DE10350359A1 - Cosmetic agent containing a copolymer with (meth) acrylamide units and an ester of p-aminobenzoic acid - Google Patents

Abstract

The present invention relates to a cosmetic composition containing at least one ester of p-aminobenzoic acid and at least one water-soluble copolymer obtained by free-radical copolymerization of acrylamide and / or methacrylamide and other water-soluble alpha, beta-ethylenically unsaturated compounds copolymerizable therewith, optionally in the presence of a water-soluble polymeric graft base, is available.

Description

The The present invention relates to a cosmetic agent which at least one ester of p-aminobenzoic acid and at least one water-soluble Contains copolymer, by radical copolymerization of acrylic acid amide and / or methacrylamide and further water-soluble α, β-ethylenically unsaturated compounds copolymerizable therewith Compounds, optionally in the presence of a water-soluble polymeric graft base, available is.

cosmetic and pharmaceutically acceptable water-soluble polymers found in cosmetics and medicine multiple use. In soaps, creams and lotions for example, they usually serve as a formulating agent, z. B. as a thickener, foam stabilizer or water absorbent or also to lessen the irritating effects of other ingredients or to improve the dermal application of active ingredients. Your The task in hair cosmetics is to improve the properties of the hair To influence hair. In pharmacy, for example, they serve as a coating agent or binder for solid dosage forms. For the hair cosmetics are film-forming polymers, for example, used as a consolidator and / or they serve as conditioners to dry and wet combability, touch, shine and to improve appearance as well as antistatic hair To give properties.

difficulties often prepares the delivery of products with a complex Property profile. So there is a need for cosmetic products, contain the polymers which are substantially smoother to form, tack-free films are that give the hair and skin a pleasant grip and at the same time a good conditioning effect or strengthening effect exhibit. In addition to cosmetic and pharmaceutical products from the consumer increasingly aesthetic Requirements made. So is currently in such products a preference for clear, opaque formulations in the form of Gels observed. To make these formulations appealing to the customer showcase, increasingly gaining transparent packaging materials, in particular made of plastics, in importance. However, because transparent, also if necessary slightly colored Plastics in general not only for visible light in one Wavelength range from 400 to 750 nm, but also for those contained in daylight Shares of ultraviolet (UV) radiation are permeable can the mechanical, chemical, olfactory and / or aesthetic properties the packaged formulations by the action of UV light deteriorate. In particular, a change in appearance, such as Yellowing and discoloration, negatively noticed by the consumer. In addition, the durability can also the formulation as a whole be greatly reduced. Because of economic and aesthetic establish In addition, the packaging material often preferably thin walled accomplished is stabilizing the packaging against light often not sufficient to packaged cosmetic or pharmaceutical Adequately protect resources. There is therefore a need for the harmful action of light, in particular of UV radiation, stabilized cosmetic or pharmaceutical agents, which are aesthetically pleasing products, how to formulate clear gels, and in particular to one change the appearance of the light, such as a yellowing or discoloration stabilized are.

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

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

Out US Pat. No. 5,334,287 discloses graft polymers which are prepared by free-radical initiated polymerization of N-vinylcarboxamides, preferably N-vinylformamide, and optionally other monomers in the presence of monosaccharides, Oligosaccharides and polysaccharides are available. As additional Monomers are in addition to a variety of other acrylamide and Called methacrylamide. A suitability of these graft copolymers as Active ingredient in cosmetic formulations is not mentioned.

The WO 02/15854 describes the use of graft copolymers, the available are by radical graft copolymerization of at least one open-chain N-vinylamide compound and optionally at least another copolymerizable monomer on a polymeric Grafting base, for cosmetic applications.

The unpublished international application PCT / EP03 / 04647 describes cosmetic and phar pharmaceutical compositions containing at least one water-soluble polymer obtainable by free-radical copolymerization of acrylic acid amide and / or methacrylamide and other water-soluble α, β-ethylenically unsaturated compounds copolymerizable therewith, if appropriate in the presence of a water-soluble polymeric graft base. They are particularly suitable for the production of products in the form of gels.

The WO 97/44422 describes laundry detergents for colored fabrics containing a sunscreen contained in order to avoid fading of the tissue in sunlight. In addition to a variety of suitable sunscreens are also aminobenzoates called.

The US patent application 20030044365 A1 describes cosmetic compositions for tanning the skin, which may contain a sunscreen. As suitable sunscreen Become a variety of other classes of compounds and derivatives of p-aminobenzoic acid called.

Of the The present invention is based on the object, cosmetic and to provide pharmaceutical agents that are resistant to a are protected from the negative influence of light. They should be in particular suitable for the preparation of products in the form of clear gels, the across from a change of the Appearance, as yellowing and discoloration are stabilized.

Surprisingly It has now been found that this task by a cosmetic means is solved, the at least one ester of p-aminobenzoic acid and at least one water-soluble Contains copolymer, which by radical copolymerization of acrylic acid amide and / or methacrylamide and further water-soluble α, β-ethylenically unsaturated compounds copolymerizable therewith Compounds, optionally in the presence of a water-soluble polymeric graft base, available is.

• A) wenigstens ein wasserlösliches oder wasserdispergierbares Copolymer, das erhältlich ist durch radikalische Copolymerisation von a) 5 bis 90 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), Acrylsäureamid und/oder Methacrylsäureamid, b) 0 bis 85 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), wenigstens einer α,β-ethylenisch ungesättigten amidgruppenhaltigen Verbindung der allgemeinen Formel I
  
  wobei R¹ für eine Gruppe der Formel CH₂=CR⁴- mit R⁴ = H oder C₁-C₄-Alkyl steht und R² und R³ unabhängig voneinander für H, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, mit der Maßgabe, das einer der Reste R² und R³ von H verschieden ist, oder R² und R³ gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für einen fünf- bis achtgliedrigen Heterocyclus stehen, oder R² für eine Gruppe der Formel CH₂=CR⁴- steht und R¹ und R³ unabhängig voneinander für H, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, oder R¹ und R³ gemeinsam mit der Amidgruppe, an die sie gebunden sind für ein Lactam mit 5 bis 8 Ringatomen stehen, c) 0 bis 40 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), wenigstens einer von den Komponenten a) und b) verschiedenen, damit copolymerisierbaren ungesättigten wasserlöslichen Verbindung, wobei der Gewichtsmengenanteil der Summe der Komponenten b) und c) wenigstens 5 Gew.-% beträgt, gegebenenfalls in Gegenwart von bis zu 25 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), wenigstens einer wasserlöslichen Komponente d), die ausgewählt ist unter d1) polyetherhaltigen Verbindungen, d2) Polymeren, die mindestens 50 Gew.-% Wiederholungseinheiten aufweisen, die sich von Vinylalkohol ableiten, d3) Stärke und Stärkederivaten, und Mischungen davon,
• B) wenigstens einen kosmetisch akzeptablen Träger, und
• C) wenigstens einen Ester der p-Aminobenzoesäure.

The invention therefore relates to a cosmetic or pharmaceutical agent containing

• A) at least one water-soluble or water-dispersible copolymer obtainable by free-radical copolymerization of a) from 5 to 90% by weight, based on the total weight of components a) to d), of acrylic acid amide and / or methacrylamide, b) from 0 to 85% by weight .-%, based on the total weight of components a) to d), of at least one α, β-ethylenically unsaturated amide-containing compound of general formula I.
  
  where R ^{1 is} a group of the formula CH ₂ = CR ⁴ - where R ⁴ = H or C ₁ -C 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 represents} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ^{3 are} independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ¹ and R ³ together with the amide group to which they are attached to a lactam with 5 to 8 ring atoms, c) 0 to 40 wt .-%, based on the total weight of components a) to d), at least one of the components a) and b) different, copolymerizable therewith unsaturated water-soluble compound, wherein the amount by weight the sum of components b) and c) is at least 5% by weight, optionally in the presence of up to 25% by weight, based on the total weight of components a) to d), 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. Have repeat 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 term alkyl includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched C ₁ -C ₇ alkyl, preferably C ₁ -C ₆ alkyl and particularly preferably C ₁ -C ₄ alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl , 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 , 3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl 2-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 be additionally mono-, di- or polyunsaturated. These include z. N-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl , n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, etc ,

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

The term heterocycloalkyl in the context of the present invention comprises saturated, cycloaliphatic groups having 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 the optionally substituted, wherein in the case of a substitution, these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, more preferably 1 substituent selected from alkyl, aryl, COOR ^a , COO ^- M ⁺ and NE ¹ E ² , preferably Alkyl, can carry. Examples of such heterocycloaliphatic groups include pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydropyranyl, dioxanyl.

aryl includes unsubstituted and substituted aryl groups and stands preferably for 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 for Pyrrolyl, pyrazolyl, imidazolyl, indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, Pyridazinyl, pyrimidinyl or pyrazinyl.

in the Following are compounds that differ from acrylic acid and methacrylic acid can derive partially shortened by inserting the syllable "(meth)" in the derived from acrylic acid Called connection.

The agents according to the invention can be formulated under normal conditions (20 ° C) advantageous as gels. "Gel-like consistency" show means that a higher one viscosity as a liquid and which are self-supporting, d. H. the one lent to them Keep shape without shape-stabilizing cladding. In contrast however, solid formulations can be gel-formulated deform easily using shear forces. The viscosity of the gel agents are preferably in a range of greater than 600 to about 60,000 mPas. Preferably, the gels are hair gels, wherein this is a viscosity of preferably 6000 to 30,000 mPas.

Under water-soluble Monomers and polymers are monomers in the context of the present invention and polymers understood to be at least 1 g / L at 20 ° C in water to solve. Water-dispersible polymers are polymers, those using shear forces for example, by stirring decompose into dispersible particles.

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 comprise polymerized acrylamide and / or methacrylamide in copolymerized form. In this way, they can be formulated into means with very little intrinsic color, or one that is imperceptible to the human eye. In addition, they are characterized by a high compatibility both with the copolymers used according to the invention and with otherwise customary ingredients of cosmetic and pharmaceutical agents. This is especially necessary for the preparation of clear products, such as clear gels, since even slight incompatibilities, which are manifested by haze or even segregation of the product, lead to impairment of the aesthetic properties. The derivatives of p-aminobenzoic acid used according to the invention are also very well suited to avoid negative changes in the means protected by them, for example a change in appearance such as yellowing and discoloration, a change in odor and / or degradation of ingredients over a long period , Thus, the durability of these agents can be ensured with appealing aesthetic properties over a long time. The means thus protected are also suitable for packaging in transparent packaging materials, for example of plastics, which allow a good view of the packaged product. The derivatives of p-aminobenzoic acid according to the invention are particularly well compatible with gelling agents, such as are commonly used in the preparation of gels.

worin
R¹², R¹³ und R¹⁴ unabhängig voneinander für Alkyl, Hydroxyalkyl oder eine Gruppe der Formel -(CH₂CH₂O)_d(CH₂CH(CH₃)O)_e-R¹⁵ stehen worin, die Reihenfolge der Alkylenoxideinheiten beliebig ist, d und e unabhängig voneinander für eine ganze Zahl von 0 bis 100 stehen, wobei die Summe aus d und e mindestens 2 beträgt, und R¹⁵ für Wasserstoff oder Alkyl steht.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 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 and d and e are independently an integer from 0 to 100, where the sum of d and e is at least 2, and R ^{15 is} hydrogen or alkyl.

