DE102005039537A1 - Use of water-soluble/water-dispersible polymer comprising e.g. ethylenic unsaturated compound and monoethylenic unsaturated amide group compound, for modification of rheologic aqueous and/or alcoholic composition such as hair gel - Google Patents

Abstract

Use of water-soluble or water-dispersible polymer by polymerization of a mixture, comprising at least one alpha ,beta - ethylenic unsaturated compound, at least one of different monoethylenic unsaturated amide group containing compound, a crosslinker, at least one monoethylenic unsaturated compound containing at least one group of alkyl substituted group, alkenyl, cycloalkyl, aryl, aryl alkyl and hetaryl and/or reactive precursor, further different monoethylenic unsaturated compound and a polyether containing compound, for modification of the rheologic aqueous and/or alcoholic compositions. Use of water-soluble or water-dispersible polymer by polymerization of a mixture, comprising 99.99-10 wt.% of at least one alpha ,beta - ethylenic unsaturated compound with at least one cationogenic and/or cationic group per molecule, 0-90 wt.% of at least one of different monoethylenic unsaturated amide group containing compound, 0.01-5 wt.% of cross linker, 0-15 wt.% of at least one monoethylenic unsaturated compound containing at least one group of 5-30C alkyl substituted group, 5-30C alkenyl, 5-8C cycloalkyl, aryl, aryl alkyl and hetaryl, and/or a reactive precursor, 0-30 wt.% of further different monoethylenic unsaturated compound and 0-70 wt.% of a polyether containing compound, where the polymerization is carried out in the presence of less than 69 wt.% of cyclohexane and less than 12 wt.% of water, and the absence of carbon dioxide, for modification of the rheologic aqueous and/or alcoholic compositions. Independent claims are included for: (1) a water-soluble or water-dispersible polymer; and (2) a cosmetic or pharmaceutical agent comprising the water-soluble or water-dispersible polymer.

Description

The The present invention relates to the use of a water-soluble or water-dispersible crosslinked polymers obtainable by Polymerization of a mixture comprising 99.99 to 10 wt .-% at least an α, β-ethylenic unsaturated Compound with at least one cationogenic and / or cationic Group per molecule, 0 to 90 wt .-% of at least one of a) different monoethylenic unsaturated amide group-containing compound and 0.01 to 5 wt .-% of a crosslinking agent for modifying the rheology of aqueous compositions.

polymers find multiple uses in hair cosmetics. Your task in The hair cosmetics is to the properties of the hair too In particular, to give the hair strengthening, the combability to improve and to convey a pleasant grip feeling.

So conditioners are used to improve dry and wet combability, Feeling, To improve gloss and appearance as well as antistatic hair To give properties. Preference is given to water-soluble polymers with polar, often cationic functionalities used that have a greater affinity to the structural conditional negative surface of the hair. Structure and mode of action of various hair treatment polymers are in Cosmetic & Toiletries 103 (1988) 23. Commercially available conditioner polymers are e.g. cationic hydroxyethylcellulose, cationic polymers based on N-vinylpyrrolidone, e.g. Copolymers of N-vinylpyrrolidone and quaternized N-vinylimidazole, acrylamide and diallyldimethylammonium chloride or silicones.

to Consolidation of hairstyles are vinyllactam homopolymers and copolymers and carboxylate group-containing polymers used. conditions For example, hair fixative resins are strong at high levels Humidity, elasticity, Washability from the hair, compatibility in the formulation and a pleasant handle of the hair.

difficulties often prepares the combination of various properties such as Example strong consolidation, pleasant grip of the hair and simultaneous thickening effect of the polymers in the hair cosmetic preparations.

This is particularly important in gel formulations. Furthermore show usual Firming polymers frequently intolerances with thickener polymers, it comes to turbidity and precipitation in the cosmetic formulations. Classic thickeners, either made of crosslinked polyacrylic acid (Carbopol) or copolymers, have the disadvantage that they due to the networking no for form the hair setting suitable films. They ensure the consistency of the gel, but will not after drying the gel on the hair more needed and disturb therefore potentially the performance characteristics of the formulation (Firming effect, moisture sensitivity).

DD-117 326 (Jeschek, H.) describes a method for increasing the Sensitivity and improve the stability of photographic Gelatin-halide silver emulsion layers by means of polyethylene glycol derivatives, characterized in that the gelatin-silver halide emulsions and / or their developers graft polymers of polyethylene glycol of average molecular weight 1500-6000 and vinyl compounds, the quaternary Contain nitrogen, added. A use for rheology modification aqueous Compositions are not described.

WHERE 03/080001 (BASF) relates to cationic graft polymers which are available by polymerization of quaternized-cationic, free-radical polymerizable monomers and optionally further free-radically copolymerizable Monomers in the presence of a polyether-containing compound with the proviso that the reaction in the presence of less than 20 wt .-% of water in the total reaction mixture he follows.

The Use for rheology modification of aqueous compositions not described.

WHERE 03/068834 describes the use of graft copolymers as Ingredient in cosmetic products. The graft copolymers are formed thereby by grafting of monoethylenically unsaturated, open-chain N-vinylamide units containing monomers on a polymeric graft base.

WO 03/106522 (BASF) describes the use of polyoxyalkylene-substituted alkylenediamine in cosmetic formulations. Also included are modified polyoxyalkylene-substituted alkylenediamines, in particular cationic polymers, and processes for their preparation. The polymers contain at least 40% by weight of polyoxyalkylene-substituted alkylenediamines.

WHERE 04/100910 (BASF) describes cosmetic compositions which at least contain a polymer which by radical polymerization α, β-ethylenic unsaturated Compounds each having at least one nitrogen-containing heterocycle contained in the presence of a polymeric grafting base, is available. In particular, vinylpyrrolidone-vinylimidazole copolymers, which in the presence of polyethylene glycol are described. In the polymerization, the solvent used is water, the polymers are not cross-linked and are not used for rheology modification used.

WHERE 03/042262 (BASF) relates to graft polymers containing a polymeric Grafting base (A), which is not monoethylenically unsaturated Having units, and polymeric side chains (B) formed from Copolymers of two different monoethylenically unsaturated Monomers (B1) and (B2), each containing at least one nitrogen-containing Heterocycle containing the proportion of side chains (B) am Total polymer 35 to 55 wt .-% is. In the polymerization is used as a solvent Water is used and the polymers are not cross-linked. Farther is the preparation of these graft polymers and their use as color transfer inhibitors in detergents, the use for rheology modification is not known.

Of the The subject of WO 03/042264 (BASF) differs from that WO 03/042262 in that the proportion of side chains (B) am Total polymer is more than 55 wt .-%.

WHERE 93/22380 (ISP) discloses hydrogels, adhesives and coatings containing crosslinked copolymers of 80-99 wt .-% N-vinylpyrrolidone and 1 to 20% by weight of N-vinylimidazole or 4-vinylpyridine, by solution polymerization were prepared in water.

DE 198 33 287 (BASF) describes the preparation of polymers of (a1) from 5 to 99.99% by weight of a free-radically polymerizable monomer which contains a quaternized or a quaternizable nitrogen atom, or mixtures of such monomers, (a2) from 5 to 95% by weight (b) from 0.01% to 20% by weight of a crosslinking monomer having at least two ethylenically unsaturated groups, and (c) from 0% to 50% by weight of another radically polymerizable monomer in supercritical carbon dioxide inert diluent with mixing at temperatures of over 31 ° C to 150 ° C and pressures above 73 bar.

DE 100 23 245 (BASF) describes hair cosmetic compositions containing (i) polymer obtainable by free-radically initiated polymerization of (a) 1 to 100% by weight, preferably 2 to 95% by weight, in particular 10 to 70% by weight, of at least one cationic monomer selected from N-vinylimidazoles and diallylamines, optionally in partially or completely quaternized form, (b) 0 to 99 wt .-%, preferably 5 to 98 wt .-%, in particular 30 to 90 wt .-%, at least one of (a) various water-soluble monomers; and (c) 0 to 50% by weight, preferably 0 to 40% by weight, in particular 0 to 30% by weight, of at least one other free-radically copolymerizable one of (a) or (b) Monomers and subsequent partial or complete quaternization or protonation of the polymer, if as monomer (a) a non or only partially quaternized monomer is used, (ii) Entkräuselungsmittel. The use of such polymers for the rheology modification of aqueous compositions is not described.

DE 197 31 907 (BASF) describes crosslinked cationic polymers of vinylimidazole and N-vinylpyrrolidone, which are prepared by gel, inverse suspension or inverse emulsion polymerization in aqueous solvent mixtures.

DE 102 41 296 (BASF) describes a process for the preparation of aqueous dispersions of crosslinked cationic water-soluble or water-swellable polymers based on the monoethylenically unsaturated monomer containing a quaternized or quaternizable nitrogen atom by radical polymerization in an aqueous salt solution in the presence of a protective colloid and their use in hair cosmetic formulations. The polymers are prepared by water-in-water emulsion polymerization.

US A 4,806,345 describes crosslinked cationic thickeners for cosmetic Formulations of quaternized dimethylaminoethyl methacrylate and Acrylamide.

WHERE 93/25595 describes crosslinked cationic copolymers based on quaternized Dialkylaminoalkylacrylate or Dialkylaminoalkylacrylamiden. When Application is the use of these crosslinked copolymers as thickeners suggested in cosmetic preparations.

DE A 32 09 224 describes the preparation of crosslinked polymers based on N-vinylpyrrolidone and (quaternized) N-vinylimidazole. These polymers are used for claimed the use as adsorbents and ion exchangers.

WHERE 96/37525 describes the preparation of crosslinked copolymers et al N-vinylpyrrolidone and quaternized vinylimidazoles in the presence of polymerization regulators and their use especially in detergents.

US A 4,058,491 discloses crosslinked cationic hydrogels of N-vinylimidazole or N-vinylpyrrolidone and a quaternized basic acrylate as well as other comonomers. These gels become complexing and controlled release of anionic active substances.

DE A 42 13 971 describes copolymers of an unsaturated Carboxylic acid, quaternized vinylimidazole and optionally other monomers and a crosslinker. The polymers are used as thickening and dispersing agents proposed.

WHERE 97/35544 describes the use of crosslinked cationic polymers with dialkylaminoalkyl (meth) acrylates or - (meth) acrylamides in Shampoo compositions.

EP A 0 893 117 and EP 1 064 924 describe the use of high molecular weight crosslinked cationic polymers as solution polymers. These have a good conditioning effect in shampoos.

DE A 19731907 describes the use of crosslinked cationic Copolymers containing N-vinylimidazoles in hair cosmetic Preparations.

Task of invention

A The object of the present invention was to find polymers which for cosmetic Applications are well suited and, for example in the field of hair cosmetics good application properties such as pleasant grip and at the same time a good conditioning effect or a good setting effect and at the same time have a thickening property. For this was especially the solubility the polymers in conventional Hair cosmetic preparations of interest.

task was also the provision of polymers that are both hair cosmetic Requirements (strengthening effect, curl retention) as well as application-related Requirements (thickening properties, clear solubility) are sufficient.

task The present invention further consisted of adding polymers find a thickening effect with film-forming properties so that these polymers e.g. in hair gel formulations can also be used as a solidifying polymer.

There was particular interest in polymers which have thickening properties even without the addition of further customary thickeners (eg Carbopol ^™ high molecular weight polyacrylic acids).

A Another object of the present invention was to provide polymers the high stability containing aqueous Compared to compositions Ensure salt loading. These polymers should also be in the pH range of 5 to 8 with cationic Compatible with polymers be.

Especially should be water-soluble or water-dispersible polymers based on inexpensive starting materials with opposite the prior art better properties in terms of rheology modification Water-containing compositions, especially in the field the (hair) cosmetic preparations are to be made available. there Already the use of small amounts of polymers should be a enable effective modification of the rheology.

Farther This effective rheology modification should also have a preferably wide pH range allows become. Furthermore, the polymers should be replaced by a cost-effective Procedure accessible and comparatively low refurbishment measures requires the products. Furthermore, the solubility in particular was the polymers in conventional cosmetic preparations of interest and those containing these polymers skin or compositions treated with the compositions and agents Hair should have good sensory properties.

in the Range of dermal cosmetic preparations, in particular emulsions, are polymeric thickeners needed, even at high salt concentrations and pH values of 5 to 8 a good thickening effect exhibit.

task So was the provision of polymers that are both (hair) cosmetic Requirements as well as application requirements (thickening Properties, clear solubility) suffice.

• a) 99,99 bis 10 Gew.-% wenigstens einer α,β-ethylenisch ungesättigten Verbindung mit wenigstens einer kationogenen und/oder kationischen Gruppe pro Molekül,
• b) 0 bis 90 Gew.-% wenigstens einer von a) verschiedenen monoethylenisch ungesättigten amidgruppenhaltigen Verbindung,
• c) 0,01 bis 5 Gew.-% eines Vernetzers,
• d) 0 bis 15 Gew.-% wenigstens einer monoethylenisch ungesättigten Verbindung d1) enthaltend wenigstens eine Gruppe ausgewählt aus der Gruppe bestehend aus, gegebenenfalls substituierten, C5-C30-Alkyl, C5-C30-Alkenyl, C5-C8-Cycloalkyl, Aryl, Arylalkyl und Hetaryl, und/oder eines reaktiven Vorproduktes (d2),
• e) 0 bis 30 Gew.-% weiterer, von a) bis d) verschiedener, monoethylenisch ungesättigter Verbindungen, in Gegenwart von
• f) 0 bis 70 Gew.-%, bezogen auf die Summe der Komponenten a) bis e) einer polyetherhaltigen Verbindung, mit der Maßgabe, dass sich die Mengen der Komponenten a) bis e) zu 100 Gew.-% addieren, wobei die Polymerisation in Gegenwart von weniger als 69 Gew.-% Cyclohexan und weniger als 12 Gew.-% Wasser, bezogen auf die Gesamtmenge aller während der Polymerisation gegenwärtigen Komponenten, und in Abwesenheit von überkritischem Kohlendioxid durchgeführt wird, zur Modifizierung der Rheologie wässriger Zusammensetzungen.

The above objects have been achieved by the use of a water-soluble or water-dispersible polymer obtainable by polymerization of a mixture comprising

• a) 99.99 to 10% by weight of at least one α, β-ethylenically unsaturated compound having at least one cationogenic and / or cationic group per molecule,
• b) 0 to 90 wt .-% of at least one of a) different monoethylenically unsaturated amide group-containing compound,
• c) 0.01 to 5% by weight of a crosslinker,
• d) 0 to 15% by weight of at least one monoethylenically unsaturated compound d1) containing at least one group selected from the group consisting of optionally substituted C5-C30-alkyl, C5-C30-alkenyl, C5-C8-cycloalkyl, aryl, Arylalkyl and hetaryl, and / or a reactive precursor (d2),
• e) 0 to 30 wt .-% of other, from a) to d) different, monoethylenically unsaturated compounds, in the presence of
• f) 0 to 70 wt .-%, based on the sum of the components a) to e) of a polyether-containing compound, with the proviso that the amounts of components a) to e) add up to 100 wt .-%, wherein the Polymerization in the presence of less than 69% by weight of cyclohexane and less than 12% by weight of water, based on the total amount of all components present during the polymerization, and in the absence of supercritical carbon dioxide to modify the rheology of aqueous compositions.

