoamers, antistats, emollients and softeners.

8. Composition according to one of the preceding claims, which contains at least one gelling agent which is selected from homopolymers and copolymers of acrylic acid and methacrylic acid and their salts; cross-linked polyacrylic acids; Copolymers of (meth) acrylic acid and polyether acrylates, in which the polyether chain is terminated with a C ₈ -C ₃₀ -alkyl radical; and mixtures thereof.

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

10. Agent according to one of the preceding claims, which is in the form of a clear gel.

11. A method for protecting a cosmetic composition containing

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

O

R ¹ C NR R ³ (I) in which

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

B) at least one cosmetically acceptable carrier, against the action of light, the agent being mixed with a stabilizing amount of at least one ester of p-aminobenzoic acid, as defined in one of claims 1 to 3.

12. Use of a stabilizer composition consisting of or containing at least one ester of p-aminobenzoic acid, as in one of the claims. Before 1 to 3 defined, for the protection of a cosmetic agent containing

O

R ¹ -NR ² R ³ (I) where

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

B) at least one cosmetically acceptable carrier,

against the influence of light.