Preferably, the compounds of formula IV are selected from ethyl-4-bis (hydroxypropyl) aminobenzoate (Amerscheen ^® P), 4-dimethylaminobenzoic acid (2-ethylhexyl) ester (Escalol ^® 507) Amyl-4-dimethylaminobenzoate, ethyl dimethylaminobenzoate 4- , butyl 4-dimethylaminobenzoate, octyl-4-dimethylaminobenzoate, lauryl-4-dimethylaminobenzoate, oleyl-4-dimethylaminobenzoate, 4-bis (polyethoxy) -4-aminobenzoesäurepolyethoxyethylester (Uvinul ^® P 25), and mixtures thereof.

handelt, worin die Summe aus d¹, d² und d³ für einen Wert von 20 bis 30, insbesondere etwa 25, steht.With particular preference the compound of the general formula IV mentioned above is a compound of the formula IV.1

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

Are particularly preferred stabilizer compositions, the 4-bis (polyethoxy) -4-aminobenzoesäurepolyethoxyethylester (Uvinul ^® P 25) containing or consisting of a single component.

The agents according to the invention contain component C) generally in an amount of 0.001 to 10 wt .-%, particularly preferably from 0.01 to 5 wt .-% and in particular from 0.05 to 1% by weight, based on the total weight of the composition.

in the The copolymers A) are described in more detail below. The inventively used Copolymers A) preferably contain no acid group-containing monomers in copolymerized form.

He follows the radical copolymerization of components a) and optionally b) and / or c) in the presence of at least one compound of the component d) copolymers A) are obtained with advantageous properties. This can for example consist of an at least partial grafting to the component d) as a grafting base. It is, however also mechanisms other than grafting are conceivable. The component A) broadly covers the products of the radical process Copolymerization of which z. B. pure graft polymers, mixtures of graft polymers with ungrafted compounds of the component d), homo- and copolymers of the monomers a) and optionally b) and / or c) and any mixtures. shares of ungrafted compounds of component d) can each According to the purpose of the copolymers A) be advantageous. them may for example have an effect as emulsifier or protective colloid get.

The Copolymer A) contains 5 to 90 wt .-%, preferably 10 to 85 wt .-%, particularly preferably 15 to 80 wt .-%, based on the total weight of the components a) to d), acrylic acid amide and / or methacrylamide in copolymerized form.

To a preferred embodiment contains the copolymer A) 5 to 85 wt .-%, particularly preferably 10 to 80 Wt .-%, at least one compound of component b) copolymerized.

Prefers the compounds of component b) are selected from N-vinyllactams, N-vinylamides more saturated Monocarboxylic acids, N-alkyl and N, N-dialkylamides α, β-ethylenic unsaturated Monocarboxylic acids and mixtures thereof.

Preferred monomers b) are N-vinyl lactams and their derivatives, the z. B. one or more C ₁ -C ₈ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. may have. These include z. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam etc. Preference is given to using N-vinylpyrrolidone and N-vinylcaprolactam.

When Monomers b) suitable N-vinylamides are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide, N-vinyl butyramide and mixtures thereof. Preference is given to N-vinylformamide used.

When Monomers b) suitable N-alkyl and N, N-dialkylamides α, β-ethylenic 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 previously mentioned monomers b) used individually and in the form of mixtures.

To a preferred embodiment contains the copolymer A) 3 to 30 wt .-%, particularly preferably 5 to 25 wt .-%, copolymerized at least one compound of component c).

Prefers the compounds of component c) are 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, and quaternary ammonium groups. Preferably, the nitrogen-containing groups are tertiary amino groups or quaternary ammonium groups. Charged cationic groups can be prepared from the amine nitrogens either by protonation, e.g. With carboxylic acids such as lactic acid or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, or by quaternization, e.g. B. with alkylating agents, such as C ₁ -C ₄ -alkyl halides or sulfates produce. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Protonation or quaternization can generally be carried out both before and after the polymerization.

Suitable compounds c) are, for. As the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, preferably C ₂ -C _{1 2} -amino alcohols. These may preferably be C ₁ -C ₈ -monoalkylated or -dialkylated on the amine nitrogen. As the acid component of these esters are z. For example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, Monobu tylmaleate and mixtures thereof. Preference is given to using acrylic acid, methacrylic acid and mixtures thereof. Preference is given to tert-butylaminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate , 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.

When Monomers c) are suitable esters of vinyl alcohol with monocarboxylic acids for example, vinyl formate, vinyl acetate and vinyl propionate.

When Monomers c) suitable vinyl- and allyl-substituted heteroaromatic Compounds are, for example, N-vinylimidazole and derivatives thereof, such as N-vinyl-2-methylimidazole etc.

suitable Monomers c) are also Allylamines and allylammonium salts, such as diallylamine, diallylmethylamine and diallyldimethylammonium chloride.

suitable Monomers c) are furthermore the amides of the abovementioned α, β-ethylenic unsaturated mono- and dicarboxylic acids with diamines, which is a tertiary and a primary or secondary Have amino group. These include z. 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. Preferred are N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide used.

worin
die Reihenfolge der Alkylenoxideinheiten beliebig ist,
k und l unabhängig voneinander für eine ganze Zahl von 0 bis 500 stehen, wobei die Summe aus k und l mindestens 5 beträgt,
R⁵ für Wasserstoff oder C₁-C₈-Alkyl steht, und
R⁶ für Wasserstoff oder C₁-C₁₈-Alkyl steht,
Y für O oder NR⁷ steht, wobei R⁷ für Wasserstoff, C₁-C₈-Alkyl oder C₅-C₈-Cycloalkyl steht.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, terminal hydroxyl-containing substances containing ether bonds. In general, they have a molecular weight in the range of about 150 to 20,000. Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers. Suitable alkylene oxides for the preparation of alkylene oxide copolymers are, for. For example, ethylene oxide, propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene oxide. The alkylene oxide copolymers may contain randomly distributed alkylene oxide units or in copolymerized form in the form of blocks. Preferred are ethylene oxide / propylene oxide copolymers. Preferred as component c) are polyether acrylates of the general formula II

wherein
the order of the alkylene oxide units is arbitrary,
k and l independently of one another represent an integer from 0 to 500, the sum of k and l being at least 5,
R ^{5 is} hydrogen or C ₁ -C ₈ alkyl, and
R ^{6 is} hydrogen or C ₁ -C ₁₈ -alkyl,
Y is O or NR ⁷ , where R ^{7 is} hydrogen, C ₁ -C ₈ -alkyl or C ₅ -C ₈ -cycloalkyl.

Prefers k stands for an integer from 1 to 500, especially 3 to 250. Preferred l stands for an integer from 0 to 100.

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

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

Preferably Y is in the formula II for O or NH.

Suitable polyether acrylates c) are z. As the polycondensation of the aforementioned α, β-ethylenically unsaturated mono- and / or dicarboxylic acids and their acid chlorides, amides and anhydrides with polyetherols. Suitable polyetherols can be easily prepared by reaction of ethylene oxide, 1,2-propy lenoxid and / or epichlorohydrin with a starter molecule, such as water or a short-chain alcohol R ⁶ -OH are produced. 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 in the DE 198 38 851 (Component e2)), which is incorporated herein by reference.

The Copolymers A) can if desired at least one crosslinker, i. a connection with 2 or more as 2 ethylenically unsaturated Embedded in double bonds in copolymerized form. Preferably, crosslinkers in an amount of 0.01 to 10 wt .-%, particularly preferably 0.1 to 3% by weight, based on the total weight of components a) to d) used.

When crosslinking monomers can Compounds with at least two ethylenically unsaturated double bonds be used, such as esters of ethylenically unsaturated Carboxylic acids, like acrylic acid or methacrylic acid and polyhydric alcohols, ethers of at least dihydric alcohols, such as for example, vinyl ethers or allyl ethers.

Examples for the underlying alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, but-2-ene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, Neopentyl glycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-bis (hydroxymethyl) cyclohexane, hydroxypivalic neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane, Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, Tripropylene glycol, tetrapropylene glycol, 3-thio-pentane-1,5-diol, and polyethylene glycols, polypropylene glycols and polytetrahydrofurans with molecular weights of 200 to 10,000. Except the Homopolymers of ethylene oxide or propylene oxide can also block copolymers from ethylene oxide or propylene oxide or copolymers containing ethylene oxide and propylene oxide groups incorporated. examples for underlying alcohols with more than two OH groups are trimethylolpropane, Glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, sorbitan, Sugars such as sucrose, glucose, mannose. Of course, the polyhydric alcohols even after reaction with ethylene oxide or propylene oxide are used as the corresponding ethoxylates or propoxylates. The polyhydric alcohols can also first be converted by reaction with epichlorohydrin in the corresponding glycidyl ether.

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

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

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

Further suitable are amides of unsaturated Carboxylic acids, such as B., acrylic and methacrylic acid, itaconic acid, maleic acid, and N-Allylamines of at least dihydric amines, such as 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine or isophorone diamine. Also suitable are the amides of allylamine and unsaturated carboxylic acids like acrylic acid, methacrylic acid, itaconic, maleic acid, or at least dibasic carboxylic acids as described above were.

Further are triallylamine or corresponding ammonium salts, eg. B. triallylmethylammonium chloride or Methyl sulfate, suitable as a crosslinker.

Farther can N-vinyl compounds of urea derivatives, at least divalent Amides, cyanurates or urethanes, for example urea, Ethyleneurea, propyleneurea or tartaramide, e.g. N, N'-divinylethyleneurea or N, N'-divinylpropyleneurea be used.

Further suitable crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane.

Especially Preferred crosslinkers are, for example, methylenebisacrylamide, divinylbenzene, Triallylamine and triallylammonium salts, divinylimidazole, N, N'-divinylethyleneurea, Reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic and acrylic acid esters of polyalkylene oxides or polyhydric alcohols with ethylene oxide and / or propylene oxide and / or epichlorohydrin have been reacted, and allyl or vinyl ethers of polyhydric alcohols, for example 1,2-ethanediol, 1,4-butanediol, diethylene glycol, trimethylolpropane, Glycerine, pentaerythritol, sorbitan and sugars such as sucrose, glucose, Mannose.

Especially preferred crosslinkers are pentaerythritol triallyl ether, allyl ether of sugars such as sucrose, glucose, mannose, divinylbenzene, N, N'-methylenebisacrylamide, N, N'-Divinylethylenharnstoff, and (meth) acrylic acid ester of glycol, butanediol, trimethylolpropane or glycerol or (meth) acrylic esters of with ethylene oxide and / or epichlorohydrin reacted glycol, butanediol, Trimethylolpropane or glycerin. Very particular preference is given to N, N'-methylenebisacrylamide, diallyltartar, Diallyl phthalate, diallyl urea, glycol di (meth) acrylate, allyl (meth) acrylate and polyallyl ethers.