• ai) Estern α,β-ethylenisch ungesättigter Mono- und Dicarbonsäuren mit Aminoalkoholen, welche am Aminstickstoff mono- oder dial-kyliert sein können,
• aii) Amiden α,β-ethylenisch ungesättigter Mono- und Dicarbonsäuren mit Diaminen, welche mindestens eine primäre oder sekundäre Aminogruppe aufweisen,
• aiii) N,N-Diallylaminen,
• aiv) vinyl- und allylsubstituierten Stickstoffheterocyclen,
• av) vinyl- und allylsubstituierten heteroaromatischen Verbindungen und
• avi) Mischungen davon.

A preferred embodiment of the invention is the use of the abovementioned polymers, where the α, β-ethylenically unsaturated compound a) is selected from

• ai) esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, which may be mono- or dialkyl-cyclized on the amine nitrogen,
• aii) amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group,
• aiii) N, N-diallylamines,
• aiv) vinyl- and allyl-substituted nitrogen heterocycles,
• av) vinyl- and allyl-substituted heteroaromatic compounds and
• avi) mixtures thereof.

in the For the purposes of the present invention, the term alkyl includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are e.g. straight-chain or branched C1-C7-alkyl, preferably C1-C6-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 C8-C30-alkyl or C8-C30-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, for example, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl ), n-tridecyl (s), n-tetradecyl (s), n-pentadecyl (s), n-hexadecyl (s), n-heptadecyl (s), n-octadecyl (s), n-nonadecyl (s) Etc..

cycloalkyl is preferably for C5-C8 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, COO ^- M ⁺ and NE ¹ E ² , preferably alkyl , can wear. 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.

arylalkyl stands for Groups containing both alkyl and aryl radicals, these being Arylalkyl groups either via the aryl or over the alkyl radical is linked to the compound carrying it.

Component a)

to Production of for the use according to the invention suitable monomers usable a) are, for example generally in WO 03/080001 on page 18, Z.27 to S.22, Z.38 as "direct Precursors a2 "designated Links. This writing will be in full at this point Circumference referred.

Suitable cationogenic monomers a) are ai) the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols. Preferred amino alcohols are C ₂ -C ₁₂ -amino alcohols which are mono- or -dialkylated on the amino nitrogen C ₁ -C ₈ . 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, monobutyl maleate and mixtures thereof.

suitable Monomers a) are also aii) the amides of the abovementioned α, β-ethylenically unsaturated Mono- and dicarboxylic acids with diamines containing at least one primary or secondary amino group exhibit. Preferred are diamines which have a tertiary and a primary or secondary Have amino group.

preferred acid components are acrylic acid, methacrylic acid and their mixtures.

wobei
R¹⁴ und R¹⁵ unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, C₁-C₈ linear- oder verzweigtkettige Alkyl, Methoxy, Ethoxy, 2-Hydroxyethoxy, 2-Methoxyethoxy und 2-Ethoxyethyl. Bevorzugt sind Wasserstoff, Methyl oder Ethyl,
R¹⁷ Wasserstoff oder Methyl ist,
R¹⁸ Alkylen oder Hydroxyalkylen mit 1 bis 24 C-Atomen, optional substituiert durch Alkyl, bevorzugt C₂H₄, C₃H₆, C₄H₈, CH₂-CH(OH)-CH₂ ist,
g 0 oder 1 ist,
Z Stickstoff für g = 1 oder Sauerstoff für g = 0 ist,
R²⁵ bzw. R²⁶ jeweils und unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, C₁-C₄₀ linear- oder verzweigtkettige Alkyl, Formyl, C₁-C₁₀ linear- oder verzweigtkettige Acyl, N,N-Dimethylaminoethyl, 2-Hydroxyethyl, 2-Methoxyethyl, 2-Ethoxyethyl, Hydroxypropyl, Methoxypropyl, Ethoxypropyl oder Benzyl. Bevorzugt sind Wasserstoff, Methyl, Ethyl, n-Propyl und Benzyl.Preferred esters ai) or amides aii) of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols or diamines are therefore aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides of the general formula I:

in which
R ¹⁴ and R ^{15 are} independently selected from the group consisting of hydrogen, C ₁ -C ₈ linear or branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl. Preference is given to hydrogen, methyl or ethyl,
R ^{17 is} hydrogen or methyl,
R ^{18 is} alkylene or hydroxyalkylene having 1 to 24 C atoms, optionally substituted by alkyl, preferably C ₂ H ₄ , C ₃ H ₆ , C ₄ H ₈ , CH ₂ -CH (OH) -CH ₂ ,
g is 0 or 1,
Z is nitrogen for g = 1 or oxygen for g = 0,
R ²⁵ and R ^{26 are} each independently selected from the group consisting of hydrogen, C ₁ -C ₄₀ linear or branched chain alkyl, formyl, C ₁ -C ₁₀ linear or branched chain acyl, N, N-dimethylaminoethyl, 2 -Hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl, ethoxypropyl or benzyl. Preference is given to hydrogen, methyl, ethyl, n-propyl and benzyl.

Preferred as component ai) are in particular
N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate,
N- (n-propyl) aminoethyl (meth) acrylate, N- (n-butyl) aminoethyl (meth) acrylate,
N- (tert-butyl) aminoethyl (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 and
N, N-dimethylaminocyclohexyl (meth) acrylate. In particular, as component ai)
N- (tert-butyl) aminoethyl acrylate and N- (tert-butyl) aminoethyl methacrylate used.

The amides may be unsubstituted, N-alkyl or N-alkylamino monosubstituted or N, N-dialkyl substituted or N, N-dialkylamino-disubstituted wherein the alkyl or alkylamino groups are C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched chain, or C ₃ -C ₄₀ carbocyclic units are derived.

Preferred components aii)
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, N- [8- (dimethylamino) octyl] methacrylamide, N- (12- (dimethylamino) dodecyl] methacrylamide,
N- [3- (diethylamino) propyl] methacrylamide and N- [3- (diethylamino) propyl] acrylamide.

wobei R²⁷ Wasserstoff oder C₁ bis C₂₄ Alkyl bedeutet. Besonders bevorzugt sind N,N-Diallylamin und N,N-Diallyl-N-Methylamin, insbesondere N,N-Diallyl-N-Methylamin. Besonders bevorzugt ist N,N,-Diallyl-N-Methylamin, das in einer quaternisierten Form beispielsweise unter der Bezeichnung DADMAC (Diallyldimethylammoniumchlorid) kommerziell erhältlich ist.Furthermore, the cationogenic monomer a) may also be selected from aiii) N, N-diallylamines of the general formula II

where R ^{27 is} hydrogen or C ₁ to C ₂₄ alkyl. Particular preference is given to N, N-diallylamine and N, N-diallyl-N-methylamine, in particular N, N-diallyl-N-methylamine. Particularly preferred is N, N, -diallyl-N-methylamine, which is commercially available in a quaternized form, for example under the name DADMAC (diallyldimethylammonium chloride).

Especially preferred cationogenic monomers a) are also aiv) vinyl and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinylimidazole derivatives, e.g. B. N-vinyl-2-methylimidazole, vinyl and allyl-substituted heteroaromatic compounds such as 2-and 4-ol 4-vinylpyridine, 2- and 4-allylpyridine.

Very particular preference is given to N-vinylimidazoles of the general formula (III) in which R ¹ to R ^{3 are} hydrogen, C ₁ -C ₄ -alkyl or phenyl

• Me = Methyl
• Ph = Phenyl

Examples of compounds of the general formula (III) are shown in Table 1 below: TABLE 1

• Me = methyl
• Ph = phenyl

Most preferred as component a) is aiv) N-vinylimidazole, ie the compound of the formula III, where all radicals R ¹ to R ^{3 are} hydrogen.

The Reaction of Compounds a) to Quaternary Compounds May During or preferably after the reaction. In a subsequent implementation can be the intermediary Polymer initially isolated and cleaned or immediately implemented. The implementation can Completely or partially. At least 10% are preferred, more preferably at least 20%, most preferably at least 30% of the incorporated monomers a) converted into the corresponding quaternary form. Of the Proportion of conversion to quaternary Compounds are preferably higher, the lower the water solubility of the monomer a).

Prefers it is, the monomers a) in predominantly, i.e. to more than 70, preferably to more than 90, more preferably more than 95, most preferably more than 99 mole% in cationogenic, that is not quaternized or protonated form for polymerization use and only during or more preferably after polymerization by quaternization into the cationic or protonated form.

Protonation / quaternization

In a preferred embodiment of the invention, the polymer is only during or particularly preferred partially or completely protonated or quaternized after the polymerization, since as component a) preferably a not or only partially quaternised or protonated monomer is used for the polymerization.

The Monomers (a) can be used either in protonated or quaternized form or preferably polymerized non-quaternized or non-protonated be in the latter case, the resulting copolymer during or preferably after the polymerization for the use according to the invention either quaternized or protonated.

In the case, that the monomers are used in quaternized form, can they are either as a dried substance or concentrated in the form solutions in for the monomers of suitable solvents, for example, in polar solvents such as water, methanol, ethanol, acetone, in the other components a) to f), provided that these are solvents are suitable or use in electrolyte solutions.

For protonation, for example, mineral acids such as HCl, H ₂ SO ₄ , and monocarboxylic acids such as formic acid and acetic acid, dicarboxylic acids and polyfunctional carboxylic acids, such as oxalic acid and citric acid and all other proton donating compounds and substances that are able to protonate the corresponding nitrogen atom. In particular, water-soluble acids are suitable for protonation.

When possible organic acids be mono- and polyhydric, optionally substituted aliphatic and aromatic carboxylic acids, mono- and polyvalent, optionally substituted aliphatic and aromatic sulfonic acids or mono- and polyhydric, optionally substituted aliphatic and aromatic phosphonic acids.

preferred organic acids are hydroxycarboxylic acids such as glycolic acid, Lactic acid, tartaric acid and citric acid called, with lactic acid is particularly preferred.

When preferred inorganic acids be phosphoric acid, phosphorous acid, Sulfuric acid, sulphurous Acid and hydrochloric acid called, wherein phosphoric acid is particularly preferred.

The Protonation of the polymer takes place either immediately after to the polymerization or only in the formulation of the cosmetic Preparation, which usually has a physiologically acceptable pH is set.

Under Protonation is understood to be at least part of the protonatable Groups of the polymer, preferably at least 20, preferably more than 50, more preferably more than 70, most preferably more than 90 mol% is protonated, so that a cationic total charge of the polymer results.

to Quaternization of the compounds a) are, for example, alkyl halides with 1 to 24 C atoms in the alkyl group, e.g. Methyl chloride, methyl bromide, Methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, Dodecyl chloride, lauryl chloride, propyl bromide, hexyl bromide, dodecyl bromide, Lauryl bromide and benzyl halides, in particular benzyl chloride and Benzyl bromide. Preferred quaternizing agent is methyl chloride. For quaternization with long-chain alkyl radicals are the corresponding Alkyl bromides such as hexyl bromide, dodecyl bromide or lauryl bromide are preferred.

Further suitable quaternizing agents are dialkyl sulfates, in particular Dimethyl sulfate or diethyl sulfate.

The Quaternization of the basic monomers a) can also be carried out with alkylene oxides such as ethylene oxide or propylene oxide in the presence of acids.

preferred Quaternizing agents are methyl chloride, dimethyl sulfate or diethyl sulfate, with methyl chloride being particularly preferred.

The Quaternization of the monomers or polymers with one of said Quaternizing can be done by well known methods.

The Polymers can according to the invention for modification the rheology of watery Compositions in the pH range from 1 to 12, preferably from 2 to 10 are used.

in the Range of pH 1 to pH 5, it is advantageous if the quaternizable Groups of polymers less than 20%, preferably less than 10%, more preferably less than 1% quaternized.

in the Range of pH 6 to pH 10, it is advantageous if the quaternizable Groups of polymers at least 10%, preferably at least 20% and at most to 99, preferably to at most 90 quaternized present.

Between pH 5 and pH 6 can the polymers, depending from their quantitative and / or qualitative monomer composition advantageously either partially quaternized or not quaternized available.

Of the Professional finds out through routine experiments, whether a particular Polymer in this pH range advantageously quaternized or not quaternized. By further routine experiments can be also the for the desired Effect most suitable degree of quaternization (= quotient of amount the quaternized groups and sum of the amounts of quaternized Groups and non-quaternized quaternizable groups).

The for the use according to the invention contains suitable polymer at the most 99.99 and at least 10, preferably at least 30 and in particular At least 60 wt .-% of the monomer or monomers a) copolymerized.

Especially for the Use of the polymers as thickeners in hair cosmetic preparations is a proportion of at least 60, preferably at least 70 wt .-% polymerized component a) advantageous.

Component b)

The for the use according to the invention contains suitable polymer 0 to 90, preferably 10 to 70 and more preferably 30 to 60 % By weight of at least one of a) different monoethylenically unsaturated amide group-containing compound b) copolymerized.

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 oder R² und R³ gemeinsam mit dem Stickstoffatom, an das sie gebunden sind, für einen fünf- bis achtgliedrigen Stickstoff-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.This further component b) is preferably selected from compounds of the general formula IV

in which
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 or R ² and R ³ together with the nitrogen atom to which they are attached represent a five- to eight-membered nitrogen heterocycle or
R ^{2 is} 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 are for a lactam with 5 to 8 ring atoms.

Preferably, the polymer used according to the invention additionally contains in copolymerized form as monomer b) at least one N-vinyllactam. Suitable N-vinyllactam b) are unsubstituted N-vinyllactams and N-vinyllactam derivatives which contain, for example, one or more C ₁ -C ₆ -alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc., may have. These include, for example, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone , N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, etc., and mixtures thereof.

Preferably, the polymer suitable for the use according to the invention contains monomers b), wherein in formula IV R ^{2 represents} CH ₂ = CH- and R ¹ and R ³ together with the amide group to which they are attached represent a lactam having 5 ring atoms.

Especially preference is given to N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, (Meth) acrylamide or mixtures thereof, wherein N-vinylpyrrolidone and methacrylamide is most preferred.

In a special embodiment contains that for the use according to the invention suitable polymer only monomers a) and b) incorporated, wherein N-vinylimidazole as a) and N-vinylpyrrolidone as b) are preferred.

The polymer suitable for the use according to the invention contains at most 90, preferably at most 70 and in particular at most 40 wt .-% of the monomer or monomers b) in copolymerized form. In one embodiment of the invention, the polymer suitable for the use according to the invention contains little at least 1, particularly preferably at least 10 and in particular at least 20% by weight of the monomer or monomers b) are copolymerized.