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

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

The used according to the invention Compounds of component d) contain substantially no carbon-carbon double bonds. According to a suitable embodiment contain the compounds of component d) no silicon atom-containing Groups.

suitable polyether-containing compounds d1) are generally water-soluble or water-dispersible, nonionic polymers, the polyalkylene glycol groups exhibit. Preferably the proportion of polyalkylene glycol groups at least 40 wt .-%, based on the total weight of compound d1). As a polyether-containing compound d1) can for example, the aforementioned polyalkylene glycols, polyesters used on the basis of polyalkylene glycols and polyether urethanes become.

Depending on the type of monomer used in 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} C ₁ -C ₂₄ -alkyl, preferably C ₁ -C ₄ -alkyl.

The compounds d1) may additionally have bridging groups, which are selected, for example, under:
-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, C ₁ -C ₃₀ -alkyl, preferably C ₁ -C ₄ -alkyl or cycloalkyl.

in der die Variablen unabhängig voneinander folgende Bedeutung haben:
R¹⁰ Wasserstoff, C₁-C₂₄-Alkyl, R⁸-C(=O)-, R⁸-NH-C(=O)-, Polyalkoholrest;
R¹¹ Wasserstoff, C₁-C₂₄-Alkyl, R⁸-C(=O)-, R⁸-NH-C(=O)-;
R⁸ C₁-C₂₄-Alkyl;
A -C(=O)-O, -C(=O)-B-C(=O)-O, -C(=O)-NH-B-NH-C(=O)-O;
B -(CH₂)_t-, gegebenenfalls substituiertes Cycloalkylen, Heterocycloalkylen oder Arylen;
n 1 bis 200, bevorzugt 1 bis 100;
s 0 bis 1000, bevorzugt 0 bis 100;
t 2 bis 12, bevorzugt 2 bis 6;
u 1 bis 1000, bevorzugt 1 bis 500;
v 0 bis 1000, bevorzugt 1 bis 500;
w 0 bis 1000, bevorzugt 1 bis 500;
x 0 bis 1000, bevorzugt 1 bis 500;
y 0 bis 1000, bevorzugt 1 bis 500;
z 0 bis 1000, bevorzugt 1 bis 500.As polyethers d1) it is preferred to use polymers of the general formula III having a molecular weight> 300

in which the variables independently of one another have the following meaning:
R ^{10 is} hydrogen, C ₁ -C ₂₄ -alkyl, R ⁸ -C (= O) -, R ⁸ -NH-C (= O) -, polyalcohol radical;
R ^{11 is} hydrogen, C ₁ -C ₂₄ -alkyl, R ⁸ -C (= O) -, R ⁸ -NH-C (= O) -;
R ^{8 is} C ₁ -C ₂₄ alkyl;
A -C (= O) -O, -C (= O) -BC (= O) -O, -C (= O) -NH-B-NH-C (= O) -O;
B is - (CH ₂ ) _t -, optionally substituted cycloalkylene, heterocycloalkylene or arylene;
n is 1 to 200, preferably 1 to 100;
s is 0 to 1000, preferably 0 to 100;
t 2 to 12, preferably 2 to 6;
u is 1 to 1000, preferably 1 to 500;
from 0 to 1000, preferably from 1 to 500;
w is 0 to 1000, preferably 1 to 500;
x 0 to 1000, preferably 1 to 500;
y is 0 to 1000, preferably 1 to 500;
z is 0 to 1000, preferably 1 to 500.

The terminal primary hydroxyl groups of the polyethers prepared on the basis of polyalkylene oxides and the secondary OH groups of polyglycerol can be present both in unprotected form and etherified with alcohols of chain length C ₁ -C ₂₄ or with carboxylic acids of chain length C ₁ -C ₂₄ or be esterified or reacted with isocyanates to urethanes. Preference is given to using polyetherurethanes.

Preferred representatives of the abovementioned alkyl radicals are branched or unbranched C ₁ -C ₁₂ -, more preferably C ₁ -C ₆ -alkyl chains.

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

advantageously, Homopolymers of ethylene oxide or copolymers are used, with an ethylene oxide content of 40 to 99 wt .-%. For the preferred ethylene oxide polymers to be used is thus the proportion of copolymerized ethylene oxide 40 to 100 mol%. Come as a comonomer for these copolymers Propylene oxide, butylene oxide and / or isobutylene oxide into consideration. Suitable are, 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. The ethylene oxide content of the copolymers is preferably 40 to 99 mol%, the propylene oxide 1 to 60 mol% and the proportion of butylene oxide in the copolymers 1 to 30 mol%. In addition to straight-chain can also branched homopolymers or copolymers as polyether-containing compounds d1) are used.

branched Polymers can be prepared by, for example, to Polyalkoholresten, z. As to pentaerythritol, glycerol or sugar alcohols such as D-sorbitol and D-mannitol but also to polysaccharides such as cellulose and starch, ethylene oxide and optionally also attaches propylene oxide and / or butylene oxides. The alkylene oxide units can be randomly distributed in the polymer or in the form of blocks.

But it is also possible to use polyesters of polyalkylene oxides and aliphatic or aromatic dicarboxylic acids, eg. As oxalic acid, succinic acid, adipic acid and terephthalic acid having molecular weights of 1500 to 25,000, such as. As described in EP-A-0 743 962, to be used as the polyether-containing compound. Furthermore can also be polycarbonates by reacting polyalkylene oxides with phosgene or carbonates such. As diphenyl carbonate, and polyurethanes by reacting polyalkylene oxides with aliphatic and aromatic diisocyanates are used.

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

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, the for example, by the polymerization of cyclic ethers, such as tetrahydrofuran, or from the reaction of one or more Alkylene oxides with a starter molecule, the two or more active Hydrogen atoms available are.

suitable Polyisocyanates are selected among compounds having 2 to 5 isocyanate groups, isocyanate prepolymers with an average number of 2 to 5 isocyanate groups, and mixtures from that. These include z. As aliphatic, cycloaliphatic and aromatic di-, tri- and polyisocyanates. Suitable diisocyanates are, for. Tetramethylene diisocyanate, Hexamethylene diisocyanate, 2,3,3-trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, Isophorone diisocyanate, 1,4-phenylene diisocyanate, 2,4- and 2,6-toluene diisocyanate and their isomer mixtures (eg 80% 2,4- and 20% 2,6-isomer), 1,5-naphthylene diisocyanate, 2,4- and 4,4'-diphenylmethane diisocyanate. A suitable one Triisocyanate is z. B. Triphe nylmethane-4,4 ', 4' '- triisocyanate. Farther suitable isocyanate prepolymers and polyisocyanates obtained by addition of the aforementioned isocyanates to polyfunctional hydroxyl or amine group-containing compounds available are. Also suitable are polyisocyanates which are produced by biuret or isocyanurate formation arise. Preference is given to hexamethylene diisocyanate, trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and mixtures thereof.

As a graft base are preferably further polymers d2), which have at least 50 wt .-% of vinyl alcohol units. Preferably, these polymers contain at least 70 wt .-%, most preferably 80 wt .-% polyvinyl alcohol. Such polymers are usually prepared by polymerization of a vinyl ester followed by at least partial alcoholysis, aminolysis or hydrolysis. Vinyl esters of linear and branched C ₁ -C ₁₂ -carboxylic acids are preferred, vinyl acetate is very particularly preferred. The vinyl esters can of course also be used in a mixture.

When Comonomers of the vinyl ester for the synthesis of the graft base d2) 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 methylsulfate, diallylammonium chloride, Styrene, alkylstyrenes in question.

Further suitable comonomers for the preparation of the graft base d2) are, for example, monoethylenically unsaturated C ₃ -C ₆ -carboxylic acids such as. As acrylic acid, methacrylic acid, crotonic acid, fumaric acid, and their esters, amides and nitriles such. Methyl acrylate, ethyl acrylate, methyl methacrylate, methacrylic acid ethyl ester, methacrylic acid stearyl ester, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyisobutyl acrylate, hydroxyisobutyl methacrylate, maleic acid monomethyl ester, maleic acid monoethylester, maleic acid ethylester, 2-ethylhexylacrylate, 2-ethylhexylmethacrylate, maleic anhydride and its half ester, alkylene glycol (meth ) acrylates, acrylamide, methacrylamide, N-dimethylacrylamide, N-tert-butylacrylamide, acrylonitrile, methacrylonitrile, vinyl ethers such. For example, methyl, ethyl, butyl or dodecyl vinyl ether, cationic monomers such as dialkylaminoalkyl (meth) acrylates and dialkylaminoalkyl (meth) acrylamides such as dimethylaminothyl acrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the salts of the latter monomers with carboxylic acids or mineral acids and the quaternized products.

preferred Graft bases d2) are polymers which are obtained by homopolymerization of vinyl acetate and subsequent at least partial hydrolysis, alcoholysis or aminolysis become.

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

to Preparation of the graft base d2) are the ester groups of original Monomers and optionally further monomers after the polymerization cleaved at least in part by hydrolysis, alcoholysis or aminolysis. In the following, this process step will generally be called saponification designated. The saponification takes place in a conventional manner Adding a base or acid, preferably by adding a sodium or potassium hydroxide in Water and / or alcohol. Particularly preferred are methanolic Sodium or potassium hydroxide solutions The saponification is used at temperatures in the range of 10 to 80 ° C, preferably in the range of 20 to 60 ° C, performed. The saponification degree depends on the amount of base or acid used, of the saponification temperature, the saponification time and the water content of the solution.

Especially preferred grafting bases d2) are polymers obtained by homopolymerization of vinyl acetate and subsequent at least partially saponification are produced. Such polyvinyl alcohol units containing polymers 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 arisen through 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 oligosaccharides or polysaccharides and mixtures thereof. Preferred products are those in US 5,334,287 in column 4, line 20 to column 5, line 45 compounds.

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

If desired, can Mixtures of compounds of component d) can be used. Advantageous are z. B. mixtures containing at least one compound d2) and at least a compound d3).

• a) 10 bis 45 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), Methacrylsäureamid,
• b) 60 bis 90 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d) Vinylpyrrolidon und/oder Vinylcaprolactam,
• c) 0 bis 25 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d) wenigstens einer von a) und b) verschiedenen, damit copolymerisierbaren ungesättigten wasserlöslichen Verbindung,

gegebenenfalls in Gegenwart von bis zu 20 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), Polymeren d2) und/oder Stärke und Stärkederivaten d3).The copolymer A) used in the agents according to the invention in a first embodiment is preferably obtainable by free-radical copolymerization of

• a) from 10 to 45% by weight, based on the total weight of components a) to d), of methacrylamide,
• b) 60 to 90% by weight, based on the total weight of components a) to d) of vinylpyrrolidone and / or vinylcaprolactam,
• c) 0 to 25 wt .-%, based on the total weight of components a) to d) of at least one of a) and b) different, thus copolymerizable unsaturated water-soluble compound,

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

• a) 20 bis 40 Gew.-% Methacrylsäureamid,
• b) 40 bis 70 Gew.-% Vinylpyrrolidon,

in Gegenwart von 1 bis 20 Gew.-% Polymeren d2) und/oder Stärke und Stärkederivaten d3).The agents according to the invention particularly preferably contain a copolymer A) which is obtainable by free-radical polymerization of

• a) 20 to 40% by weight of methacrylamide,
• b) 40 to 70% by weight of vinylpyrrolidone,

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

• a) 30 bis 40 Gew.-% Methacrylsäureamid,
• b) 20 bis 60 Gew.-% Vinylpyrrolidon und
• 1 bis 20 Gew.-% Vinylcaprolactam.