Crosslinker c)

In a further preferred embodiment The invention is for the preparation of the inventive use crosslinkers c) selected from suitable polymers Compounds with at least 2 ethylenically unsaturated, non-conjugated Double bonds per molecule.

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

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 acid neopentylglycol 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, as well as polyethylene glycols, Polypropylene glycols and polytetrahydrofurans with molecular weights of every 200 to 10,000.

Except the Homopolymers of ethylene oxide or propylene oxide can also Block copolymers of ethylene oxide or propylene oxide or copolymers, the ethylene oxide and propylene oxide groups incorporated incorporated become.

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. Preferred multivalent Alcohols in this context are also di- and trisaccharides.

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

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

Suitable as crosslinkers c) are also straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons having at least two double bonds feature, which are not conjugated in aliphatic hydrocarbons allowed to, e.g. Divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, Trivinylcyclohexane or polybutadienes with molecular weights of 200 to 20,000.

Other suitable crosslinkers are the amides of (meth) acrylic acid, itaconic acid and maleic acid and also N-allylamines of at least difunctional amines. Such amines are, for example, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine. Also suitable are the amides of allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least divalent car Bonsäuren, as described above.

Further are triallylamine and triallylmonoalkylammonium salts, e.g. Triallylmethylammonium chloride or Methyl sulfate, suitable as a crosslinker.

Suitable are also N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes, for example of Urea, ethyleneurea, propyleneurea or tartaramide, e.g. N, N'-Divinylethylenharnstoff or N, N'-divinylpropyleneurea.

Suitable are also alkylene bisacrylamides such as methylenebisacrylamide and N, N '- (2,2) butane and 1,1'-bis (3,3'-vinylbenzimidazolite-2-one) -1,4-butane.

Other suitable crosslinkers are, for example, alkylene glycol di (meth) acrylates such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol acrylate, Tetraethylene glycol dimethacrylate, diethylene glycol acrylate, diethylene glycol methacrylate, Vinyl acrylate, allyl acrylate, allyl methacrylate, divinyl dioxane, pentaerythritol ally ether as well as mixtures of these crosslinkers.

Further suitable crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane.

Especially Crosslinkers preferably used are, for example, methylenebisacrylamide, Triallylamine and triallylalkylammonium salts, divinylimidazole, pentaerythritol triallyl ether, N, N'-Divinylethylenharnstoff, 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.

All particularly preferred as crosslinkers are pentaerythritol triallyl ether, Methylenebisacrylamide, N, N'-divinylethyleneurea, Triallylamine and triallylmonoalkylammonium salts, and acrylic esters of ethylene glycol, butanediol, trimethylolpropane or glycerol or acrylate of glycol reacted with ethylene oxide and / or epichlorohydrin, Butanediol, trimethylolpropane or glycerol. Most preferred is pentaerythritol triallyl ether.

Of course you can too Mixtures of the aforementioned compounds can be used. The crosslinker is preferably soluble in the reaction medium. Is the solubility of the crosslinking agent in the reaction medium low, it may be in a monomer or dissolved in a monomer mixture or in one solvent solved are added, which mixes with the reaction medium. Especially preferred are those crosslinkers which are soluble in the monomer mixture.

The Crosslinkers c) are used for the use according to the invention in amounts of at least 0.01, preferably at least 0.05, especially preferably at least 0.1 and at most 5, preferably at most 2 and more preferably at most 1 wt .-% used.

In a particularly preferred embodiment The invention pentaerythritol triallyl ether in an amount of From 0.1% to 0.7% by weight, most preferably in an amount of 0.3 wt .-% to 0.6 wt .-% used.

The Wt .-% - amount of crosslinker c) refers to those for the production amount of the mixture of components a) to. used e).

Further monoethylenic unsaturated Compound d)

According to the invention the mixture to be polymerized further 0 to 15 wt .-% of at least one monoethylenically unsaturated Compound d1) containing at least one group selected from the group consisting of optionally substituted C5-C30 alkyl, C5-C30 alkenyl, C5-C8 cycloalkyl, aryl, arylalkyl and hetaryl and / or of a reactive precursor (d2).

component d) bears im for the use according to the invention suitable polymer is a hydrophobic group.

The compounds d1) may be hydrophobic monomers, for example esters or amides of (meth) acrylic acid with aliphatic C5 to C30 alcohols or amines such as He xyl (meth) acrylate or - (meth) acrylamide, n-heptyl (meth) acrylate or - (meth) acrylamide, n-octyl (meth) acrylate or - (meth) acrylamide, n-nonyl (meth) acrylate or - (meth) acrylamide, n-decyl (meth) acrylate or - (meth) acrylamide, n-undecyl (meth) acrylate or - (meth) acrylamide, n-dodecyl (meth) acrylate or - (meth ) acrylamide, n-tridecyl (meth) acrylate or - (meth) acrylamide, n-tetradecyl (meth) acrylate or - (meth) acrylamide, n-pentadecyl (meth) acrylate or - (meth) acrylamide, n- Hexadecyl (meth) acrylate or - (meth) acrylamide, n-heptadecyl (meth) acrylate or - (meth) acrylamide, n-octadecyl (meth) acrylate or - (meth) acrylamide and n-nonadecyl (meth) acrylate or - (meth) acrylamide.

at The compounds d1) may also be hydrophobic, for example Rests substituted (meth) acrylic acid esters of polyalkylene glycols such as alkyl substituted (meth) acrylic acid polyethylene glycol esters.

Suitable as d1) are also long-chain allyl or vinyl ethers such as C5-C30-alkyl-vinyl ethers or C5-C30-alkenyl-vinyl ethers.

Suitable as d1) are also free-radically polymerizable, olefinically unsaturated group-containing derivatives of polyisobutene. Preferred compounds d1) thereof are, for example, reaction products of polyisobutene succinic anhydride (PIBSA) with hydroxyalkyl (meth) acrylates and polyisobutene succinimide (PIBSA) with hydroxyalkyl (meth) acrylates
WO 04/035635, page 12, Z.26 to S.27, Z2 describes in detail processes for the preparation of polyisobutene derivatives, which can then be converted by conventional reactions with components containing olefinically unsaturated groups to give suitable compounds d) , This description is hereby incorporated by reference. Polyisobutene derivatives which may be converted to suitable compounds d) are for example the products BASF) are (under the tradenames Glissopal ^® or Kerocom ^® each commercially available.

In a particularly preferred embodiment The invention as component d) 2 to 10 wt .-% octadecyl vinyl ether and / or behenyl acrylate and / or stearyl methacrylate.

In a further particularly preferred embodiment of the invention, esters of (meth) acrylic acid with polyethylene glycol mono-C ₁₆ -C ₂₂ -alkyl ethers are used as component d). Preferred polyethylene glycol mono C ₁₆ -C ₂₂ alkyl ethers contain from 25 to 80 units of ethylene oxide per molecule.

For example, the (meth) can be used as such compounds d) acrylic acid esters are used with 80 Lutensol ^® AT 25, Lutensol ^® AT 50 or Lutensol ^® AT.

Also suitable are methacrylic acid esters of ethoxylated (for example, with 25 mol of ethylene oxide) C ₁₆ -C ₁₈ -Fettalkoholgemischen as for example as PLEX ^® O-6877 or PLEX ^® O-6954 (Degussa) are commercially available.

Under reactive precursors d2) are within the scope of this invention radically polymerizable monomers understood before or after its copolymerization by a, if appropriate, polymer-analogous, Implementation with at least one group selected from the group consisting from, optionally substituted, C5-C30-alkyl, C5-C30-alkenyl, C5-C8-cycloalkyl, Aryl, arylalkyl and hetaryl can be covalently linked. When Examples are monoethylenically unsaturated compounds which have a Wear epoxide group, called. These epoxide groups may be, for example after the copolymerization into a polymer by reaction with C5-C30-alcohols be covalently linked to a C5-C30 alkyl chain.

Preferred compounds d) are selected from the group consisting of C ₁₈ -C ₃₀ -alkyl (meth) acrylates and C ₁₈ -C ₃₀ -alkyl vinyl ethers.

The for the use according to the invention contains suitable polymer at the most 20, preferably at most 15 and more preferably at most 10 and preferably at least 1, more preferably at least 2-10 wt .-% of the component or components d).

Especially for the Use of the polymers as thickeners in skin cosmetic preparations is a proportion of at least 2, preferably at least 4 wt .-% copolymerized Component d) advantageous.

Polyether-containing compound f)

The for the use according to the invention suitable polymer is available by polymerization in the presence of 0 to 70 wt .-%, based on the amount of components a) to e), a polyether-containing compound f).

suitable polyether-containing compounds f) 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 f). As a polyether-containing compound f) can for example, polyalkylene glycols, polyesters based on polyalkylene glycols as well as polyether urethanes are used.

Component f) is preferably polyethers from the group of polyalkylene oxides based on ethylene oxide, propylene oxide and butylene oxides, polytetrahydrofuran and polyglycerol. Depending on the type of monomer used in their preparation, the polyether-containing compounds f) contain the following structural units:
- (CH ₂ ) ₂ -O-, - (CH ₂ ) ₃ -O-, - (CH ₂ ) ₄ -O-, -CH ₂ -CH (CH ₃ ) -O-, -CH ₂ -CH (CH ₂ -CH ₃ ) -O-, -CH ₂ -CHOR ^a -CH ₂ -O-,
wherein R ^{a is} C ₁ -C ₂₄ alkyl, preferably C ₁ -C ₄ alkyl.

Suitable are both homopolymers and copolymers, wherein the Copolymerisate the alkylene oxide randomly distributed or as blocks can contain.

The compounds f) can additionally have bridging groups, which are selected, for example, under:
-C (= O) -O-, -OC (= O) -O-, -C (= O) -NR ^b -, -OC (= O) -NR ^b -, -NR ^c - (C = O ) -NR ^b -,
wherein R ^b and R ^c independently of one another represent hydrogen, C ₁ -C ₃₀ -alkyl, preferably C ₁ -C ₄ -alkyl, or cycloalkyl.

Preferably, the polyethers f) have a number average molecular weight M _n of at least 300.

auf, worin:
R⁷ für Hydroxy, Amino, C₁-C₂₄-Alkoxy, R¹³-COO-, R¹³-NH-COO- oder einen Polyalkoholrest steht,
R⁸, R⁹ und R¹⁰ unabhängig voneinander für -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -CH₂-CH(CH₃)-, -CH₂-CH(CH₂-CH₃)- oder -CH₂-CHOR¹⁴-CH₂- stehen,
R¹¹ für Wasserstoff, Amino-C₁-C₆-alkyl, C₁-C₂₄-Alkyl, R¹³-C(=O)- oder R¹³-NH-C(=O)- steht,
R¹² für eine C₁-C₂₀-Alkylengruppe steht, deren Kohlenstoffkette durch 1 bis 10 nichtbenachbarte Sauerstoffatome unterbrochen sein kann;
R¹³ für C₁-C₂₄-Alkyl steht,
R¹⁴ für Wasserstoff, C₁-C₂₄-Alkyl oder R¹³-CO- steht,
A für -C(=O)-O-, -C(=O)-B-C(=O)-O- oder -C(=O)-NH-B-NH-C(=O)-O- steht,
B für -(CH₂)_t-, gewünschtenfalls substituiertes Cycloalkylen, gewünschtenfalls substituiertes Heterocycloalkylen oder gewünschtenfalls substituiertes Arylen steht,
n für 1 oder, wenn R⁷ einen Polyalkoholrest bedeutet, 1 bis 8 steht,
s für 0 bis 500, bevorzugt 0 bis 100 steht,
t für 1 bis 12, bevorzugt 2 bis 6, steht,
u unabhängig voneinander jeweils für 1 bis 5000, bevorzugt 1 bis 1000, steht,
v unabhängig voneinander jeweils für 0 bis 5000, bevorzugt 1 bis 1000, steht,
w unabhängig voneinander jeweils für 0 bis 5000, bevorzugt 1 bis 1000, steht.The polyethers f) preferably have the general formula Va or Vb

in which:
R ^{7 is} hydroxy, amino, C ₁ -C ₂₄ -alkoxy, R ¹³ -COO-, R ¹³ -NH-COO- or a polyalcohol radical,
R ⁸ , R ⁹ and R ¹⁰ are each independently - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH ₂ -CH (CH ₃ ) -, -CH ₂ - CH (CH ₂ -CH ₃ ) - or -CH ₂ -CHOR ¹⁴ -CH ₂ - stand,
R ^{11 is} hydrogen, amino-C ₁ -C ₆ -alkyl, C ₁ -C ₂₄ -alkyl, R ¹³ -C (= O) - or R ¹³ -NH-C (= O) -,
R ^{12 is} a C ₁ -C ₂₀ alkylene group whose carbon chain may be interrupted by 1 to 10 non-adjacent oxygen atoms;
R ^{13 is} C ₁ -C ₂₄ -alkyl,
R ^{14 is} hydrogen, C ₁ -C ₂₄ -alkyl or R ¹³ -CO-,
A is -C (= O) -O-, -C (= O) -BC (= O) -O- or -C (= O) -NH-B-NH-C (= O) -O- .
B is - (CH ₂ ) _t -, optionally substituted cycloalkylene, optionally substituted heterocycloalkylene or optionally substituted arylene,
n is 1 or, if R ^{7 is} a polyalcohol radical, 1 to 8,
s is 0 to 500, preferably 0 to 100,
t is 1 to 12, preferably 2 to 6,
each independently of one another represents from 1 to 5,000, preferably from 1 to 1,000,
each independently represents 0 to 5000, preferably 1 to 1000,
each independently represents 0 to 5,000, preferably 1 to 1,000.

preferred Components f) are the polyethers of the formula Va.

The terminal primary hydroxyl groups of the polyethers prepared on the basis of alkylene oxides, tetrahydrofuran or glycerol and the secondary OH groups of polyglycerol can both be present as a free etherified with C ₁ -C ₂₄ alcohols, esterified with C ₁ -C ₂₄ carboxylic acids or with Isocyanates be converted to urethanes. Examples of suitable alcohols for this purpose are: primary aliphatic alcohols, such as methanol, ethanol, propanol and butanol, primary aromatic alcohols, such as phenol, isopropylphenol, tert-butylphenol, octylphenol, nonylphenol and naphthol, secondary aliphatic alcohols, such as isopropanol, tertiary aliphatic alcohols Alcohols such as tert-butanol and polyhydric alcohols, for example, diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol and butanediol, and triols such as glycerol and trimethylolpropane. However, the hydroxyl groups can also be exchanged by reductive amination, for example with hydrogen-ammonia mixtures under pressure for primary amino groups or converted by cyanethylation with acrylonitrile and hydrogenation in Aminopropylenendgruppen. The closure of the hydroxyl end groups can be done not only subsequently by reaction with the alcohols or with alkali metal, amines and hydroxylamines, but these compounds can be used as Lewis acids, such as boron trifluoride, also at the beginning of the polymerization as a starter. Finally, the hydroxyl groups can also be closed by reaction with alkylating agents, such as dimethyl sulfate.

The alkyl radicals in the formulas Va and Vb can be branched or unbranched C ₁ -C ₂₄ -alkyl radicals, as defined above, preference being given to C ₁ -C ₁₂ -alkyl radicals and C ₁ -C ₆ -alkyl radicals being particularly preferred.

The average molecular weight M _{n of} the polyethers is at least 300 and at most 100,000. It is preferably 500 to 50,000, more preferably 2,000 to 35,000, and most preferably 2,000 to 9,000.

advantageously, Polytetrahydrofurans, homopolymers and copolymers of Ethylene oxide, propylene oxide, butylene oxide and isobutylene oxide, which are linear or can be branched, as a grafting base b). The term homopolymers is intended here according to the invention also such Include polymers which except the polymerized alkylene oxide unit still contain the reactive molecules, to initiate the polymerization of cyclic ethers or to end group closure of the polymer were used.

Preferred compounds f) are, for example, the polyether-containing compounds, BASF) are commercially available (under the trade names Pluriol ^™, Pluronic ^™, Lutensol ^™, Pluracol ^™ and Plurafac ^™ respectively BASF), Lupranol ^™ (Elastogran) or PolyTHF ^® (.

In general, polyol macromers can also be used as component f). Such polyol macromers are known in the art. In particular, the in US 5,093,412 and WO 05/003200 disclosed polyol macromers, which are incorporated herein by reference.

In a preferred embodiment of the invention, the polymerization is carried out in the presence of polyalkylene oxide-containing silicones as compounds f). Suitable polyalkylene oxide-containing silicones are described, for example, in the following documents, the disclosure of which is hereby incorporated by reference in its entirety:
DE-PS 16 94 366: It relates to polysiloxane-polyoxyalkylene block copolymers whose polysiloxane block is constructed in a conventional manner and whose polyoxyalkylene block from 25 to 70 weight percent of a polyoxyalkylene having an average molecular weight of 1600 to 4000 and an ethylene oxide content of 20 to 100 weight percent , The radical propylene oxide and optionally higher alkylene oxides, and 30 to 75 weight percent of a polyoxyalkylene having an average molecular weight of 400 to 1200 and an ethylene oxide content of 65 to 100 weight percent, balance propylene oxide and optionally higher alkylene oxides.

DE-OS 25 41 865: The polysiloxane-polyoxyalkylene block copolymers are re their polyoxyalkylene blocks so defined that the a polyoxyalkylene block having an average molecular weight of 900 to 1300 has and to 30 to 55 wt .-% of ethylene oxide, the remainder of propylene oxide, and the other polyoxyalkylene block has an average molecular weight of 3800 to 5000 and to 30 to 50 wt .-% of ethylene oxide, balance Propylene oxide exists.

EP-A 0 275 563: The block copolymer described comprises three different polyoxyalkylene blocks, namely a block containing 20 to 60% by weight of oxyethylene units a molecular weight of 3000 to 5500, another block of 20 to 60 wt .-% oxyethylene units and a molecular weight of 800 to 2900 and a third block only of polyoxypropylene units and a molecular weight of 130 to 1200.

preferred polyalkylene oxide-containing silicones are described by EP-A 0 670 342. EP-A 0 670 342 describes on S.3, Z.22 to S.4, Z.56 polysiloxanes with 1) at least two polyether radicals A and B, where the polyoxyalkylene radical A with an average molecular weight of 600 to 5500 from 20 to 100 % By weight of oxyethylene units and 80 to 0% by weight of oxypropylene units and the polyoxyalkylene radical B having an average molecular weight from 700 to 5000 from 0 to <20 % By weight of oxyethylene units and 100 to 80% by weight of oxypropylene units and 2) Si-bonded hydrocarbon radicals having 6 to 30 carbon atoms.

Particularly suitable silicone derivatives are those known under the INCI-name Dimethicone copolyols or silicone surfactants such as those available under the trade names Abil ^® (Goldschmidt), Alkasil ^® (Rhône-Poulenc), Silicone Polyol Copolymer ^® (Genesee), Belsil ^® (Wacker) , Silwet ^® (Witco) or Dow Corning ^® (Dow Corning) These include compounds having the CAS numbers 64365-23-7; 68937-54-2; 68938-54-5; 68937-55-3.

Especially suitable silicone derivatives are those described in WO 99/04750 p. 10, Z.24 to S.12, Z.8 and S.13, Z.3 to Z.34 compounds.

WHERE 01/013884 p.24, Z.22 to p.26, Z.41 describes further particularly preferred polyalkylene oxide-containing silicones.

On the aforementioned publications and citations from the prior art is referred to in its entirety.

Particularly preferably, the polymerization of the mixture of components a) to e) in the presence of, based on the amount of components a) to e), 5 to 25 wt .-% of polyethylene glycol having molecular weight M _n of at least 2,000 to at most 35,000, preferably at most 9000 and / or 5 to 25 wt .-% esters of (meth) acrylic acid with polyethylene glycol mono-C ₁₆ -C ₂₂ -alkyl ethers.

The Polymerization of the mixture of components a) to e) is preferably in the presence of at most 50, more preferably at most 40 wt .-% of component f), based on the sum of the amounts of Components a) to e) performed.

In a further embodiment The invention relates to the polymerization of the mixture of the components a) to e) is in the presence of 5 to 70, preferably 10 to 50, especially preferably 20 to 40 wt .-% of component f) based on the sum the amounts of components a) to e) performed.

Other monomers e)

The for the use according to the invention suitable polymers can if desired 0 to 30 wt .-% further, different from a) to d), monoethylenic unsaturated Contain compounds in copolymerized form.

Preferably, these additional monomers e) are chosen from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₃₀ alkanols, C ₂ -C ₃₀ - alkanediols and C ₂ -C ₃₀ amino alcohols, amides, α, β- ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C ₃₀ -diamines and C ₂ -C ₃₀ -aminoalcohols which have a primary or secondary amino group, amides of α, β-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, N-vinylamides of saturated monocarboxylic acids, esters of vinyl alcohol and allyl alcohol with C ₁ -C ₃₀ -monocarboxylic acids, vinyl ethers, α, β-ethylenically unsaturated mono- and dicarboxylic acids, vinylaromatics, vinyl halides, vinylidene halides, C ₁ -C ₈ -monoolefins , non-aromatic hydrocarbons having at least two conjugated double bonds and mixtures thereof.

Suitable additional monomers e) are methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl ethacrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, n-octyl (meth) acrylate, 1,1,3, 3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-unde cyl (meth) acrylate, tride-cyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, arrachinyl (meth) acrylate, Behenyl (meth) acrylate, lignocerenyl (meth) acrylate, cerotinyl (meth) acrylate, melissiyl (meth) acrylate, palmitoleinyl (meth) acrylate, oleyl (meth) acrylate, linolyl (meth) acrylate, linolenyl (meth) acrylate, Stearyl (meth) acrylate, lauryl (meth) acrylate and mixtures thereof.

Suitable additional monomers e) are also the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols, preferably C ₂ -C ₁₂ -aminoalcohols. These may preferably be C ₁ -C ₈ -monoalkylated or -dialkylated on the amine nitrogen. Suitable acid components of these esters are, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Preference is given to using acrylic acid, methacrylic acid and mixtures thereof. Preferred are
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.

suitable additional Monomers e) are also N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide, tert-butyl (meth) acrylamide, n-octyl (meth) acrylamide, 1,1,3,3-tetramethylbutyl (meth) acrylamide, Ethylhexyl (meth) acrylamide, n-nonyl (meth) acrylamide, n-decyl (meth) acrylamide, n-undecyl (meth) acrylamide, tridecyl (meth) acrylamide, myristyl (meth) acrylamide, Pentadecyl (meth) acrylamide, palmityl (meth) acrylamide, heptadecyl (meth) acrylamide, Nonadecyl (meth) acrylamide, arrachinyl (meth) acrylamide, behenyl (meth) acrylamide, Lignocerenyl (meth) acrylamide, cerotinyl (meth) acrylamide, melissinyl (meth) acrylamide, Palmitoleinyl (meth) acrylamide, o-leyl (meth) acrylamide, Linolyl (meth) acrylamide, linolenyl (meth) acrylamide, stearyl (meth) acrylamide, Lauryl (meth) acrylamide and mixtures thereof.

suitable additional Monomers e) are furthermore 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylate Etc.

suitable additional Monomers e) are furthermore N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide and N- [4- (dimethylamino) cyclohexyl] methacrylamide.

suitable additional Monomers e) are furthermore acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpropionamide and mixtures from that.

When additional Monomers e) are also monoethylenically unsaturated mono- and dicarboxylic acids with 3 to 25, preferably 3 to 6 carbon atoms, which are also in the form of their salts or anhydrides can be used. Examples of these are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic, citraconic, mesaconic, glutaconic, Aconitsäu-re, fumaric acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, vinylsulfuric acid, vinylphosphoric acid, 10-undecenoic acid, 4-pentenoic acid, cinnamic acid, 3-butenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, citraconic acid, mesaconic acid, styrenesulfonic acid, styrenesulfuric acid, acrylic acid (3-sulfopropyl) ester, Itaconic acid-bis- (3-sulfopropyl) ester, Methacrylic acid (3-sulfopropyl) ester, 3-Allyloxy-2-hydroxypropane-1-sulfonic acid, 2-acrylamido-2-methylethane-sulfonic acid, 2-sulfoethyl acrylate, Itaconic acid-bis- (2-sulfoethyl) ester, Methacrylic acid (2-sulfoethyl) ester, methacrylic acid (3-sulfopropyl) ester, 3-Allyloxy-2-hydroxypropane-1-sulfonic acid, 3-allyloxy-2-hydroxyethane-1-sulfonic acid and their alkali metal and ammonium salts, especially their sodium and Potassium salts.

suitable additional Monomers e) are furthermore ethylene, propylene, isobutylene, butadiene, Styrene, α-methylstyrene, o-chlorostyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, Vinyl fluoride, vinylidene fluoride, ethers of vinyl alcohol and 1 to 18 C-atoms having monoalcohols, such as methyl vinyl ether, Esters of vinyl alcohol and 1 to 18 carbon atoms monocarboxylic acids, such as Vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate and mixtures thereof.

When Component e) most preferred is methyl (meth) acrylate.

polymerization

to Preparation of the polymers, the mixture to be polymerized Components a) to e) Presence of f) both with the aid of Radical forming initiators as well as by the action of higher energy Radiation, including the action of high-energy electrons be understood to be polymerized.

When Initiators for The radical polymerization can be customary for this Peroxo and / or azo compounds be used, for example, alkali metal or Ammoniumperoxidisulfate, 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'-azo-bis (2-methyl-butyronitrile). Are suitable also initiator mixtures or redox initiator systems, e.g. Ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tertiary butyl hydroperoxide / sodium disulfite, tertiary butyl hydroperoxide / sodium hydroxymethanesulfinate.

Prefers organic peroxides are used.

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. So-called triplet sensitizers, such as benzyldiketals, can also be used become. 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 UV-low light sources, such as fluorescent tubes with a high blue content.

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

The Polymerization takes place in the temperature range from 40 to 200 ° C, preferably in the range of 50 to 140 ° C, more preferably in the range of 60 to 110 ° C. It is usually under atmospheric pressure carried out, However, under reduced or elevated pressure, preferably between 1 and 5 bar, expire.

The Polymerization can be carried out, for example, as solution polymerization, polymerization in substance, emulsion polymerization, reverse emulsion polymerization, Suspension polymerization, reverse suspension polymerization or precipitation polymerization carried out without restricting the methods that can be used.

Especially Preferably, the polymerization is carried out as a precipitation polymerization.

at The polymerization in substance can be done so that the Component f) in the mixture of components a) to e) dissolves and after Addition of a polymerization initiator polymerized the mixture.

The Polymerization can also be carried out semi-continuously, by first a part, e.g. 10% of the mixture to be polymerized from the Component f), the monomers a) to e) and initiator presents, the Mixture heated to polymerization and after starting the polymerization of the rest of the mixture to be polymerized after Progress of the polymerization admits. The polymers can also be obtained by that one the component f) is introduced in a reactor to the polymerization temperature heated and the mixture of monomers a) to e) and polymerization initiator either at once, intermittently or preferably continuously inflicts and polymerized.

If desired, the above-described polymerization may also be carried out in a solvent. Suitable solvents are, 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 ether of dihydric alcohols, diethylene glycol, tri ethylene glycol, glycerin, dioxane, butyl acetate, ethyl acetate and toluene, with ethyl acetate, butyl acetate and mixtures thereof being particularly preferred.

at the polymerization can Also substances are used, with the help of which the molecular weight The polymers can be controlled and commonly used as Regulator.

regulator

The radical polymerization of the monomer mixture may be in the presence at least one controller. Regulators are preferably in an amount used of 0.0005 to 5 wt .-%, more preferably of 0.001 to 2.5 wt .-% and insbesonde re from 0.01 to 1.5 wt .-%, based on the total weight of component a) to e) used.

When Regulators (polymerization regulators) are generally compounds with high transfer constant designated. Regulators accelerate chain transfer reactions and cause thus a reduction in the degree of polymerization of the resulting Polymers without affecting the gross reaction rate.

at The controllers can be used between mono-, bi- or polyfunctional controllers differ depending on the number of functional groups in the molecule that belong to one or more chain transfer reactions to lead can. Suitable regulators are described, for example, in detail by K.C. Berger and G. Brandrup in J. Brandrup, E.H. Immergut, Polymer Handbook, 3rd ed., John Wiley & Sons, New York, 1989, p. II / 81-II / 141.

When Regulators are, for example, aldehydes such as formaldehyde, acetaldehyde, Propionaldehyde, n-butyraldehyde, isobutyraldehyde.

Further can also be used as regulators: formic acid, its salts or esters, such as ammonium formate, 2,5-diphenyl-1-hexene, hydroxylammonium sulfate, and hydroxylammonium phosphate.

Further suitable regulators are halogen compounds, for. For example, alkyl halides, such as carbon tetrachloride, chloroform, bromotrichloromethane, bromoform, Allyl bromide, and benzyl compounds such as benzyl chloride or benzyl bromide.

Further suitable regulators are allyl compounds, such as. B. allyl alcohol, functionalized allyl ethers, such as allyl ethoxylates, alkyl allyl ethers, or glycerol monoallyl ether.

Prefers are used as regulator compounds that bind sulfur in Form included.

links of this type are, for example, inorganic hydrogen sulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, Sulfoxides and sulfones. These include Di-n-butylsulfide, di-n-octylsulfide, diphenylsulfide, thiodiglycol, Ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, Diethanol sulfide, di-t-butyl trisulfide, dimethyl sulfoxide, dialkyl sulfide, Dialkyl disulfide and / or diaryl sulfide.