Furthermore, the compositions according to the invention particularly preferably contain a copolymer A) which is obtainable by free-radical polymerization of

• a) from 30 to 40% by weight of methacrylamide,
• b) 20 to 60 wt .-% vinyl pyrrolidone and
• 1 to 20% by weight of vinylcaprolactam.

• a) 20 bis 40 Gew.-% Methacrylsäureamid,
• b) 40 bis 70 Gew.-% Vinylpyrrolidon und
• c) 1 bis 20 Gew.-% wenigstens einer von a) und b) verschiedenen, damit copolymerisierbaren wasserlöslichen Verbindung.

Furthermore, the compositions according to the invention preferably contain a copolymer A) which is obtainable by free-radical polymerization of

• a) 20 to 40% by weight of methacrylamide,
• b) 40 to 70 wt .-% vinyl pyrrolidone and
• c) 1 to 20 wt .-% of at least one of a) and b) different, water-soluble compound copolymerizable therewith.

• a) 5 bis 50 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), Methacrylsäureamid,
• b) 40 bis 85 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), wenigstens einer Verbindung, ausgewählt unter Vinylpyrrolidon, Vinylcaprolactam, N,N-Dimethylacrylamid und Mischungen davon,
• c) 0,2 bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d) wenigstens einer von a) und b) verschiedenen, damit copolymerisierbaren ungesättigten wasserlöslichen Verbindung, die ausgewählt ist unter Vinylimidazol und Derivaten davon, Polyetheracrylaten und Mischungen davon,

gegebenenfalls in Gegenwart von bis zu 10 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), Polymeren d2), die sich von Vinylalkohol ableiten, und gegebenenfalls in Gegenwart von bis zu 1 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), wenigstens eines Vernetzers.The copolymer A) used in the compositions according to the invention is preferably obtainable in a second embodiment by free-radical copolymerization of

• a) from 5 to 50% by weight, based on the total weight of components a) to d), of methacrylamide,
• b) from 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 wt .-%, based on the total weight of components a) to d) at least one of a) and b) different, copolymerizable therewith unsaturated water-soluble compound which is selected from vinylimidazole and derivatives thereof, polyether acrylates and Mixtures thereof,

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

• a) 7 bis 45 Gew.-% Methacrylsäureamid,
• b) 50 bis 80 Gew.-% wenigstens einer Verbindung ausgewählt unter Vinylpyrrolidon, Vinylcaprolactam, N,N-Dimethylacrylamid und Mischungen davon,
• c) 0,3 bis 10 Gew.-% wenigstens einer Verbindung, die ausgewählt ist unter Vinylimidazol und Derivaten davon, Polyetheracrylaten und Mischungen davon,

in Gegenwart von 0,1 bis 10 Gew.-% Polymeren d2), die sich von Vinylalkohol ableiten.Furthermore, the compositions according to the invention preferably contain a copolymer A) which is obtainable by free-radical polymerization of

• a) 7 to 45% by weight of methacrylamide,
• b) from 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 from 0.1 to 10% by weight of polymers d2) derived from vinyl alcohol.

• a) 10 bis 45 Gew.-%, vorzugsweise 10 bis 43 Gew.-%, Methacrylsäureamid,
• b) 50 bis 80 Gew.-% Vinylpyrrolidon und Vinylcaprolactam und
• c) 0,3 bis 10 Gew.-% Vinylimidazol und/oder eines Derivats davon.

The agents according to the invention particularly preferably contain a copolymer A) which is obtainable by free-radical polymerization of

• a) from 10 to 45% by weight, preferably from 10 to 43% by weight, of methacrylamide,
• 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 bis 45 Gew.-%, vorzugsweise 20 bis 45 Gew.-%, besonders bevorzugt 20 bis 43 Gew.-%, und insbesondere 30 bis 40 Gew.-%, Methacrylsäureamid,
• b) 50 bis 80 Gew.-%, vorzugsweise 55 bis 70 Gew.-%, Vinylpyrrolidon und c) 0,5 bis 5 Gew.-%, vorzugsweise 1 bis 4 Gew.-%, Vinylimidazol.

Furthermore, the compositions according to the invention preferably contain a copolymer A) which is obtainable by free-radical polymerization of

• a) from 10 to 45% by weight, preferably from 20 to 45% by weight, particularly preferably from 20 to 43% by weight, and in particular from 30 to 40% by weight, of methacrylamide,
• b) 50 to 80 wt .-%, preferably 55 to 70 wt .-%, vinylpyrrolidone and c) 0.5 to 5 wt .-%, preferably 1 to 4 wt .-%, vinylimidazole.

The Preparation of the copolymers A) takes place according to customary methods known to the person skilled in the art Process, preferably by solution polymerization.

The Polymerization temperatures are preferably in the range from about 30 to 120 ° C, more preferably 40 to 100 ° C. The polymerization usually takes place under atmospheric Pressure, but it can also be under reduced or elevated pressure expire. A suitable pressure range is between 1 and 5 bar.

to Preparation of the polymers can the monomers optionally in the presence of component d) both with the help of radical-forming initiators as well as by action high-energy radiation, including the action of higher energy Electrons are understood to be polymerized.

As initiators for the radical polymerization, the peroxo and / or azo compounds customary for this purpose can be used, 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 permalate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide tert-butyl hydroperoxide, azo-bis-isobutyronitrile, azo-bis (2-amidonopropane) dihydrochloride or 2-2'-azobis (2-methyl-butyronitrile). Also suitable are initiator mixtures or redox initiator systems, such as. As ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydropero xid / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate.

The Polymerization can also be effected by the action of ultraviolet radiation, optionally in the presence of UV initiators. For the Polymerization under the influence of UV rays is usually used for this purpose in consideration photoinitiators or sensitizers. These are, for example, compounds such as benzoin and benzoin ethers, α-methylbenzoin or α-phenylbenzoin. Also known as triplet sensitizers, such as benzyldiketals, can be used. As UV radiation sources serve, for example in addition to high-energy UV lamps, such as carbon arc lamps, mercury vapor lamps or xenon lamps also low-UV light sources, such as fluorescent tubes with high blue content.

The used amounts of initiator or initiator mixtures used monomers are generally between 0.01 and 10 wt .-%, preferably between 0.1 and 5 wt .-%.

The Polymerization can be done, for example, in substance. In the Bulk polymerization using a grafting base d) can this in at least one monomer and possibly other comonomers solved and after addition of a polymerization initiator, the mixture be polymerized. The polymerization can also be semicontinuous carried out be by first a part, for. B. 10% of the mixture to be polymerized from Grafting base d), at least one monomer of group a), possibly further comonomers and initiator, the mixture to polymerization heated and after the onset of polymerization, the rest of the to be polymerized mixture after progress of the polymerization admits. The polymers can also be obtained by that the graft base d) in a reactor, heated to the polymerization temperature and at least one monomer of group a), possibly further comonomers and polymerization initiator either at once, batchwise or preferably continuously adds and polymerized.

Prefers is the polymerization in a solvent. Suitable solvents are watery Solvent, 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 and glycols such as ethylene glycol, propylene glycol and butylene glycol and the methyl or ethyl ethers of dihydric alcohols, diethylene glycol, Triethylene glycol, glycerin and dioxane. Particularly preferred is the polymerization in water or a water / alcohol mixture, for example in a water / ethanol mixture. The relationship from alcohol to water is in such mixtures preferably in one Range from 1: 1 to 1: 7 vol.%.

to Adjustment of the molecular weight, the polymerization in the presence at least one controller done. As regulators, the usual, known in the art Compounds, such. B. sulfur compounds, for. Mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid or dodecyl mercaptan and tribromochloromethane or other compounds regulating the molecular weight of the act polymers obtained can be used. To be favoured used silicone-free regulator.

to Achieving as possible pure polymers with low residual monomer content can be attached to the Polymerization (main polymerization), a post-polymerization step connect. The postpolymerization may be in the presence of one or the other Initiator system as the main polymerization take place. Preferably the postpolymerization takes place at least at the same, preferably at a higher Temperature as the main polymerization. The temperature at the main and the postpolymerization is preferably at most 90 ° C.

Farther you lead to achieve as possible pure polymers with low residual monomer content the polymerization preferably at a pH in the range of 6 to 8, especially preferably from 6.4 to 7.4, by, under the polymerization conditions optionally formed ammonia, optionally with monomers too unwanted By-products may react to remove. The pH is adjusted by Adding a suitable acid, like lactic acid.

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

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

Becomes in the preparation of the polymers, an organic solvent used, this can by conventional, known in the art Method, for. B. by distillation at reduced pressure can be removed.

The polymer solutions can by various drying methods, such. B. spray drying, fluidized Spray Drying, drum drying or freeze drying in powder form. Preference is given to spray drying used. The resulting polymer dry powders can be advantageously by dissolving respectively.

redispersing in water again in an aqueous solution or transfer dispersion. Powdered copolymers have the advantage of better storability, a simpler of transportation and usually show a lower propensity for microbial attack.

• i) Wasser,
• ii) wassermischbaren organischen Lösungsmitteln, vorzugsweise C₁-C₄-Alkanolen,
• iii) Ölen, Fetten, Wachsen,
• iv) von iii) verschiedenen Estern von C₆-C₃₀-Monocarbonsäuren mit ein-, zwei- oder dreiwertigen Alkoholen,
• v) gesättigten acyclischen und cyclischen Kohlenwasserstoffen,
• vi) Fettsäuren,
• vii) Fettalkoholen

und Mischungen davon.The cosmetically acceptable carrier B) is preferably selected from

• i) water,
• ii) water-miscible organic solvents, preferably C ₁ -C ₄ -alkanols,
• iii) oils, fats, waxes,
• iv) of iii) various esters of C ₆ -C ₃₀ monocarboxylic acids with mono-, di- or trihydric alcohols,
• v) saturated acyclic and cyclic hydrocarbons,
• vi) fatty acids,
• vii) fatty alcohols

and mixtures thereof.