Especially preferred are organic compounds containing sulfur in bonded Form included.

Prefers Compounds used as polymerization regulators are thiols (compounds, get the sulfur in the form of SH groups, also called mercaptans designated). Preferred regulators are mono-, bi- and polyfunctional Mercaptans, mercaptoalcohols and / or mercaptocarboxylic acids.

Examples for this Compounds are allyl thioglycolates, ethyl thioglycolate, cysteine, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropane-1,2-diol, 1,4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, thioacetic Thiourea and alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan.

Especially preferred thiols are cysteine, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropane-1,2-diol, thioglycerol, thiourea.

Examples of bifunctional regulators that contain two sulfur-bonded species are bifunctional ones Thiols such. As dimercaptopropanesulfonic acid (sodium salt), dimercaptosuccinic acid, dimercapto-1-propanol, dimercaptoethane, dimercaptopropane, dimercaptobutane, dimercaptopentane, dimercaptohexane, ethylene glycol bis-thioglycolate and butanediol-bis-thioglycolate.

Examples for polyfunctional Regulators are compounds containing more than two sulfur in bound form contain. Examples of this are trifunctional and / or tetrafunctional mercaptans.

preferred trifunctional regulators are trifunctional mercaptans, such as. B. Trimethylolpropane tris (2-mercaptoethanoate, trimethylolpropane tris (3-mercaptopropionate), Trimethylolpropane tris (4-mercapto-butanate), trimethylolpropane tris (5-mercaptopentanate), Trimethylolpropane tris (6-mercaptohexanate), trimethylolpropane tris (2-mercaptoacetate), Glyceryl thioglycolate, glyceryl thiopropionate, glyceryl thioethylate, Glyceryl thiobutanate, 1,1,1-propanetriyl tris (mercaptoacetate), 1,1,1-propanetriyl tris (mercaptoethanoate), 1,1,1-propanetriyl tris (mercaptoproprionate), 1,1,1-propanetriyl tris (mercaptobutanate), 2-hydroxymethyl-2-methyl-1,3-propanediol tris (mercaptoacetate), 2-hydroxymethyl-2-methyl-1,3-propanediol tris (mercaptoethanoate), 2-hydroxymethyl-2-methyl-1,3-propanediol tris (mercaptopropionate), 2-hydroxymethyl-2-methyl-1,3-propanediol tris (mercaptobutanate).

Especially preferred trifunctional regulators are glyceryl thioglycolate, trimethylolpropane tris (2-mercaptoacetate), 2-hydroxymethyl-2-methyl-1,3-propanediol tris (mercaptoacetate).

preferred tetrafunctional mercaptans are pentaerythritol tetrakis (2-mercaptoacetate), Pentaerythritol tetrakis (2-mercaptoethanoate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (4-mercaptobutanate), Pentaerythritol tetrakis (5-mercaptopentanate), pentaerythritol tetrakis (6-mercaptohexanate).

in der
n ein Wert von 0 bis 2 ist,
R¹ eine C₁-C₁₆-Alkylgruppe oder Phenylgruppe bedeutet,
R² eine C₁-C₁₈-Alkylgruppe, die Cyclohexyl- oder Phenylgruppe bezeichnet,
Z für eine C₁-C₁₈ Alkylgruppe, C₂-C₁₈-Alkylengruppe oder C₂-C₁₈-Alkinylgruppe steht, deren Kohlenstoffatome durch nicht benachbarte Sauerstoff- oder Halogenatome ersetzt sein können, oder für eine der Gruppen

in denen
R₃ eine C₁-C₁₂-Alkylgruppe bedeutet und
R₄ eine C₁-C₁₈-Alkylgruppe bezeichnet.Further suitable polyfunctional regulators are Si compounds which are formed by reacting compounds of the formula (IVa). Further suitable as polyfunctional regulator Si compounds of the formula

in the
n is a value from 0 to 2,
R ^{1 represents} a C ₁ -C ₁₆ alkyl group or phenyl group,
R ^{2 is} a C ₁ -C ₁₈ alkyl group which denotes cyclohexyl or phenyl group,
Z is a C ₁ -C ₁₈ alkyl group, C ₂ -C ₁₈ alkylene group or C ₂ -C ₁₈ alkynyl group, whose carbon atoms may be replaced by nonadjacent oxygen or halogen atoms, or one of the groups

in which
R _{3 is} a C ₁ -C ₁₂ alkyl group and
R ₄ denotes a C ₁ -C ₁₈ alkyl group.

All mentioned regulator can used individually or in combination with each other.

In an embodiment no regulator is used in the invention.

Preference is given to polymers obtainable by free-radical polymerization of
From 99.99 to 10% by weight of component a), in particular N-vinylimidazole,
0 to 90% by weight of component b), in particular N-vinylpyrrolidone,
0.01 to 5% by weight of a crosslinker c), in particular pentaerythritol triallyl ether,
0 to 20 wt .-% of a component d), in particular octadecyl vinyl ether and / or stearyl methacrylate
0 to 30 wt .-% of a component e) in the presence of
0 to 70 wt .-% based on the sum of components a) to e) of a polyether-containing compound f), in particular polyethylene glycol,
with the proviso that the amounts of components a) to e) add up to 100 wt .-%, wherein the polymerization in the presence of less than 69 wt .-% cyclohexane and less than 12 wt .-% water, based on the Total amount of all components present during the polymerization, and in the absence of supercritical carbon dioxide is performed.

Further preferred are polymers which are obtainable by free-radical graft copolymerization of
97.95 to 40% by weight of component a), in particular N-vinylimidazole,
From 1 to 60% by weight of component b), in particular N-vinylpyrrolidone,
0.05 to 2% by weight of a crosslinker c), in particular pentaerythritol triallyl ether,
1 to 15% by weight of a component d), in particular octadecyl vinyl ether and / or stearyl methacrylate
0 to 20 wt .-% of a component e) in the presence of
0 to 50 wt .-% based on the sum of components a) to e) of a polyether-containing compound f), in particular polyethylene glycol,
with the proviso that the amounts of components a) to e) add up to 100 wt .-%, wherein the polymerization in the presence of less than 69 wt .-% cyclohexane and less than 12 wt .-% water, based on the Total amount of all components present during the polymerization, and in the absence of supercritical carbon dioxide is performed.

• a) 96,9 bis 60 Gew.-% Komponente a), insbesondere N-Vinylimidazol,
• b) 1 bis 40 Gew.-% Komponente b), insbesondere N-Vinylpyrrolidon und/oder Methacrylamid
• c) 0,1 bis 1 Gew.-% eines Vernetzers c), insbesondere Pentaerythrittriallylether,
• d) 2 bis 10 Gew.-% einer Komponente d) insbesondere Octadecylvinylether und/oder Stearylmethacrylat und/oder Behenylacrylat und/oder Ester der (Meth)acrylsäure mit Polyethylenglykolmono-C₁₆-C₂₂-alkylethern,
• e) 0 bis 10 Gew.-% einer Komponente e) in Gegenwart von
• f) 0 bis 35 Gew.-% bezogen auf die Summe der Komponenten a) bis e) einer polyetherhaltigen Verbindung f), insbesondere Polyethylenglykol und/oder Polyethylenglykolmono-C₁₆-C₂₂-alkylether und/oder Polytetrahydrofuran, mit der Maßgabe, dass sich die Mengen der Komponenten a) bis e) zu 100 Gew.-% addieren, wobei die Polymerisation in Gegenwart von weniger als 69 Gew.-% Cyclohexan und weniger als 12 Gew.-% Wasser, bezogen auf die Gesamtmenge aller während der Polymerisation gegenwärtigen Komponenten, und in Abwesenheit von überkritischem Kohlendioxid durchgeführt wird.

Very particular preference is given to polymers obtainable by free-radical graft copolymerization of

• a) 96.9 to 60% by weight of component a), in particular N-vinylimidazole,
• b) 1 to 40 wt .-% of component b), in particular N-vinylpyrrolidone and / or methacrylamide
• c) 0.1 to 1% by weight of a crosslinker c), in particular pentaerythritol triallyl ether,
• d) 2 to 10% by weight of a component d), in particular octadecyl vinyl ether and / or stearyl methacrylate and / or behenyl acrylate and / or esters of (meth) acrylic acid with polyethylene glycol mono-C ₁₆ -C ₂₂ -alkyl ethers,
• e) 0 to 10 wt .-% of a component e) in the presence of
• f) 0 to 35 wt .-% based on the sum of components a) to e) of a polyether-containing compound f), in particular polyethylene glycol and / or polyethylene glycol mono-C ₁₆ -C ₂₂ -alkyl ethers and / or polytetrahydrofuran, with the proviso that the amounts of components a) to e) add up to 100 wt .-%, the polymerization in the presence of less than 69 wt .-% cyclohexane and less than 12 wt .-% water, based on the total amount of all during the polymerization present components, and in the absence of supercritical carbon dioxide.

The preferred method for the preparation of the inventive use suitable polymers is the precipitation polymerization. For this Polymerization become solvents used in which the starting materials for the polymerization and soluble the resulting polymer insoluble are. Suitable solvents are, for example, aromatic hydrocarbons such as toluene, xylenes, Benzene or aliphatic hydrocarbons such as n-alkanes, cyclohexane, Esters of acetic acid such as ethyl acetate, butyl acetate, ethers such as e.g. Diethyl ether, dipropyl ether, Dibutyl ether, methyl tert-butyl ether, Diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone and mixtures of these solvents. Mixtures of e.g. Ethyl acetate and butyl acetate are particularly suitable because in this solvent mixture the polymers are obtained in easily separable form (sedimentation is accelerated) and as well the reaction temperature in mixtures of butyl acetate and ethyl acetate above the boiling point of ethyl acetate can be selected with simultaneous evaporation by boiling ethyl acetate.

The Polymerization is carried out in the presence of less than 69% by weight of cyclohexane and less than 12% by weight of water, based on the total amount of all while the polymerization current Components, performed.

Prefers the polymerization is in the presence of less than 50, especially preferably less than 40 and in particular less than 30 wt .-% Cyclohexane performed.

Prefers the polymerization is in the presence of less than 10, especially preferably less than 8 and in particular less than 5 wt .-% water carried out.

In a preferred embodiment is that for the polymerization used to solvent at least 30, preferably 50 and in particular 70 wt .-% of ethyl acetate or n-butyl acetate or mixtures thereof.

When Initiators can all initiators are used, as used in Lösungspolymeriation become. Preferably, from 0.01 to 1.5% by weight of initiator is used used on the monomers used.

The precipitation becomes common at temperatures of 20 to 150 ° C, preferably 40 to 120 ° C, in particular 60 to 100 ° C carried out.

The precipitation becomes common when pressed from 1 to 15 bar, in particular 1 to 6 bar performed.

The solvent or solvent mixture determined by the corresponding boiling temperatures the maximum Reaction temperature if polymerized under atmospheric pressure. However, polymerization under pressure is also possible.

As a general rule can the precipitation polymerization be carried out at solids contents up to about 40 wt .-%. It is preferred a range between 25 and 40 wt .-%. Especially at high solids contents it is advisable to polymerize in the presence of a protective colloid polymer perform. Suitable protective colloid polymers are those which are good in the used solvents solve and do not react with the monomers. Suitable as protective colloids Polymers are z.b. Copolymers of maleic acid with vinyl alkyl ethers and / or Olefins having 8 to 20 carbon atoms or corresponding copolymers of maleic half with C10-C20 alcohols or mono- and diamides of maleic acid with C10-C20-alkylamines and polyvinyl alcohol ethers with alkyl groups, which carry 1 to 20 carbon atoms or else polyvinylmethyl, -ethyl, -isobutyl or octadecyl ether. The amount of protective colloid polymer used is usually in the range of 0.05 to 4 wt .-% (based on Monomers), preferably from 0.1 to 2% by weight. It is often beneficial Use mixtures of several protective colloid polymers.

The Polymerization is carried out in which you solvent, Component f), protective colloid polymer and possibly crosslinker c), heats up, and the polymerization by addition of initiator and Monomers a), b), d) and e) (possibly dissolved in the same solvent or solvent mixture) performs. you but can also submit subsets of the monomers and the initiator (e.g., 10%), heat this mixture to polymerization temperature and after the start of the reaction, the rest of the mixture to be polymerized after the progress of the Polymeristion present. It is also possible to use the used crosslinkers in subsets and the rest together Add with the remaining components. At lower solids contents It is also possible, all To submit feedstocks in a batch reaction.

In a preferred embodiment the polymerization is for the preparation of the inventive use suitable polymers are carried out in feed mode. there be individual or all reactants in whole or in part, batchwise or continuously, together or in separate feeds too a reaction mixture.

separate inlets are advantageous, for example, when the solubilities of components a) to e) in certain solvents differ significantly. For example, in the copolymerization vinylimidazole as a) and methacrylamide as b) and the further components c) to e) a process with separate feeds advantageous because vinylimidazole and methacrylamide in their solubilities clearly distinguish.

monomers and initiator generally in a time of 1 to 10 hours metered in, preferably from 2 to 5 hours.

In the polymerization for the preparation of the polymers suitable for the use according to the invention, other polymers, such as, for example, polyamides, polyurethanes, polyesters, homopolymers and copolymers of ethylenically unsaturated monomers, may optionally also be present. Examples of such partially used in cosmetics polymers are known under the trade names Amerhold ^™ , Ultrahold ^™ , Ultrahold Strong ^™ , Luviflex ^TM VBM, Luvimer ^™ , Acronal ^™ , Acudyne ^™ , Stepanhold ^™ , Lovocryl ^™ , Versatyl ^™ , Amphomer ^™ or Eastma AQ ^™ , Luviset ^™ brands, Sokalan ^™ brands, Luviquat ^™ brands

The precipitated polymer is subsequently removed from the reaction mixture isolated, for what any general method for isolating the polymers in the conventional precipitation can be used. Such methods are filtration, centrifugation, Evaporation of the solvent or combinations of these methods. For further purification of the polymer of unpolymerized components, the polymer is washed. For that can in principle, the same solvents use as for the polymerization is suitable. If the polymers after the polymerization It is advantageous for alkylation and polymerization to be alkylated the same solvent to use.

Should The polymer should be dried, so it is recommended after the polymerization or after alkylation to make a solvent exchange and for Drying low-boiling solvents such as. To use acetone.

Neutralization

In front the use according to the invention in aqueous Compositions will be the polymer in a preferred embodiment the invention after the polymerization and before or after the filtration neutralized.

ever after the choice of the monomers a) to e) can for neutralization acids or Bases will be necessary.

When Neutralizing agent for basic group-carrying monomers become organic or inorganic acids used.

When possible organic acids be mono- and polyhydric, optionally substituted aliphatic and aromatic carboxylic acids, mono- and polyvalent, optionally substituted aliphatic and aromatic sulfonic acids or mono- and polyhydric, optionally substituted aliphatic and aromatic phosphonic acids, acid groups carrying polymers or ascorbic acid called.

preferred organic acids are hydroxycarboxylic acids, i.e. Derivatives of carboxylic acids, in which one or more H atoms replaced by Hyroxylgruppen are.

When examples for hydroxy be glycolic acid, Lactic acid, tartaric acid and citric acid.

When preferred inorganic acids be phosphoric acid, phosphorous acid, Sulfuric acid, sulphurous Acid and hydrochloric acid called.

When Neutralizing agent for acid groups carrying monomers can For example, mineral bases such as sodium carbonate, alkali metal hydroxides and Ammonia, organic bases such as amino alcohols especially 2-amino-2-methyl-1-propanol, Monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, Tri [(2-hydroxy) 1-propyl] amine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol and Diamines, such as lysine, are used.

modification the rheological properties

Under Modification of rheological properties becomes quite general the change the deformation and flow behavior understood by matter. The most important rheological properties are viscosity, Thixotropy, intrinsic viscosity, Rheopexy and dilatancy. These terms are known to the person skilled in the art.

Under viscosity usually understood the "tenacity" of a liquid. It results from the intermolecular forces in a liquid, is therefore dependent of cohesion (intramolecular) and adhesion (Intermolecular). The viscosity characterizes the flow behavior a liquid. High viscosity means thick liquid, a low, on the other hand, thin liquid.

Under Thixotropy is usually understood the property of a fluid, a lower one after shearing viscosity to show and the original viscosity to rebuild at standstill.

Rheopexy is usually understood as the property of a fluid, after shear show higher viscosity. This behavior is closely related to the dilatancy, where the viscosity is higher only during shear.

Under Modification of the rheology is in the context of this invention in particular the increase the viscosity of liquids understood, usually also called "thickening" Viscosity increase can extend to the formation of gels or solids.

Aqueous compositions

One Another object of the invention are cosmetic or pharmaceutical Composition containing at least one as previously defined for the use according to the invention suitable polymer.

Prefers are watery as an agent Compositions containing the at least one polymer in an amount in the range of 0.01 to 5 wt .-%.

Especially preferred agents are (hair) cosmetic aqueous compositions.

The The polymers described above are outstandingly suitable for the preparation cosmetic and pharmaceutical agents. They serve, for example, as polymeric film formers in personal care preparations, what the application cosmetic preparations on keratinous surfaces such as skin, hair, nails as well also oral care preparations includes. They are universal in a wide variety of cosmetic Preparations can be used and formulated and with the usual Components compatible. In the cosmetic preparations, those for the use according to the invention unfold special effects of suitable polymers. The polymers can Among other things, the moisturization and conditioning of the skin and to improve the skin feel contribute.

The Polymers act in the formulations in particular as thickeners and conditioner.

By Addition of for the use according to the invention suitable polymers may be significant in certain formulations Improvement of skin compatibility be achieved.

• 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
• viii) Mischungen davon.

In addition to the polymers suitable for use according to the invention, the agents according to the invention have at least one cosmetically or pharmaceutically acceptable carrier B) which 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
• viii) mixtures thereof.

The funds 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 cyclic 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 described, which is hereby incorporated by reference.

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 products may be skin-cosmetic or hair-cosmetic Act means.

Preferably the means are in the form of a spray, gel, foam, an ointment, Cream, emulsion, suspension, lotion, milk or paste. If desired, can also liposomes or microspheres be used.

The Cosmetic, dermatological or pharmaceutical agents may additionally be cosmetic, dermatological or pharmaceutically active agents and adjuvants.

Preferably the means comprise at least one as defined above, for the use according to the invention suitable polymer, at least one as defined above carrier B) and at least one different component selected therefrom among cosmetically active substances, emulsifiers, surfactants, preservatives, Perfume oils, others Thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, Bleaching agents, gelling agents, care products, colorants, tinting agents, Tanning agents, Dyes, pigments, bodying agents, moisturizers, restockers, Collagen, protein hydrolysates, lipids, antioxidants, defoamers, antistatic agents, Emollients and plasticizers.

thickener

The cosmetic, dermatological or pharmaceutical agents may be used in addition to for the use according to the invention suitable polymer still contain other thickeners. Prefers It is, however, to use no further thickening agents.

Common thickener in such formulations are crosslinked polyacrylic acids and their derivatives, polysaccharides and their derivatives, such as xanthan gum, Agar-agar, alginates or tyloses, cellulose derivatives, e.g. B. carboxymethylcellulose or hydroxycarboxymethylcellulose, fatty alcohols, monoglycerides and fatty acids, Polyvinyl alcohol and polyvinylpyrrolidone. Preference is given to nonionic Thickener used.

Cosmetic and / or dermatological active ingredients

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.

Artificial skin tanning agents that are suitable for tanning the skin without natural or artificial irradiation with UV rays, z. B. dihydroxyacetone, alloxan and walnut shell extract. Suitable keratin-hardening substances are generally active ingredients, as used in antiperspirants, such as. As potassium aluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc. Antimicrobial agents are used to destroy microorganisms or to inhibit their growth and thus serve so probably as a preservative or as a deodorizing substance, which reduces the formation or intensity of body odor. These include z. As usual preservatives known in the art, such as p-hydroxybenzoic acid, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are, for. As zinc ricinoleate, triclosan, Undecylensäurealkylolamide, citric acid triethyl, chlorhexidine etc.

suitable Light filter active substances are substances that UV rays in UV-B and / or Absorb UV-A region. Suitable UV filters are z. B. 2,4,6-triaryl-1,3,5-triazines, at where the aryl groups each carry at least one substituent can, preferably selected before is hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially Methoxycarbonyl and ethoxycarbonyl and mixtures thereof. Suitable are furthermore p-aminobenzoic acid esters, cinnamic, Benzophenones, camphor derivatives and UV-blocking pigments, such as titanium dioxide, talc and zinc oxide.

to Use in compositions containing water Light stabilizers are all those described in EP-A 1 084 696 in paragraphs [0036] to [0053] mentioned compounds, to which reference is made in full is taken.

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

antimicrobial medium

Furthermore, antimicrobial agents can also be used in the compositions containing water. These generally include all suitable preservatives with specific activity against gram-positive bacteria, eg triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether), chlorhexidine (1,1'-hexamethylenebis [5- (4-chlorophenyl) -biguanide) and TTC (3,4,4'-trichlorocarbanilide). Commercially available products are Phenonip ^®, Euxyl® ^® 400, Euxyl® ^® 100 or Euxyl® ^® 500th

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

Also numerous fragrances have antimicrobial properties. Specific Combinations with particular activity against Gram-positive bacteria be for used the composition of so-called Deopfarums.

Also a big Number of essential oils or their characteristic ingredients such as e.g. Clove oil (eugenol), mint oil (Menthol) or thyme oil (Thymol), show a pronounced antimicrobial effectiveness.

The Antibacterial substances are usually in concentrations from about 0.1 to 0.3 wt .-% used.

suitable Repellent agents are compounds that are capable of certain To keep animals, especially insects, from human beings or to expel them. This includes z. B. 2-ethyl-1,3-hexanediol, N, N-diethyl-m-toluamide, etc.

suitable hyperemic substances that increase the blood flow to the skin stimulate, z. As 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 and their salts, sulfur, etc.

suitable Antidandruff agents are for. 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, dermatological or pharmaceutical agents may be considered as cosmetic and / or pharmaceutical active substance (as well as optionally as adjuvant) at least one cosmetically or pharmaceutically acceptable Polymer included.

Prefers are funds in addition at least one nonionic, one anionic, one cationic or contain an ampholytic polymer.

Anionic polymers preferred as additional polymers are, for example, homopolymers 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 ^® (Noveon). Also hydrophobically modified crosslinked polyacrylate polymers, such as Carbopol ^® Ultrez 21 (Noveon) are preferred.

Further examples for suitable additional anionic polymers are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes and polyureas.

Prefers are still funds, in addition contain a polyurethane as anionic polymer.

Particularly suitable as additional polymers are those in the DE 4225045 A1 described water-soluble or water-dispersible polyurethanes, which is incorporated herein by reference in its entirety. Particularly suitable is Luviset PUR ^® (BASF).

Also particularly preferred are silicone-containing polyurethanes, as described in the DE 19807908 A1 are fully incorporated herein by reference. Particularly suitable is Luviset ^® Si-PUR (BASF).

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 polymers are also copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (z. B. Luvimer 100P ^®), copolymers of ethyl acrylate and methacrylic acid (eg. B. Luviumer MAE ^®), copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold ^® 8, strong), copolymers of vinyl acetate, crotonic acid and optionally further Vinylester (z. B. Luviset ^® brands), maleic anhydride copolymers, 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, such as (National Starch) and Gafset ^® (GAF) are commercially available and, for example, under the names Resyn ^® vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ^® (BASF) , Other suitable polymers are the VBM-35 under the name Luviflex ^® (BASF) available vinylpyrrolidone / acrylate terpolymer and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyester.

Furthermore, for example, the group of suitable anionic polymers comprises Balance ^® CR (National Starch; Acrylate Copolymer), Balance ^® 0/55 (National Starch; Acrylate Copolymer), Balance ^® 47 (National Starch; octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer), Aquaflex ^® FX 64 (ISP; isobutylene / ethylmaleimide / hydroxyethylmaleimide copolymer) Aquaflex ^® SF-40 (ISP / National Starch; VP / vinyl caprolactam / DMAPA acrylates copolymer), Alliance ^® LT-120 (ISP, Rohm &Haas; acrylate / C1-2 succinate / hydroxyacrylate copolymer), Aquarez ^® HS (Eastman, polyester-1), and ^® Diaformer Z-400 (Clariant; methacryloylethylbetaine / methacrylate copolymer), ^® Diaformer Z-711 (Clariant; methacryloylethyl N-oxide / methacrylate copolymer), Diaformer ^® Z-712 (Clariant; methacryloylethyl N-oxide / methacrylate copolymer), Omnirez ^® 2000 (ISP; monoethyl ester of poly (methyl vinyl ether / maleic acid in ethanol), Amphomer ^® HC (National Starch; acrylate / octylacrylamide copolymer ), Amphomer ^® 28-4910 (Nationa l Starch; octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer), Advantage ^® HC 37 (ISP; Terpolymer of vinylcaprolactam / vinylpyrrolidone / dimethylaminoethyl methacrylate), Advantage ^® LC55 and LC80 or LC A and LC E, Advantage ^® Plus (ISP; VA / Butyl Maleate / Isobornyl Acrylate Copolymer), Aculyne ^TM 258 (Rohm &Haas; acrylate / Hydroxyesteracrylat copolymer (), Luviset ^® PUR (BASF, polyurethane-1), Luviflex ^® Silk BASF), Eastman ^® AQ 48 (Eastman), Styleze ^® CC-10 (ISP, VP / DMAPA Acrylates copolymer), Styleze ^® 2000 (ISP; VP / Acrylates / lauryl Methacrylate copolymer), DynamX ^® (National Starch; poly urethane-14 AMP-Acrylates copolymer), Resyn ^® XP (National Starch; Acrylates / octylacrylamide copolymer), Fixomer ^® A-30 (Ondeo Nalco, polymethacrylic acid (and) acrylamidomethylpropane sulfonic acid), Fixate G-100 ^® (Noveon; AMP-Acrylates / allyl Methacrylate copolymer).

Suitable additional polymers are also those in the US 3,405,084 described terpolymers of vinyl pyrrolidone, C ₁ -C ₁₀ alkyl, cycloalkyl and aryl (meth) acrylates and acrylic acid. Suitable additional poly mers are furthermore the terpolymers of vinylpyrrolidone, tert.-butyl (meth) acrylate and (meth) acrylic acid described in EP-A-0 257 444 and EP-A-0 480 280. Suitable additional polymers are furthermore the copolymers described in DE-A-42 23 066, which contain at least one (meth) acrylic acid ester, (meth) acrylic acid and also N-vinylpyrrolidone and / or N-vinylcaprolactam in copolymerized form. The disclosure of these documents is hereby incorporated by reference.

suitable Carboxylic acid group-containing Polymers are also polyurethanes containing carboxylic acid groups.

The EP-A-636361 discloses suitable block copolymers with polysiloxane blocks and Polyurethane / polyurea, the carboxylic acid and / or sulfonic acid groups exhibit. Suitable silicone-containing polyurethanes are also in the WO 97/25021 and EP-A-751 162. Suitable polyurethanes are also described in DE-A-42 25 045, which is here in full Scope is referred to.

• i) mindestens einer Verbindung, die zwei oder mehrere aktive Wasserstoffatome pro Molekül enthält,
• ii) mindestens einem Carbonsäuregruppen enthaltenden Diol oder einem Salz davon und
• iii) mindestens einem Polyisocyanat.

These polyurethanes are constructed in principle

• i) at least one compound containing two or more active hydrogen atoms per molecule,
• ii) at least one carboxylic acid group-containing diol or a salt thereof and
• iii) at least one polyisocyanate.

at Component i) is z. To diols, diamines, amino alcohols, and mixtures thereof. The molecular weight of these compounds is preferably in a range of about 56 to 280. If desired can up to 3 mol% of said compounds by triols or triamines be replaced.

useful Diols i) are z. As ethylene glycol, propylene glycol, butylene glycol, Neopentyl glycol, cyclohexanedimethylol, di-, tri-, tetra-, penta- or hexaethylene glycol and mixtures thereof. Preference is given to neopentyl glycol and / or cyclohexanedimethylol used. Suitable amino alcohols i) are z. B. 2-aminoethanol, 2- (N-methylamino) ethanol, 3-aminopropanol, 4-aminobutanol, 1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol, 4-methyl-4-aminopentan-2-ol, etc. Suitable diamines i) are, for. B. Ethylenediamine, propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane and α, β-diaminopolyether, which can be prepared by amination of polyalkylene oxides with ammonia are.

at Component i) may also be a polymer having a number average Molecular weight in the range of about 300 to 5000, preferably about 400 to 4000, especially 500 to 3000. Useful polymers i) are z. As polyester diols, polyetherols and mixtures thereof. polyetherols are preferably polyalkylene glycols, for. For example, polyethylene glycols, Polypropylene glycols, polytetrahydrofurans, etc., block copolymers from ethylene oxide and propylene oxide or block copolymers from ethylene oxide, Propylene oxide and butylene oxide, the alkylene oxide random distributed or in the form of blocks incorporated in copolymerized form. Suitable polytetrahydrofurans i) can by cationic polymerization of tetrahydrofuran in the presence of acidic catalysts, such as. For example, sulfuric acid or fluorosulfuric acid produced become. Such production processes are known to the person skilled in the art. Useful polyester diols i) preferably have a number average Molecular weight in the range of about 400 to 5000, preferably 500 to 3000, especially 600 to 2000, on. As polyester diols i) All those who are commonly used for the manufacture of Polyurethanes are used, in particular those based on aromatic dicarboxylic acids, like terephthalic acid, isophthalic acid, phthalic acid, Na or K sulfoisophthalic acid etc., aliphatic dicarboxylic acids, like adipic acid or succinic acid etc., and cycloaliphatic dicarboxylic acids such as 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid. When Diols are especially aliphatic diols into consideration, such as ethylene glycol, Propylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, Polyethylene glycols, polypropylene glycols, 1,4-dimethylolcyclohexane, Etc.

suitable Compounds ii), the two active hydrogen atoms and at least a carboxylic acid group per molecule have z. For example, dimethylolpropanoic acid and mixtures containing dimethylolpropanoic acid.

at Component iii) is conventional aliphatic, cycloaliphatic and / or aromatic polyisocyanates, such as tetramethylene diisocyanate, Hexamethylene diisocyanate, methylene diphenyl diisocyanate, 2,4- and 2,6-toluene diisocyanate and their isomer mixtures, o- and m-xylylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-cyclohexylene diisocyanate, dicyclohexylmethane diisocyanate and mixtures thereof, in particular isophorone diisocyanate and / or dicyclohexylmethane diisocyanate. If desired, can up to 3 mol% of said compounds replaced by triisocyanates be.