The inventive compositions have z. An oil or fat component B) selected from: low polarity hydrocarbons such as mineral oils; linear saturated hydrocarbons, preferably having more than 8 C atoms, such as tetradecane, hexadecane, octadecane, etc .; cyclic hydrocarbons, such as decahydronaphthalene; branched hydrocarbons; animal and vegetable oils; To grow; Wax esters; Petroleum jelly; Esters, preferably esters of fatty acids, such as. The esters of C ₁ -C ₂₄ monoalcohols with C ₁ -C ₂₂ monocarboxylic acids such as isopropyl isostearate, n-propyl myristate, isopropyl myristate, n-propyl palmitate, iso-propyl palmitate, hexacosanyl palmitate, octacosanyl palmitate, triacontanyl palmitate, dotriacontanyl palmitate, tetratriacontanyl palmitate, Hexancosanyl stearate, octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, tetratriacontanyl stearate; Salicylates such as C ₁ -C ₁₀ salicylates, e.g. Octyl salicylate; Benzoate esters such as C ₁₀ -C ₁₅ alkyl benzoates, benzyl benzoate; other cosmetic esters such as fatty acid triglycerides, propylene glycol monolaurate, polyethylene glycol monolaurate, C ₁₀ -C ₁₅ alkyl lactates, etc., and mixtures thereof.

suitable silicone oils B) are z. B. linear polydimethylsiloxanes, poly (methylphenylsiloxanes), cyclic siloxanes and mixtures thereof. The number average molecular weight the polydimethylsiloxanes and poly (methylphenylsiloxanes) are preferably in a range of about 1000 to 150000 g / mol. Preferred cyc lische Siloxanes have 4- to 8-membered rings. Suitable cyclic Siloxanes are z. B. under the name cyclomethicone commercially available.

Preferred oil or Fat components B) are selected under paraffin and paraffin oils; Petroleum jelly; natural Fats and oils, like castor oil, Soybean oil, Peanut oil, Olive oil, Sunflower oil, Sesame oil, Avocado oil, cocoa butter, Almond oil, Peach kernel oil, Castor oil, Cod liver oil, lard, spermaceti, sperm oil, sperm oil, wheat germ oil, macadamia nut oil, evening primrose oil, jojoba oil; Fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, Oleyl alcohol, cetyl alcohol; Fatty acids, such as myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid, and linolenic acid of which various saturated, unsaturated and substituted fatty acids; Grow, such as beeswax, carnauba wax, candililla wax, spermaceti and mixtures of the aforementioned oil or fat components.

suitable cosmetically and pharmaceutically acceptable oil or fat components B) are in Karl-Heinz Schrader, basics and formulations of cosmetics, 2nd edition, publisher Hüthig, Heidelberg, pp. 319-355, to which reference is hereby made.

suitable hydrophilic carrier B) are selected under water, 1-, 2- or polyhydric alcohols with preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, Propylene glycol, glycerine, sorbitol, etc.

at the cosmetic according to the invention Means can be skin, dermatological or hair cosmetic Act means.

Preferably are the agents of the invention in the form of a gel, foam, spray, ointment, cream, emulsion, Suspension, lotion, milk or paste in front. If you wish too Liposomes or microspheres be used. Particularly preferred are the agents of the invention in the form of a gel, especially in the form of a clear gel.

The according to the invention cosmetically or pharmaceutically active agents may additionally be cosmetically and / or contain dermatologically active agents and adjuvants.

Preferably contain the cosmetic according to the invention At least one copolymer A as defined above, at least a carrier B as defined above, a light stabilizer C and at least one other component thereof, the selected is among cosmetically active substances, emulsifiers, surfactants, Preservatives, perfume oils, thickeners, Hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, bleaches, gelling agents, Care products, Dyes, Tints, Tanning agents, Dyes, pigments, bodying agents, moisturizers, restockers, Collagen, protein hydrolysates, Lipids, antioxidants, defoamers, Antistatic agents, emollients, plasticisers.

In a preferred embodiment contain the agents of the invention at least one gelling agent (thickener). As gel formers can in principle all usual in cosmetics Gel former can be used. These include slightly crosslinked polyacrylic acid, for example Carbomer (INCI), cellulose derivatives, e.g. B. hydroxypropyl cellulose, Hydroxyethyl cellulose, cationic modified celluloses, polysaccharides, z. Xanthan gum, caprylic / capric triglyceride, sodium acrylate copolymers, Polyquaternium-32 (and) Paraffinum Liquidum (INCI), sodium acrylate copolymers (and) Paraffinum Liquidum (and) PPG-1 trideceth-6, acrylamidopropyltrimonium chloride / acrylamide copolymers, steareth-10 Allyl ethers, acrylate copolymers, Polyquaternium-37 (and) paraffin Liquidum (and) PPG-1 trideceth-6, polyquaternium 37 (and) propylene glycol dicaprate dicaprylate (and) PPG-1 trideceth-6, polyquaternium-7, polyquaternium-44.

Preferred thickeners, especially for the formulation of gels, are anionic polymers, for example homo- and copolymers of acrylic acid and methacrylic acid and salts thereof. These include crosslinked polymers of acrylic acid, such as those available under the INCI name Carbomer. Such crosslinked homopolymers of acrylic acid are available commercially for example under the name Carbopol ^® by the company BF Goodrich. A preferred product is Carbopol ^® 940. Also preferred are hydrophobically modified crosslinked polyacrylate polymers, such as Carbopol ^® Ultrez 21 from Noveon. 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. Particularly suitable polymers are copolymers of (meth) acrylic acid and polyether acrylates, wherein the polyether chain is terminated with a C ₈ -C ₃₀ -alkyl radical. These include z. B. Acrylate / beheneth-25-methacrylate copolymers, which are available under the name Aculyn ^® from Rohm and Haas. Particularly suitable thickeners are z. B Aculyn ^® 22 (copolymer of acrylates and methacrylic acid with stearyl (20 EO units)) and Aculyn ^® 28 (copolymer of acrylates and methacrylic acid with behenyl (25 EO units)).

suitable cosmetically and / or dermatologically active agents are, for. B. coloring Active ingredients, skin and hair pigmentation agents, toning agents, Tanning agents, Bleach, keratin-curing Substances, antimicrobial agents, light filter agents, repellent agents, hyperemic substances, keratolytic and keratoplastic active substances, anti-dandruff agents, antiphlogistics, keratinizing acting substances, antioxidant or radical scavengers active ingredients, skin moisturizing or moisturizing substances, moisturizing Active ingredients, antierythimatös or anti-allergic active ingredients and mixtures thereof.

Artificially skin-tanning Active ingredients that are suitable to the skin without natural or artificial To irradiate irradiation with UV rays, z. B. dihydroxyacetone, Alloxan and walnut shell extract. Suitable keratin-hardening substances are usually active substances, as they are also used in antiperspirants be used, such. Potassium aluminum sulfate, aluminum hydroxychloride, Aluminum lactate, etc. Antimicrobial agents are used to destroy microorganisms or to inhibit their growth and thus serve both as a preservative as well as a deodorizing substance which causes the formation or the intensity of body odor reduced. These include z. Usual, Preservatives known to the person skilled in the art, such as p-hydroxybenzoic acid esters, Imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are z. B. zinc ricinoleate, Triclosan, undecylenic acid alkylolamides, triethyl citrate, Chlorhexidine etc. Suitable light filtering agents are substances that are ultraviolet rays absorb in the UV-B and / or UV-A range. Suitable UV filters are z. B. 2,4,6-triaryl-1,3,5-triazines in which the aryl groups each may carry at least one substituent, which is preferably selected under hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially Methoxycarbonyl and ethoxycarbonyl and mixtures thereof.

Suitable are still cinnamic acid esters, Benzophenones, camphor derivatives, and UV-blocking pigments, such as titanium dioxide, Talc and zinc oxide. Suitable repellent agents are compounds, which are capable of certain animals, especially insects, from To hold people or to drive away. This includes z. 2-ethyl-1,3-hexanediol, N, N-diethyl-m-toluamide, etc. Suitable hyperemic substances which stimulate the circulation of the skin are z. Essential oils such as mountain pine, lavender, Rosemary, juniper berry, horse chestnut extract, birch leaf extract, Hayflower extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, Eucalyptus oil, etc. Suitable keratolytic and keratoplastic substances are z. Salicylic acid, Calcium thioglycolate, thioglycolic acid and their salts, sulfur, etc. Suitable anti-dandruff agents are z. Sulfur, sulfur polyethylene glycol sorbitan monooleate, Sulfuricinol polyethoxylate, zinc pyrithione, aluminum pyrithione, etc. Suitable antiphlogistics, which counteract skin irritation, are z. B. allantoin, bisabolol, dragosantol, chamomile extract, panthenol, Etc.

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

Examples of anionic polymers are homo- and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes, eg. B. Luviset PUR ^® Fa. BASF, and polyureas. Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (z. B. Luvimer 100P ^®), copolymers of ethyl acrylate and methacrylic acid (eg. B. 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 other vinyl esters (eg Luviset ^® brands), maleic anhydride, optionally reacted with alcohol, anionic polysiloxanes, eg. B. carboxy, t-butyl acrylate, methacrylic acid (z. B. Luviskol ^® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as. C ₄ -C ₃₀ alkyl esters of meth (acrylic acid), C ₄ -C ₃₀ -alkyl vinyl esters, C ₄ -C ₃₀ -alkyl vinyl ethers and hyaluronic acid. Examples of anionic polymers are also vinyl acetate / crotonic acid copolymers, as are, for example, under the names Resyn ^® (National Starch) and Gafset ^® (GAF), and vinyl pyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF) , Other suitable polymers are the commercially available under the name Luviflex VBM-35 ^® (BASF) vinylpyrrolidone / acrylate terpolymer and polyamides or sodium sulfonate sodium sulfonate polyester.

Further suitable polymers are cationic polymers with the name Polyquaternium according to INCI, z. B. Copolymers of Vinylpyroolidon / N-vinylimidazolium salts (Luviquat ^® FC, Luviquat ^® HM, Luviquat ^® MS, Luviquat Care ^®), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat ^® PQ 11), copolymers of N-vinyl caprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat Hold ^®); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamidocopolymers (Polyquaternium-7) and chitosan. Suitable cationic (quaternized) polymers are also Merquat ^® (polymer based on dimethyldiallylammonium chloride), Gafquat ^® (quaternary polymers are formed by reacting polyvinylpyrrolidone with quaternary ammonium compounds), Polymer JR (hydroxyethylcellulose with cationic groups) and cationic polymers based on plants, z. As guar polymers, such as the Jaguar ^® brands Fa. Rhodia.

Further 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 derivatives, polyaspartic acid salts and derivatives. These included a Luviflex® ^® Swing (partially hydrolyzed copolymer of polyvinyl acetate and polyethylene glycol, Messrs. BASF).

Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinyl caprolactam, z. B. Luviskol ^® Plus (BASF), or polyvinylpyrrolidone and their copolymers, in particular with vinyl esters, such as vinyl acetate, z. B. Luviskol ^® VA 37 (BASF); Polyamides, z. B. based on itaconic acid and aliphatic diamines, as z. B. in DE-A-43 33 238 are described.

Suitable polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer ^® (National Starch) available Octylacryl amide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers and zwitterionic polymers, as described for example in the 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 metal and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are 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, for. As polyether siloxanes, such as Tegopren ^® (Goldschmidt) or Belsil ^® (Wacker).

The Formulation basis of pharmaceutical agents according to the invention contains preferably pharmaceutically acceptable excipients. pharmaceutical acceptable in the field of pharmacy, food technology and adjacent areas of known adjuvants, in particular those in relevant pharmacopoeia (eg DAB Ph. Eur. BP NF) and other excipients, whose properties do not conflict with a physiological application.

suitable Excipients can be: lubricants, wetting agents, emulsifying and suspending agents, preservatives Agents, anti-oxidants, anti-irritants, chelating agents, emulsion stabilizers, Film formers, gelling agents, odor masking agents, resins, hydrocolloids, Solvents Solubilizers, Neutralizing agents, permeation enhancers, pigments, quaternary ammonium compounds, refatting and superfatting agents, Ointment, cream or oil bases, Silicone derivatives, stabilizers, sterilants, blowing agents, drying agents, Opacifiers, Thickeners, waxes, softeners, white oils. A related embodiment based on expert Knowledge, as for example in Fiedler, H. P. Encyclopedia of excipients for pharmacy, Cosmetics and adjacent areas, 4th ed., Aulendorf: ECV Editio Kantor Verlag, 1996, shown are.

to Production of dermatological according to the invention Means can the active ingredients mixed with a suitable excipient (excipient) or diluted become. Excipients can solid, semi-solid or liquid Be materials that act as a vehicle, carrier or medium for the drug can serve. If desired, the admixing of further auxiliaries takes place in the person skilled in the art known way.

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

preferred Skin cleansers are soaps of liquid to gel consistency, like transparent soaps, luxury soaps, de-icing soaps, cream soaps, baby soaps, Skin protection soaps, abrasive soaps and syndets, pasteurized soaps, soft soaps and washing pastes, liquid Washing, shower and bath preparations, like washing lotions, shower baths and gels, bubble baths, oil baths and Scrub preparations.

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

Especially it is preferably skin care products, personal hygiene products, Foot care, Sunscreens, repellents, shaving, hair removal, Anti-acne, make-up, mascara, lipsticks, eye shadow, kohl pencils, Eyeliner, rouges and eyebrow pencils.

at the skin care agents according to the invention These are in particular W / O or O / UV skin creams, day and night creams, Eye creams, face creams, anti-wrinkle creams, moisturizing creams, Bleaching creams, vitamin creams, skin lotions, body lotions and moisturizing lotions.

skin cosmetic and dermatological agents based on the polymers described above A) show advantageous effects. The polymers can, inter alia, for moisturization and condition the skin and improve the skin feel. The polymers can also act as thickeners in the formulations. By adding the polymers of the invention In certain formulations, a significant improvement in the skin compatibility be achieved.

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

The agents according to the invention are suitable for use because of the contained component C) as a sunscreen.

ever according to application the agents according to the invention in a form suitable for skin care, such. B. as a cream, foam, Gel, pen, mousse, milk, spray (pump spray or propellant spray) or lotion. Particularly preferred is an insert in the form of a gel, especially in the form of a clear gel.

The skin cosmetic preparations in addition to the polymers A) and suitable carriers, other active ingredients customary in skin cosmetics and adjuvants as described above. These are preferably Emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, component C) various light stabilizers, bleaching agents, colorants, Tints, Tanning agents, Collagen, protein hydrolysates, Stabilizers, pH regulators, dyes, salts, thickeners, Gel former, bodying agent, silicones, humectants, moisturizers and more usual ones Additives.

Preferred oil and fat components of the skin cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as. As paraffins, silicone oils and aliphatic hydrocarbons having more than 8 carbon atoms, animal and vegetable oils, such as. As 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. As jojoba oil, fatty alcohols, Vaseline, hydrogenated lanolin and acetylated lanolin and mixtures thereof.

you can the polymers of the invention also with conventional Mix polymers if special properties are set should.

to Setting certain properties such. B. improvement of feel to the touch, the spreading behavior, the water resistance and / or the binding of Active ingredients and excipients, such as pigments, can be used in skin and cosmetic dermatological preparations additionally also conditioning Contain substances based on silicone compounds. suitable Silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, Polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.

The Production of cosmetic or dermatological preparations takes place according to usual, known to those skilled in the process.

Prefers are the cosmetic and dermatological means in the form of Emulsions, in particular as water-in-oil (W / O) or oil-in-water (O / W) emulsions in front. But it is also possible to choose other types of formulations, 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. The emulsions contain in addition to the copolymer A) and the light stabilizer C) usually conventional ingredients such as fatty alcohols, fatty acid esters and especially 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 emulsion type specific additives and the preparation of suitable emulsions is described for example in Schrader, bases and formulations of cosmetics, Hüthig book Verlag, Heidelberg, 2nd edition, 1989, third part, where hereby incorporated by reference.

A suitable emulsion, for. For example a skin cream, etc., contains generally an aqueous one Phase, by means of a suitable emulsifier in an oil or Fat phase is emulsified.

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. Preferably, the proportion of the fatty phase is about 20 to 60 wt .-%. Preferably, the proportion of the aqueous phase about 20 and 70%, each based on the total weight of the emulsion. The emulsifiers are those commonly 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; Monoesters and diesters of C ₁₂ -C ₁₈ fatty acids and glycerol or polyglycerol; Condensates of ethylene oxide and propylene glycols; oxypropylenated / oxyethylated C ₁₂ -C ₁₈ fatty alcohols; polycyclic alcohols, such as sterols; high molecular weight aliphatic alcohols such as lanolin; Mixtures of oxypropylenated / polyglycerinated 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 are contained in the fatty phase of the emulsions could be, are: hydrocarbon oils, like paraffin oil, purCellin, Perhydrosqualene and solutions microcrystalline waxes in these oils; animal or vegetable oils, such as Sweet almond oil, avocado oil, calophilum oil, lanolin and derivatives thereof, castor oil, Sesame oil, Olive oil, jojoba oil, Sheathing oil, hoplostethus oil; mineral oils whose Start of distillation under atmospheric pressure at about 250 ° C and their Distillation endpoint at 410 ° C lies, such. Vaseline oil; Saturated esters 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 cetyl ricinoleate.

The Fat phase can also be found in other oils soluble Silicone oils, such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.

Around the retention of oils to favor, can in addition to the polymers A) waxes are used, such as. Carnauba wax, Candililla wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.

in the Generally, the water-in-oil emulsions are prepared that the fat phase and the emulsifier are placed in a mixing container become. You warm up this at a temperature of about 50 to 75 ° C, then gives the oil-soluble Active ingredients and / or adjuvants and added with stirring to water, which was previously heated to about the same temperature and wherein optionally the water soluble Ingredients solved before Has. One stirs, until you get an emulsion of the desired Fineness receives and lets then cool to room temperature, optionally with less stirring becomes.

To a further preferred embodiment the agents according to the invention are a shower gel, a shampoo formulation or a bathing preparation. Preference is given to shower gels, especially 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. Other suitable active ingredients and / or auxiliaries are generally selected among lipids, perfume oils, dyes, organic acids, Preservatives and antioxidants as well as thickeners / gelling agents, Skin conditioners and moisturizers.

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

In the washing, shower and bath preparations can all in body cleansers usually used anionic, neutral, amphoteric or cationic surfactants be used.

Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoylsarcosinates, acyl taurates, acyl isothionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali and alkaline earth metal salts, e.g. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine Sal ze. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.

To counting z. Sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, Ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, Ammonium laurylsulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.

suitable amphoteric surfactants are for. B. alkylbetaines, alkylamidopropyl betaines, Alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or propionates, alkyl amphodiacetates or dipropionates.

For example can Cocodimethyl sulphopropyl betaine, lauryl betaine, cocamidopropyl betaine or sodium cocamphopropionate.

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

In addition, the Washing, shower and bath preparations usual cationic Contain surfactants, such as. B. quaternary ammonium compounds, for example Cetyltrimethylammonium chloride.

In addition, you can also more usual cationic polymers are used, such. B. copolymers Acrylamide and dimethyldiallylammonium chloride (Polyquaternium-7), cationic cellulose derivatives (Polyquaternium-4, -10), guar hydroxypropyltrimethylammonium chloride (INCI: Hydroxylpropyl Guar Hydroxypropyltrimonium Chloride), Copolymers from N-vinylpyrrolidone and quaternized N-vinylimidazole (Polyquaterinium-16, -44, -46), copolymers from N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Polyquaternium-11) and others.

Farther can the shower gel / shampoo formulations thickener, such. For example, common salt, PEG-55, propylene glycol oleate, PEG-120 methyl glucose dioleate and others, as well as preservatives, other active ingredients and excipients and water included.

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

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

Preferably are the hair treatment compositions according to the invention in the form of a mousse, hair mousse, hair gel, shampoo, Hair sprays or hair foam before. Hairsprays include both aerosol sprays as well as pump sprays without propellant. Hair foams include both aerosol foams as well pump foams without propellant.

• a) 0,1 bis 20 Gew.-%, bevorzugt 1 bis 10 Gew.-%, mindestens eines Polymers A), wie zuvor definiert,
• b) 0 bis 40 Gew.-% wenigstens eines Trägers (Lösungsmittels), der ausgewählt ist unter C₂-C₅-Alkoholen, insbesondere Ethanol,
• c) 0,01 bis 5 Gew.-%, bevorzugt 0,2 bis 3 Gew.-%, wenigstens eines Verdickers,
• d) 0 bis 50 Gew.-% eines Treibmittels,
• e) 0 bis 10 Gew.-%, bevorzugt 0,1 bis 3 Gew.-%, mindestens eines von a) verschiedenen Festigerpolymers, vorzugsweise eines wasserlöslichen nichtionischen Polymers,
• f) 0 bis 1 Gew.-% wenigstens eines Rückfetters, vorzugsweise ausgewählt unter Glycerin und Glycerinderivaten,
• g) 0 bis 30 Gew.-% weiterer Wirk- und/oder Hilfsstoffe, z. B. wenigstens eine Siliconverbindung,
• h) 0,001 bis 10 Gew.-%, bevorzugt 0,01 bis 5 Gew.-%, insbesondere 0,05 bis 1 Gew.-% wenigstens eines Esters der p-Aminobenzoesäure,
• i) Wasser ad 100 Gew.-%.

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 defined above,
• b) 0 to 40% by weight of at least one support (solvent) selected from C ₂ -C ₅ -alcohols, in particular ethanol,
• c) from 0.01 to 5% by weight, preferably from 0.2 to 3% by weight, of at least one thickener,
• d) 0 to 50% by weight of a propellant,
• e) 0 to 10 wt .-%, preferably 0.1 to 3 wt .-%, of at least one of a) different Festigerpolymer, preferably a water-soluble nonionic polymer,
• f) 0 to 1% by weight of at least one refining agent, preferably selected from glycerol and glycerol derivatives,
• g) 0 to 30 wt .-% of other active ingredients and / or adjuvants, for. At least one silicone compound,
• h) from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, in particular from 0.05 to 1% by weight, of at least one ester of p-aminobenzoic acid,
• i) water ad 100 wt .-%.

The Hair treatment products can continue to be in the form of hair sprays or hair foams. hairsprays and hair mousses preferably comprise predominantly or exclusively water-soluble or water-dispersible components. Are those in the hairsprays according to the invention and hair foams water-dispersible compounds used, they can be in the form of aqueous Microdispersions with particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm, are used. The solids content of these preparations usually lie here in a range of about 0.5 to 20 wt%. These microdispersions need usually no emulsifiers or surfactants for their stabilization.

preferred Hair treatment compositions are in the form of an aqueous dispersion or in Form of an alcoholic or watery-alcoholic solution in front. Examples of suitable alcohols are ethanol, propanol, isopropanol and mixtures thereof.