Suitable additional polymers are furthermore cationic polymers. These include z. As polymers called Polyquaternium INCI, z. B. Copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^™ FC, Luviquat ^™ HM, Luviquat ^™ MS, Luviquat ^™ Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat ^™ PQ 11), copolymers of N-vinylcaprolactam / 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 ^™ (dimethyldiallylammonium chloride-based polymer), Gafquat ^™ (quaternary polymers formed by reaction of polyvinylpyrrolidone with quaternary ammonium compounds), Polymer ^™ JR (hydroxyethylcellulose with cationic groups), and plant-based cationic polymers , z. As guar polymers, such as the Jaguar ^TM brands of Fa. Rhodia.

Suitable additional polymers are also amphoteric or zwitterionic polymers, such as the octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer ^™ (National Starch) and zwitterionic polymers, as described, for example, in German patent applications DE 39 29 973 . DE 21 50 557 . DE 28 17 369 and DE 37 08 451 are disclosed. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, commercially available under the name Amersette ^™ (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon ^™ ).

As additional polymers suitable neutral polymers are, for. As polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinyl and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose derivatives, polyaspartic acid salts and derivatives. These include, for example, Luviflex ^™ swing (partially saponified copolymer of polyvinyl acetate and polyethylene glycol, BASF).

Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinyl caprolactam, z. B. Luviskol ^TM Plus (BASF), or polyvinylpyrrolidone and their copolymers, especially 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 nonionic, siloxane-containing, water-soluble or -dispersible polymers, for. As polyether siloxanes, such as Tegopren ^™ (Goldschmidt) or Belsil ^™ (Wacker).

The for the use according to the invention suitable polymers can also used for rheology modification of skin cleansers become.

Skin cleanser are soaps of liquid to gel Consistency, such as transparent soaps, luxury soaps, de-icing soaps, cream soaps, Baby soaps, skin soaps, abrasive soaps and syndets, paste-like soaps, Greases and washing pastes, liquid washing, shower and bath preparations, like washing lotions, shower baths and gels, bubble baths, oil baths and Scrub preparations, shaving foams, lotions and creams.

The for the use according to the invention suitable polymers can also for rheology modification of cosmetic care products and for the protection of the skin, nail care products or preparations for decorative Cosmetics are used.

such Skin cosmetics are z. For example, facewash, face masks, deodorants and other cosmetic lotions. Means for use in the decorative Cosmetics include, for example, concealers, theatrical paints, mascara and eyeshadows, lipsticks, kohl pencils, eyeliners, rouges, powders and eyebrow pencils.

In addition, the for the use according to the invention suitable polymers in nose strips for pore cleaning, in anti-acne agents, Repellents, shaving products, depilatories, personal hygiene products, foot care products and used in baby care.

at The skin care products are in particular W / O or O / W skin creams, Day and night creams, eye creams, face creams, anti-wrinkle creams, Moisturizing creams, bleaching creams, vitamin creams, skin lotions, skin lotions and moisturizing lotions.

skin cosmetic and dermatological agents preferably contain from 0.05 to 20% by weight, preferably 0.1 to 15 wt .-%, most preferably 0.1 to 10 wt .-% of for the use according to the invention suitable polymers, based on the total weight of the composition.

Especially Light stabilizers, for their rheology modification for the inventive use suitable polymers are used have the property of the residence time of the UV-absorbing ingredients in comparison to common To increase aids such as polyvinylpyrrolidone.

ever according to application the agents in a form suitable for skin care, such. As a cream, Foam, gel, pen, mousse, milk, spray (pump spray or propellant Spray) or lotion.

The skin cosmetic preparations in addition to the rheology modifying polymer and suitable excipients more usual in skin cosmetics Active ingredients and adjuvants as described above. To counting preferably emulsifiers, preservatives, perfume oils, cosmetic Active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, Panthenol, sunscreen, bleach, dye, tinting agent, Tanning agents, Collagen, protein hydrolysates, Stabilizers, pH regulators, Dyes, salts, other thickeners, gelling agents, bodying agents, 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.

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 especially 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.

The Emulsions are prepared by known methods. The Emulsions contain, in addition to at least one for the use according to the invention suitable polymer usually usual Ingredients, such as fatty alcohols, fatty acid esters and in particular fatty acid triglycerides, fatty acids, Lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water. The selection the emulsion type-specific additives and the preparation of suitable Emulsions are described, for example, in Schrader, Grundlagen and recipes of cosmetics, Hüthig Buch Verlag, Heidelberg, 2nd edition, 1989, third part, what hereby expressly Reference is made.

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.

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 cetylricinoleate.

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.

Farther can also waxes are used, such as. Carnauba wax, candililla wax, Beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al-Oleate, myristates, Linoleates and stearates.

Farther For example, an emulsion may be present as an O / W emulsion. Such an emulsion usually contains an oil phase, Emulsifiers containing the oil phase stabilize in the water phase, and an aqueous phase, usually thickened present. As emulsifiers are preferably O / W emulsifiers, such as polyglycerol esters, sorbitan esters or partially esterified glycerides, into consideration.

To a further preferred embodiment The rheology-modifying polymers are particularly advantageous in shower gels, shampoo formulations or bath preparations used.

Such In addition, formulations usually contain 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, acyltaurates, acylisothionates, alkylphosphates, Alkyl ether phosphates, alkyl ether carboxylates, alpha olefin sulfonates, in particular the alkali and alkaline earth metal salts, e.g. Sodium, Potassium, magnesium, calcium, as well as ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can between 1 to 10 ethylene oxide or propylene oxide units, preferred 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.

Farther can the shower gel / shampoo formulations further thickeners, such as. B. 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.

A particularly preferred embodiment the invention are hair treatment agents.

Hair treatment compositions preferably contain a suitable for the use according to the invention tes polymer in an amount in the range of about 0.1 to 20 wt .-%, preferably 0.3 to 15 wt .-%, based on the total weight of the composition.

Preferably are the hair treatment compositions according to the invention in the form of a mousse, hair mousse, hair gel, shampoo, Hair sprays, hair mousse, top fluids, perms, hair coloring and bleach or "hot oil treatments". Depending on the application can the hair cosmetic preparations as (aerosol) spray, (aerosol) foam, Gel, gel spray, cream, lotion or wax can be applied. hairsprays include both aerosol sprays and pump sprays without propellant gas. hair foams include both aerosol foams as well as pump foams without propellant. Hair sprays and hair foams 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.

In a preferred embodiment of the invention, the agents according to the invention contain a proportion volatile Organic components (VOC) of at most 80 wt .-%, especially preferably at most 55% by weight.

• a) 0,05 bis 20 Gew.-% wenigstens eines für die erfindungsgemäße Verwendung geeigneten Polymers,
• b) 20 bis 99,95 Gew.-% Wasser und/oder Alkohol,
• c) 0 bis 50 Gew.-% wenigstens eines Treibgases,
• d) 0 bis 5 Gew.-% wenigstens eines Emulgators,
• e) bis zu 25 Gew.-% weitere Bestandteile

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

• a) 0.05 to 20% by weight of at least one polymer suitable for the use according to the invention,
• b) from 20 to 99.95% by weight of water and / or alcohol,
• c) 0 to 50% by weight of at least one propellant gas,
• d) 0 to 5% by weight of at least one emulsifier,
• e) up to 25% by weight of further constituents

Under Alcohol are all alcohols commonly used in cosmetics, z. For example, ethanol, isopropanol, n-propanol.

Under other constituents are the additives customary in cosmetics, for example propellants, defoamers, surfactants Compounds, d. H. Surfactants, emulsifiers, foaming agents and solubilizers. The used surface-active Connections can anionic, cationic, amphoteric or neutral. Other common ingredients can also be z. Preservatives, perfume oils, opacifiers, active ingredients, UV filters, Nursing substances such as panthenol, collagen, vitamins, protein hydrolysates, Alpha and beta hydroxycarboxylic acids, protein hydrolysates, Stabilizers, pH regulators, dyes, viscosity regulators, Gelling agents, dyes, salts, humectants, moisturizers, Complexing agents and other common additives.

All for cosmetic Appropriate ingredients may also be suitable for the hair cosmetic Means are used. Furthermore, this includes all in cosmetics known styling, setting and conditioner polymers.

to Setting certain properties, the preparations may also be Contain conditioning substances based on silicone compounds. Suitable silicone compounds are, for example, polyalkylsiloxanes, Polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes, silicone resins or dimethicone copolyols (CTFA) and amino functional silicone compounds like amodimethicones (CTFA).

When Emulsifiers can all in hair foams usually used emulsifiers are used. Suitable emulsifiers can nonionic, cationic or anionic or amphoteric.

Especially for aerosol foams suitable blowing agents are mixtures of dimethyl ether and, optionally halogenated, hydrocarbons such as propane, butane, pentane or HFC-152 a. Here are depending on other solvents and desired Application of the proportions to vary the propellant.

Examples for nonionic Emulsifiers (INCI nomenclature) are Laurethe, z. Laureth-4; Cetethe, z. Cetheth-1, polyethylene glycol cetyl ether; Cetearethe, z. Cetheareth-25, Polyglycol fatty acid glycerides, hydroxylated Lecithin, lactyl ester of fatty acids, Alkylpolyglycosides.

Examples for cationic Emulsifiers are cetyldimethyl-2-hydroxyethylammonium dihydrogen phosphate, Cetyltrimonium chloride, cetyltrimmonium bromide, cocotrimonium methylsulfate, Quaternium-1 to x (INCI).

anionic Emulsifiers can for example, selected are selected from the group of alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, Alkylarylsulfonates, alkylsuccinates, alkylsulfosuccinates, N-alkoylsarcosinates, acyltaurates, Acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, Alpha olefin sulfonates, in particular the alkali and alkaline earth metal salts, z. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can be used between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule exhibit.

• a) 0,1 bis 10 Gew.-% wenigstens eines für die erfindungsgemäße Verwendung geeigneten Polymers,
• b) 80 bis 99,85 Gew.-% Wasser und/oder Alkohol,
• c) 0 bis 20 Gew.-% weitere Bestandteile.

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

• a) 0.1 to 10% by weight of at least one polymer suitable for the use according to the invention,
• b) 80 to 99.85% by weight of water and / or alcohol,
• c) 0 to 20 wt .-% further ingredients.

Of the Use of for the use according to the invention suitable polymers as gelling agent is advantageous if special rheological or other performance properties of Gels are to be adjusted. Due to the excellent compatibility with the for the use according to the invention suitable polymers can also other, usual in cosmetics Gel former can be used. These include slightly crosslinked polyacrylic acid, for example Carbomer (INCI), cellulose derivatives, e.g. Hydroxypropyl cellulose, hydroxyethyl cellulose, cationically modified celluloses, polysaccharides, e.g. Xanthan gum, Caprylic / capric triglyceride, sodium acrylate copolymers, polyquaternium-32 (and) Paraffinum Liquidum (INCI), Sodium Acrylate Copolymers (and) Paraffinum Liquidum (and) PPG-1 trideceth-6, acrylamidopropyltrimonium chloride / acrylamide copolymers, Steareth-10 Allyl Ether Acrylate Copolymers, Polyquaternium-37 (and) Paraffinum Liquidum (and) PPG-1 Trideceth-8, Polyquaternium 37 (and) Propylene glycol dicaprate dicaprylate (and) PPG-1 trideceth-6, polyquaternium-7, Polyquaternium-44th

• a) 0,05 bis 10 Gew.-% wenigstens eines für die erfindungsgemäße Verwendung geeigneten Polymers,
• b) 25 bis 94,95 Gew.-% Wasser,
• c) 5 bis 50 Gew.-% Tenside,
• d) 0 bis 5 Gew.-% eines weiteren Konditioniermittels,
• e) 0 bis 10 Gew.-% weitere kosmetische Bestandteile.

The polymers can be used according to the invention as thickeners in shampoos. Contain preferred shampoo formulations

• a) from 0.05 to 10% by weight of at least one polymer suitable for the use according to the invention,
• b) from 25 to 94.95% by weight of water,
• c) 5 to 50% by weight of surfactants,
• d) 0 to 5% by weight of a further conditioning agent,
• e) 0 to 10 wt .-% of other cosmetic ingredients.

Especially Polymers containing copolymerized methacrylamide as component b), are for the use as a thickener for Shampoos and other surfactant-containing compositions suitable.

In the shampoo formulations all in shampoos usually used anionic, neutral, amphoteric or cationic Surfactants are used.

suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, Alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoylsarcosinates, acyltaurates, acylisothionates, alkylphosphates, Alkyl ether phosphates, alkyl ether carboxylates, alpha olefin sulfonates, in particular the alkali and alkaline earth metal salts, e.g. Sodium, Potassium, magnesium, calcium, as well as ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can between 1 to 10 ethylene oxide or propylene oxide units, preferred 1 to 3 ethylene oxide units in the molecule.

Suitable For example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, Ammonium lauryl ether sulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, Ammonium laurylsulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.

suitable amphoteric surfactants are, for example, 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, alkyl polyglycosides or sorbitan ether esters suitable.

In addition, the Shampoo formulations usual contain cationic surfactants, such as. B. quaternary ammonium compounds, for example Cetyltrimethylammonium chloride.

In the shampoo formulations customary conditioners can be used to achieve certain effects. These include, for example, the aforementioned cationic polymers having the INCI name Polyquaternium, in particular copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^® FC, Luviquat ^® HM, Luviquat ^® MS, Luviquat ^® Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat ^® PQ 11), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat Hold ^®); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7). Furthermore, protein hydrolysates can be used, as well as conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins. Other suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA). Furthermore, cationic guar derivatives such as guar hydroxypropyltrimonium chloride (INCI) can be used.