Further can the hair treatment compositions according to the invention generally common contain cosmetic adjuvants, such as plasticizers, such as Glycerin and glycol; emollients; perfumes; surfactants; from component C) various UV absorbers; dyes; antistatic agents; medium to improve combability; Preservatives; and defoamer.

If the agents according to the invention are formulated as a hair spray, they contain a sufficient amount a propellant, for example a low-boiling hydrocarbon or ethers, such as propane, butane, isobutane or dimethyl ether. When Propellants are also useful compressed gases, such as nitrogen, air or carbon dioxide. The amount of propellant can be kept low in order not to unnecessarily increase the VOC content. It is then generally not more than 55% by weight, based on the total weight of the agent. If desired, but are also higher VOC contents of 85 wt .-% and above possible.

The previously described polymers A) can also be used in combination with other hair polymers are used in the compositions. suitable Polymers are those previously described.

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

• a) 0,5 bis 20 Gew.-%, bevorzugt 1 bis 10 Gew.-%, mindestens eines Polymers A), wie zuvor definiert,
• b) 50 bis 99,5 Gew.-%, bevorzugt 55 bis 99 Gew.-%, eines Trägers (Lösungsmittels), ausgewählt unter Wasser und wassermischbaren Lösungsmitteln, bevorzugt C₂-C₅-Alkoholen, insbesondere Ethanol, und Mischungen davon,
• c) 0 bis 70 Gew.-%, bevorzugt 0,1 bis 50 Gew.-%, eines Treibmittels, vorzugsweise ausgewählt unter Dimethylether und Alkanen, wie z. B. Propan/Butan-Gemischen,
• d) 0 bis 10 Gew.-%, bevorzugt 0,1 bis 10 Gew.-%, mindestens eines von a) verschiedenen Haarpolymers, vorzugsweise eines in Wasser löslichen oder dispergierbaren Polymers,
• e) 0 bis 0,5 Gew.-%, bevorzugt 0,001 bis 2 Gew.-%, mindestens einer wasserlöslichen oder wasserdispergierbaren Siliconverbindung,
• f) 0,001 bis 10 Gew.-%, bevorzugt 0,01 bis 5 Gew.-%, insbesondere 0,05 bis 1 Gew.-% wenigstens eines Esters der p-Aminobenzoesäure,

sowie gegebenenfalls weitere Wirkstoffe und/oder Hilfsstoffe, wie zuvor definiert.A preferred hair treatment agent in the form of a hair spray or hair foam contains:

• a) from 0.5 to 20% by weight, preferably from 1 to 10% by weight, of at least one polymer A), as defined above,
• b) 50 to 99.5% by weight, preferably 55 to 99% by weight, of a carrier (solvent) selected from water and water-miscible solvents, preferably C ₂ -C ₅ -alcohols, in particular ethanol, and mixtures thereof,
• c) 0 to 70 wt .-%, preferably 0.1 to 50 wt .-%, of a blowing agent, preferably selected from dimethyl ether and alkanes, such as. For example propane / butane mixtures,
• d) 0 to 10% by weight, preferably 0.1 to 10% by weight, of at least one hair polymer other than 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) from 0.001 to 10% by weight, preferably from 0.01 to 5% by weight, in particular from 0.05 to 1% by weight, of at least one ester of p-aminobenzoic acid,

and optionally further active ingredients and / or adjuvants, as defined above.

The inventive agent can as component e) at least one nonionic, siloxane-containing, water-soluble or dispersible polymer, in particular selected from the polyether siloxanes described above. The amount this component is then generally about 0.001 to 2 wt .-%, based on the total weight of the agent.

The Copolymers A) are advantageously suitable as auxiliaries in pharmacy, preferably as or in coating agent (s) for the textile, Paper, printing and leather industry.

• A) wenigstens ein wasserlösliches oder wasserdispergierbares Copolymer, das erhältlich ist durch radikalische Copolymerisation von a) 5 bis 90 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), Acrylsäureamid und/oder Methacrylsäureamid, b) 0 bis 85 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), wenigstens einer α,β-ethylenisch ungesättigten amidgruppenhaltigen Verbindung der allgemeinen Formel I
  
  wobei R¹ für eine Gruppe der Formel CH₂=CR⁴- mit R⁴ = H oder C₁-C₄-Alkyl steht und R² und R³ unabhängig voneinander für H, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, mit der Maßgabe, das einer der Reste R² und R³ von H verschieden ist, oder R² und R³ gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für einen fünf- bis achtgliedrigen Heterocyclus stehen, oder R² für eine Gruppe der Formel CH₂=CR⁴- steht und R¹ und R³ unabhängig voneinander für H, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, oder R¹ und R³ gemeinsam mit der Amidgruppe, an die sie gebunden sind für ein Lactam mit 5 bis 8 Ringatomen stehen, c) 0 bis 40 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), wenigstens einer von den Komponenten a) und b) verschiedenen, damit copolymerisierbaren ungesättigten wasserlöslichen Verbindung, wobei der Gewichtsmengenanteil der Summe der Komponenten b) und c) wenigstens 5 Gew.-% beträgt, gegebenenfalls in Gegenwart von bis zu 25 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), wenigstens einer wasserlöslichen Komponente d), die ausgewählt ist unter d1) polyetherhaltigen Verbindungen, d2) Polymeren, die mindestens 50 Gew.-% Wiederholungseinheiten aufweisen, die sich von Vinylalkohol ableiten, d3) Stärke und Stärkederivaten, und Mischungen davon, und
• B) wenigstens einen kosmetisch akzeptablen Träger,

gegen die Einwirkung von Licht, wobei man das Mittel mit einer stabilisierend wirkenden Menge wenigstens eines Esters der p-Aminobenzoesäure, wie zuvor definiert, versetzt.Another object of the present invention is a process for the protection of a cosmetic agent containing

• A) at least one water-soluble or water-dispersible copolymer obtainable by radica aische copolymerization of a) 5 to 90 wt .-%, based on the total weight of components a) to d), acrylic acid amide and / or methacrylamide, b) 0 to 85 wt .-%, based on the total weight of components a) to d), at least one α, β-ethylenically unsaturated amide-containing compound of general formula I.
  
  where R ^{1 is} a group of the formula CH ₂ = CR ⁴ - where R ⁴ = H or C ₁ -C 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 represents} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ^{3 are} independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ¹ and R ³ together with the amide group to which they are attached to a lactam with 5 to 8 ring atoms, c) 0 to 40 wt .-%, based on the total weight of components a) to d), at least one of the components a) and b) different, copolymerizable therewith unsaturated water-soluble compound, wherein the amount by weight the sum of components b) and c) is at least 5% by weight, optionally in the presence of up to 25% by weight, based on the total weight of components a) to d), 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. 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 treated with a stabilizing amount of at least one ester of p-aminobenzoic acid as defined above.

The above to suitable and preferred embodiments of the polymers A), the carrier B) and the ester of p-aminobenzoic acid C) apply here accordingly.

• A) wenigstens ein wasserlösliches oder wasserdispergierbares Copolymer, das erhältlich ist durch radikalische Copolymerisation von a) 5 bis 90 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), Acrylsäureamid und/oder Methacrylsäureamid, b) 0 bis 85 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), wenigstens einer α,β-ethylenisch ungesättigten amidgruppenhaltigen Verbindung der allgemeinen Formel I
  
  wobei R¹ für eine Gruppe der Formel CH₂=CR⁴- mit R⁴ = H oder C₁-C₄-Alkyl steht und R² und R³ unabhängig voneinander für H, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, mit der Maßgabe, das einer der Reste R² und R³ von H verschieden ist, oder R² und R³ gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für einen fünf- bis achtgliedrigen Heterocyclus stehen, oder R² für eine Gruppe der Formel CH₂=CR⁴- steht und R¹ und R³ unabhängig voneinander für H, Alkyl, Cycloalkyl, Heterocycloalkyl, Aryl oder Hetaryl stehen, oder R¹ und R³ gemeinsam mit der Amidgruppe, an die sie gebunden sind für ein Lactam mit 5 bis 8 Ringatomen stehen, c) 0 bis 40 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), wenigstens einer von den Komponenten a) und b) verschiedenen, damit copolymerisierbaren ungesättigten wasserlöslichen Verbindung, wobei der Gewichtsmengenanteil der Summe der Komponenten b) und c) wenigstens 5 Gew.-% beträgt, gegebenenfalls in Gegenwart von bis zu 25 Gew.-%, bezogen auf das Gesamtgewicht der Komponenten a) bis d), wenigstens einer wasserlöslichen Komponente d), die ausgewählt ist unter d1) polyetherhaltigen Verbindungen, d2) Polymeren, die mindestens 50 Gew.-% Wiederholungseinheiten aufweisen, die sich von Vinylalkohol ableiten, d3) Stärke und Stärkederivaten, und Mischungen davon, und
• B) wenigstens einen kosmetisch akzeptablen Träger,

gegen die Einwirkung von Licht.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 defined above, for the protection of a cosmetic composition containing

• A) at least one water-soluble or water-dispersible copolymer obtainable by free-radical copolymerization of a) from 5 to 90% by weight, based on the total weight of components a) to d), of acrylic acid amide and / or methacrylamide, b) from 0 to 85% by weight .-%, based on the total weight of components a) to d), of at least one α, β-ethylenically unsaturated amide-containing compound of general formula I.
  
  where R ^{1 is} a group of the formula CH ₂ = CR ⁴ - where R ⁴ = H or C ₁ -C 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 represents} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ^{3 are} independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ¹ and R ³ together with the amide group to which they are attached to a lactam with 5 to 8 ring atoms, c) 0 to 40 wt .-%, based on the total weight of the components a) to d), at least one of the Components a) and b) different, water-soluble compound copolymerizable therewith, wherein the amount by weight of the sum of components b) and c) is at least 5 wt .-%, optionally in the presence of up to 25 wt .-%, based on the total weight the 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, and
• B) at least one cosmetically acceptable carrier,

against the action of light.

The above to suitable preferred embodiments of the polymers A), the carrier B) and the ester of p-aminobenzoic acid C) apply accordingly.

The The invention will be apparent from the following non-limiting Examples closer explained.

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

10% of feed 1, 20% of feed 2 and 10% of feed 3 in 490 g of water were initially taken in a stirred apparatus with reflux condenser, internal thermometer and four separate feed devices, and the mixture was heated to about 60 ° C. with stirring. After the initial polymerization, recognizable by an incipient increase in viscosity, the remainder of feed 1 was added at 65 ° C. within three hours, the remainder of feed 2 within 1.5 hours and the remainder of feed 3 within four hours. In an alternative embodiment, the pH of the reaction solution was adjusted by means of feed 5 to 6.4 to 7.4. After the end of the addition, polymerization was continued for a further 2 hours at this temperature. Subsequently, the feed 4 was added within 30 minutes at 65 ° C for postpolymerization and after the end of the addition was postpolymerized at this temperature for a further two hours and at a temperature of 80 to 90 ° C for a further two hours. In an alternative embodiment, the reaction mixture was subsequently treated with steam at a pH of about 6 for a further 1 h. An approximately 30% aqueous microdispersion is obtained. To stabilize the solution with 100 ppm of Euxyl ^® K 100 of Schülke & Mayr (5-chloro-2-methyl-3- (2H) -isothiazolone / 2-methyl-3- (2H) -isothiazolone / benzyl alcohol). When using water / ethanol mixtures can be dispensed with the use of a stabilizer.

Powdered products can by spray drying or freeze-drying. By analogy, all products were polymerized in the following list.

Table 1:

AT THE

acrylamide

MAM

methacrylamide

VP

N-vinylpyrrolidone

VCap

N-vinyl caprolactam

VFA

Nvinylformamide

DMAA

dimethylacrylamide

350-MA

polyethylene glycol methacrylate (Mn = 350)

Q DMAEMA

Dimethylaminoethylmethacrylate dimethyl sulfate

C-Dry

MD1934 degraded starch (dextrose equivalents DE = 38; Fa Cerestar)

PVOH

partially saponified polyvinyl alcohol (Mowiol ^® 4-88, Fa. Clariant)

General Preparation Method for Examples 51 to 65: Solution Polymerization with Postpolymerization and Water Treatment (Example 63)

In a stirring device with reflux condenser, internal thermometer and 4 separate feeders were 30.5 g of feed 1, 117 g of feed 2 and 4 g of feed 3 in 150 g of water submitted and the mixture with stirring to about 65 ° C heated. After the initial polymerization, recognizable by a beginning increase in viscosity, was at 65 ° C the remainder of feed 1 within 3 hours, the remainder of feed 2 in 5 hours and the remainder of feed 3 within 6 hours added, the internal temperature was increased to about 67 ° C. After the end of the Addition, the reaction mixture was about 2 hours in this Leave temperature. The polymer solution was water vapor Treated for 30 minutes. Subsequently was the feed 4 within 30 minutes and feed 5 within Added 5 minutes, and the polymer solution Postpolymerized for about three hours at a temperature of about 70 ° C. About 800 g of an approximately 22% polymer solution were obtained. The solution was treated with steam for about 1 hour and at a temperature of about 100 ° C stirred for another 2 hours.

To stabilize the solution having 100 ppm Euxyl (5-chloro-2-methyl-3- (2) -isothiazolone / 2-methyl-3- (2H) -isothiazolone / benzyl alcohol) was added ^® K100 Fa. Schulke & Mayr.

Powdered products were by spray drying or freeze-drying.

Analogous all products listed in Table 2 below were polymerized.

Table 2:

VI:

vinylimidazole

VCap:

N-vinyl caprolactam

DMAA:

dimethylacrylamide

350-MA:

Polyethylene glycol methacrylate (M _n 350)

PVOH:

partially saponified polyvinyl alcohol (Mowiol ^® 4-88, Fa. Clariant)

Application properties

Standard formulation:

Out 0.5 wt .-% of a commercial polyacrylic acid (Carbopol 940, BF Goodrich), neutralized with triethanolamine (TEA), a gel is formulated when applied to the hair in the mouth Essentially no conditioning or strengthening effect shows. The performance properties are shown in Table 3, Comparative Example A, reproduced.

Comparative Examples B - D:

Of the Gel formulation from the standard formulation are each 3 wt .-% a commercial one Hair polymer (Ex B: polyacrylic acid amide, C: polyvinylformamide, D: polyvinylpyrrolidone). The application technology Properties are shown in Table 2. The products are regarding their stickiness still in need of improvement.

According to the invention:

Of the Gel formulation from the standard formulation are each 3 wt .-% the copolymers 1 to 67 added as a hair cosmetic agent. This results in clear formulations with good conditioning or Setting action. The application properties are also in Table 3.

Rating:

A) clarity

B) Viscosity grade viscosity 1 very strong (reference: Gel from 0,5% Carbopol 940 / TEA) 2 firmly 3 moderately firm 4 fluently 5 low viscosity

C) stickiness

The tack was determined at a relative humidity of 75% and at ambient temperature directly on dried films of the gel formulations. grade stickiness 1 not sticky 2 slightly sticky 3 moderately sticky 4 sticky 5 very sticky

Table 3:

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

Use in hair cosmetics

1. "Ultra Hold" hair gel

To prepare the hair gel, the component A is added to a flask, the component B stirred and dispersed until the particles sink to the bottom. Thereafter, component C is added and stirred until a homogeneous gel is formed. 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 prepare the hair gel, the component A is added to a flask, the component B stirred and dispersed until the particles sink to the bottom. Thereafter, component C is added and stirred until a homogeneous gel is formed. Component D is mixed and stirred until dissolved. Then component D is added to the gel.
pH value: 6.9, viscosity (Brookfield): 33850 mPas, transmission: 98.1% (600 nm)

3. "Strong Hold" gel:

To prepare the hair gel component A is added to a flask, the component B stirred and dispersed until the particles sink to the bottom. Thereafter, component C is added and stirred until a homogeneous gel is formed. 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 the component A, the thickener is allowed to swell in water and stirred until the solution is homogeneous. Then it is neutralized with component B. To produce the component C, the Cremophor ^® is dissolved in water, then weighed component D and stirred until a clear solution is formed. While stirring, the combined components C and D are added to the combined components A and B.
pH value: 7.2, viscosity (Brookfield): 13000 mPas, transmission: 96.9% (600 nm)

5. "Wet Look" gel:

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

6. "Hold and Feel" gel:

To prepare the hair gel, component A is stirred and component B is added. Because of the many air bubbles in the formulation must be centrifuged.
pH value: 7.0, viscosity (Brookfield): 90200 mPas, transmission: 97.0% (600 nm)

7. "Fantasy" hair gel:

To prepare the hair gel, the component A is added to a flask, the component B stirred and dispersed until the particles sink to the bottom. Thereafter, component C is added and stirred until a homogeneous gel is formed. 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 (12)

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

where R ^{1 is} a group of the formula CH ₂ = CR ⁴ - where R ⁴ = H or C ₁ -C 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 represents} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ^{3 are} independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ¹ and R ³ together with the amide group to which they are attached to a lactam with 5 to 8 ring atoms, c) 0 to 40 wt .-%, based on the total weight of components a) to d), at least one of the components a) and b) different, copolymerizable therewith unsaturated water-soluble compound, wherein the amount by weight the sum of components b) and c) is at least 5% by weight, optionally in the presence of up to 25% by weight, based on the total weight of components a) to d), 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. D) starch and starch derivatives, and mixtures thereof, B) at least one cosmetically acceptable carrier, and C) at least one ester of p-aminobenzoic acid. 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 represent alkyl, hydroxyalkyl or a group of the formula - (CH ₂ CH ₂ O) _d (CH ₂ CH (CH ₃ ) O) _e -R ¹⁵ wherein the order of the alkylene oxide units is arbitrary, d and e are independently an integer from 0 to 100, wherein the sum of d and e is at least 2, and R ^{15 is} hydrogen or alkyl. Composition according to claim 2, wherein the compound of general formula IV is a compound of formula IV.1

in which the sum of d ¹ , d ² and d ³ is from 20 to 30, in particular about 25. Means according to one of the preceding claims, wherein the component b) comprises at least one compound which is selected N-vinyllactams, N-vinylamides of saturated monocarboxylic acids, N-alkyl and N, N-dialkylamides α, β-ethylenic unsaturated Monocarboxylic acids and mixtures thereof. Means according to one of the preceding claims, wherein component c) comprises at least one compound selected among 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 α, β-ethylenically unsaturated Mono- and dicarboxylic acids with diamines, which is a tertiary and a primary or secondary Having amino group; Polyether acrylates and mixtures thereof. Composition according to one of the preceding claims, wherein component B) is selected from i) water, ii) water-miscible organic solvents, preferably C ₁ -C ₄ -alkanols, iii) oils, fats, waxes, iv) of iii) various esters of C ₆ -C ₃₀ monocarboxylic acids with mono-, di- or trihydric alcohols, v) saturated acyclic and cyclic hydrocarbons, vi) fatty acids, vii) fatty alcohols and mixtures thereof. Agent according to one of the preceding claims, containing Furthermore at least one of the components A), B) and C) different Ingredient that selected is among cosmetically active substances, emulsifiers, surfactants, Preservatives, perfume oils, thickeners, Hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, bleaches, gelling agents, Care products, Dyes, Tints, Tanning agents, Dyes, pigments, bodying agents, moisturizers, restockers, Collagen, protein hydrolysates, Lipids, antioxidants, defoamers, Antistatic agents, emollients and plasticisers. Composition according to one of the preceding claims, containing at least one gelling agent selected from homo- and copolymers of acrylic acid and methacrylic acid and their salts; crosslinked 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. Composition according to one of the preceding claims in the form gel, foam, spray, ointment, cream, emulsion, suspension, Lotion, milk or paste. Composition according to one of the preceding claims, which in the form of a clear gel. A process for the protection of a cosmetic composition comprising A) at least one water-soluble or water-dispersible copolymer obtainable by free-radical copolymerization of a) from 5 to 90% by weight, based on the total weight of components a) to d), of acrylic acid amide and / or Methacrylic acid amide, b) 0 to 85 wt .-%, based on the total weight of components a) to d), of at least one α, β-ethylenically unsaturated amide group-containing compound of general formula I.

where R ^{1 is} a group of the formula CH ₂ = CR ⁴ - where R ⁴ = H or C ₁ -C 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 represents} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ^{3 are} independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ¹ and R ³ together with the amide group to which they are attached to a lactam with 5 to 8 ring atoms, c) 0 to 40 wt .-%, based on the total weight of components a) to d), at least one of the components a) and b) different, copolymerizable therewith unsaturated water-soluble compound, wherein the amount by weight the sum of components b) and c) is at least 5% by weight, optionally in the presence of up to 25% by weight, based on the total weight of components a) to d), 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. Starch and starch derivatives, and mixtures thereof, and B) at least one cosmetically acceptable carrier, against the action of light, wherein the agent is reacted with a stabilizing amount of at least one ester of the p-type. Aminobenzoic acid as defined in any one of claims 1 to 3. Use of a stabilizer composition consisting of or containing at least one ester of p-aminobenzoic acid as defined in any of claims 1 to 3 for the protection of a cosmetic composition comprising A) at least one water-soluble or water-dispersible copolymer obtainable by free-radical copolymerization of a) from 5 to 90% by weight, based on the total weight of components a) to d), of acrylic acid amide and / or methacrylamide, b) from 0 to 85% by weight, based on the total weight of components a) to d), at least one α, β-ethylenically unsaturated amide-containing compound of general formula I.

where R ^{1 is} a group of the formula CH ₂ = CR ⁴ - where R ⁴ = H or C ₁ -C 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 represents} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ^{3 are} independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or netaryl, or R ¹ and R ³ together with the amide group to which they are attached to a lactam with 5 to 8 ring atoms, c) 0 to 40 wt .-%, based on the total weight of components a) to d), at least one of the components a) and b) different, copolymerizable therewith unsaturated water-soluble compound, wherein the amount by weight the sum of components b) and c) is at least 5% by weight, optionally in the presence of up to 25% by weight, based on the total weight of components a) to d), 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. 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.