Another object of the invention are aqueous compositions containing at least one suitable for use in the invention polymer and polyvinylpyrrolidone. Polyvinylpyrrolidones having a K value of at least 30, preferably at least 60, particularly preferably at least 90, are suitable for this purpose. Such polyvinylpyrrolidones are commercially available, for example, under the trade name Luviskol ^™ (BASF). Even at low concentrations of polymer and polyvinylpyrrolidone [0.5% by weight] suitable for use according to the invention, such compositions surprisingly show very good properties, especially as gels, such as high viscosity and clarity of the aqueous composition and very good firmness when applied to the hair.

By the following examples illustrate the invention in detail without restricting it to it.

manufacturing the for the use according to the invention suitable polymers

In a stirred Reactor with nitrogen supply, Reflux cooler and Metering device, the template was heated to 90 ° C under nitrogen. After that, feed 1 was during 4 hours and feed 2 during 5 hours (1/3 in 3 hours, 2/3 in 2 hours). After completion from feed 2 was at 100 ° C heated and postpolymerized for a further 2 hours at this temperature. It was then cooled to room temperature (about 23 ° C), diluted with feed 3 and the precipitated polymer is filtered off, washed with acetone, sucked dry and dried in a vacuum drying oven (water pump vacuum) at 75 ° C.

Used abbreviations:

• n-BuAc:

  n-butyl acetate

  PEG:

  polyethylene glycol

  VI:

  N-vinylimidazole

  QVI:

  N-Vinylimidazoliummethyl chloride (Methyl chloride quaternized VI)

  VP:

  N-vinylpyrrolidone

  VFA:

  Nvinylformamide

  V-Cap:

  N-vinyl caprolactam

  AS:

  acrylic acid

  MAM:

  methacrylamide

  PIB:

  polyisobutene

  PETAE:

  pentaerythritol

  C18VE:

  octadecyl

  C18AC:

  stearyl

  C22AC:

  behenyl

So far Unless otherwise stated, the amounts given in the following table in grams [g], the proportions are weight ratios (W / w).

Determination of curl retention Basic formula: (aerosol hairspray) 5% by weight Active substance to be tested polymer (100% neutral with AMP) 15% by weight ethanol 40% by weight water 40% by weight Dimethyl ether.

For the determination The Curl Retention were hair strands of about 2 g in weight and 15.5 cm in length and used from middle brown, Caucasian human hair.

Treatment of the hair strands:

The hair tresses were washed twice with an aqueous Texapon ^® NSO solution. Subsequently, the hair strands were rinsed with warm water until no more foam was visible and rinsed with deionized water, combed and placed on filter paper to dry.

to Making a water wave, the hair strands were 15 minutes to swell in a solution Ethanol and water (1: 1) inserted.

• L = Länge der Haare (15,5 cm)
• L₀ = Länge der Haarlocke nach dem Trocknen
• L_t = Länge der Haarlocke nach Klimabehandlung

The lock of hair was carefully combed before curling preparation. With a rubber band, the strand of hair was attached to a plexiglass rod. It was then combed and wound spirally. With a cotton cloth and rubber band, the lock was firmly fixed and dried overnight at 70 ° C. The cooled strands were carefully opened and stripped off the Plexiglas rod without deforming the water wave. From a distance of 15 cm from the aerosol hair spray solution prepared as above about 1.8 g were sprayed evenly on the curl. The curl was turned evenly. In a horizontal position, the curls were dried for 1 hour at room temperature. After drying, the curls were fixed in a holder. Using a scale, the length L _{0 of} the curls was read and tracked the length expansion during the wet climate storage. After 5 h of storage at 25 ° C. and 90% RH in the climatic chamber, the length Lt of the lock obtained was read off and the Curl retention was calculated according to the following equation:

• L = length of the hair (15.5 cm)
• L ₀ = length of hair lock after drying
• L _t = length of hair lock after climate treatment

When Curl retention was the mean of the 5 individual measurements given.

Determination of consolidation (Flexural rigidity):

The setting effect of the polymers was measured by measuring the bending stiffness of thin strands of hair (in each case about 3 g and 24 cm in length). For this purpose, the weighed, dry strands of hair were immersed in the below-mentioned polymer solution (solvent: ethanol / water 55:45 w / w), whereby a uniform wetting of the hair strand and distribution of the polymer solution was ensured by three times immersing and removing and then expressing between filter paper. The excess film former solution was then stripped between the thumb and forefinger and the strands of hair were hand-formed into strands to give a round cross-section. At 20 ° C and 65% relative humidity was dried overnight in a climate room. The tests were carried out in a climatic chamber at 20 ° C and 65% relative humidity by means of a tensile / pressure tester. The lock of hair was placed symmetrically at the ends on two cylindrical rollers of the sample holder. Right in the middle of the strand was now bent from above with a rounded stamp about 40 mm (breaking the polymer film). The required force (Fmax) was determined with a load cell (50 N). Here, one measurement value represents the arithmetic mean of the individual measurements on 5 to 10 identically treated Haarstähnen. The values determined were added to those of a commercially available comparative polymer (Amphomer ^® LV-71) in Real and set in%.

determination the dynamic viscosity

The viscosities the solutions of the polymers 1 to 13 were measured using the viscometer Brookfield DV-II under usual Conditions with spindle 4 at 12 rpm in a standard 150ml beaker.

The viscosities the solutions the polymers 14 to 54 were with the viscometer Brookfield DV-II + Pro among usual Conditions with spindle 6 at 20 rpm in a standard 250 ml beaker.

Quaternization of the polymers

Methylation with methyl chloride:

The Methylation with methyl chloride was carried out on conventional, known in the art Way. For example, the polymer to be quaternized suspended in n-butyl acetate in a weight ratio of 1: 4 and in heated in an autoclave. gaseous Methyl chloride was added until the desired mass increase was achieved.

Alkylation with alkyl bromide

The Alkylation with alkyl bromide is carried out on conventional, known in the art Way. For example, those for the desired degree of quaternization calculated amount of alkyl bromide and the same amount of solvent to in the solvent suspended polymer added. Then it is heated to reflux and stirred under reflux for 4 hours. After that is cooled, optionally with solvent diluted sucked off, washed, sucked off again and then at 75 ° C in Dryed vacuum oven.

Comparative formulation

From 0.5% by weight of a commercial polyacrylic acid ^thickener (Carbopol® 940) neutralized with triethanolamine (TEA), a gel is formulated which, when applied to hair, exhibits substantially no conditioning effect. This standard formulation is added in each case 3% by weight of a commercially available hair polymer. The performance properties are given in the table below. With good thickening, the other hair cosmetic properties are in need of improvement.

Inventive formulation

• * ad 100 Gew.-% Wasser
• ** Bt = Biegefestigkeit
• *** C.R. = Curl Retention; wurde bei 25°C 90% relativer Feuchtigkeit bestimmt

From 0.5% by weight of a polymer suitable for use according to the invention, a gel is formulated. These are added 1 and 3 wt .-% of a commercial hair polymer. This results in clear gel formulations with even a very low amount of commercial hair polymer good conditioner or Festigerwirkung. The performance properties are given in the table below. With good thickening, the other hair cosmetic properties are clearly superior to the state of the art.

• * ad 100% by weight of water
• ** Bt = flexural strength
• *** CR = curl retention; was determined at 25 ° C 90% relative humidity

Thickening effect of suitable for use in the invention polymers in skin cosmetic preparations (emulsions) in comparison with Capigel ^® 98 or

Ultrez ^® 21

applications

I) Hair cosmetic preparations

The quantities given below are in% by weight, unless expressly stated otherwise. The amounts of the polymers used according to the invention are given in wt .-% polymer as a solid. When the polymer is used in the form of a solution or dispersion, it is necessary to use the appropriate amount of solution or dispersion of the amount of polymer (as indicated in the following examples). qs means "quantum satis" and is known to the person skilled in the art of cosmetic preparations 0.5% Polymer of Example 1 (Q) 3% Luviskol ^™ K90 0.50% panthenol qs perfume oil qs preservative ad 100% water A2) hair gel 0.5% Polymer of Example 1 (Q) 2.5% Luviskol ^™ K90 0.5% Luviquat ^TM Hold 0.50% panthenol qs perfume oil qs preservative ad 100% water A3) hair gel 0.5% Polymer of Example 1 (Q) 2.5% Luviskol ^™ K90 0.5% Luviquat ^TM Supreme 0.50% panthenol qs perfume oil qs preservative ad 100% water A4) hair gel 0.5% Polymer of Example 1 (Q) 2.0% Luviskol ^™ K90 1% Luviquat ^TM Hold 0.50% panthenol qs perfume oil qs preservative ad 100% water A5) hair gel 0.5% Polymer of Example 1 (Q) 2.0% Luviskol ^™ K90 1% Luviset ^TM Clear 0.50% panthenol qs perfume oil qs preservative ad 100% water A6) hair gel 0.5% Polymer of Example 1 (Q) 2.0% Luviskol ^™ K90 1% Polyquaternium 11 0.50% panthenol qs perfume oil qs preservative ad 100% water

These examples are repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). Hair gels with very good properties are obtained in each case. A7) hair fixer gel % 0.5 Polymer of Example 1 (Q) 3.0 Luviskol ^TM VA64W 0.20 panthenol qs perfume oil qs preservative ad 100 water A8) hair fixer gel % 0.5 Polymer of Example 1 (Q) 2.5 Luviskol ^TM VA 64W 1.0 Luviskol ^™ K90 0.20 panthenol qs perfume oil qs preservative ad 100 water A9) hair fixer gel % 0.5 Polymer of Example 1 (Q) 2.0 Luviskol ^TM VA64W 2.0 Luviskol ^TM K30 0.20 panthenol qs perfume oil qs preservative ad 100 water

These examples are repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). Hair fixative gels with very good properties are obtained in each case. A10) 2.00 Polymer 1 (Q) 6.00 Corn Starch Modified (Amaze, National Starch) 0.50 chitosan qs perfume oil qs PEG-40 Hydrogenated Castor Oil 0.10 PEG-14 Dimethicone 0.10 preservative 91.40 Aqua the.

production:

Mix all components until a homogeneous mixture is obtained. This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). A11) 2.00 Polymer 1 (Q) 5.00 VP / DMAPA acrylates copolymer (Styleze CC-10 ^®) 84.85 Aqua the. qs perfume oil qs PEG-40 Hydrogenated Castor Oil 0.10 Dimethicone Copolyol 0.10 preservative 2.00 hydroxypropyl

production:

Mix all components until a homogeneous mixture is obtained. This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). A12) 2.00 Polymer 1 (Q) 1.00 VP / Acrylates / Lauryl Methacrylate Copolymer (ISP: Styleze 2000) 0.26 Aminomethyl propanol 90.64 Aqua the qs perfume oil qs PEG-40 Hydrogenated Castor Oil 0.10 sorbitol 0.10 preservative 2.00 Hydroxypropyl Guar (Rhodia Inc., N-Hance Hydroxypropyl Guar)

production:

Mix all components until a homogeneous mixture is obtained. This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). A13) 6.00 Polymer 1 (Q) 2.00 Acrylates / C1-2 succinates / hydroxy acrylate copolymer (Rohm & Haas, Alli LT-120) 0.19 Aminomethyl propanol qs perfume oil qs PEG-40 Hydrogenated Castor Oil 0.10 PEG-8 0.10 preservative 0.50 hydroxyethyl

production:

Mix all components until a homogeneous mixture is obtained. This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). A14) 7.00 Polymer 1 (Q) 7.00 Methacrylic Acid / Sodium Acrylamidomethyl Propane Sulfonate Copolymer (Ondeo Nalco, Fixomer A30) 0.70 Triethanolamine qs, perfume oil qs PEG-40 Hydrogenated Castor 0.10 panthenol 0.10 preservative 84,90 Aqua the. 1.00 Polyacrylamide / C13-14 isoparaffin / laureth-7 (Seppic, Sepigel 305)

production:

Mix all components until homogeneous mixture is obtained. This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). A15) 2.00 Polymer 1 (Q) 1.00 polyvinylformamides qs perfume oil qs PEG-40 Hydrogenated Castor Oil 0.10 preservative 0.10 Ethylhexyl methoxycinnamate 0.10 PEG-14 Dimethicone

production:

Mix all components until homogeneous mixture is obtained. This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). A16) Conditioning Hairgel, superstrong 1.00 Polymer 1 (Q) 0.50 Luviquat Hold (Polymquaternium-46) 3.00 Luviskol VA 64 (VP / VA Copolymer) 0.50 panthenol 0.50 Dimethiconol (DC-193, Dow Corning) 0.10 EDTA qs preservative ad 100 water

production:

Mix everything until homogeneous mixture is obtained. Stir for 15 minutes. This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). In each case a conditioning hair gel with very good properties is obtained. A17) gel fluid 3.00 Kollicoat IR ^® (BASF) qs preservative 2.00 Polymer 1 (Q) 1.00 Hydroxypropyl guar 5.00 Alcohol 0.20 Niacinamide 0.50 panthenol 0.50 Dimethocone Copolyol 0.20 Amodimethocone

production:

Mix everything until homogeneous mixture is obtained. Stir for 15 minutes. This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). In each case, a gel fluid with very good properties is obtained. A18) Hair pudding 3.00 Kollicoat IR qs preservative 2.00 Luviset Clear 1.00 Polymer 1 (Q) 0.50 Dimethicone Copolyol 0.10 EDTA 0.20 Benzophenone-4 ad 100 water

production:

Everything mix until homogeneous mixture is obtained. Stir for 15 minutes. This Example becomes with the polymers of the examples 1 to 54 and 2 (Q) to 54 (Q) repeated. There will be a hair pudding with very good Get properties.

A19) "Wet Look" Styling Gel

This Example becomes with the polymers of the examples 1 to 54 and 2 (Q) to 54 (Q) repeated. It will each have a "wet look" styling gel with very good properties receive.

A20) Hair Gel, Superstyle, Ultra Strong

This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). There will be a Hair Gel, Superstyle, Ultra Strong with very good properties. A21) hair fixer gel % 0.5 Polymer 1 (Q) 1.0 Luviskol ^™ K90 0.20 panthenol qs perfume oil qs preservative ad 100 water A22) hair fixer gel % 0.3 Polymer 1 (Q) 1.0 Luviskol ^™ K90 0.20 panthenol qs perfume oil qs preservative ad 100 water A23) Hair fixative gel % 0.5 Polymer 1 (Q) 1.5 Luviskol ^™ K90 0.20 panthenol qs perfume oil qs preservative ad 100 water A24) hair fixer gel % 0.5 Polymer 1 (Q) 2 Luviskol ^™ K90 0.20 panthenol qs perfume oil qs preservative ad 100 water A25) hair fixer gel % 0.5 Polymer 1 (Q) 2.5 Luviskol ^™ K90 0.20 panthenol qs perfume oil qs preservative ad 100 water A26) hair fixer gel % 0.5 Polymer 1 (Q) 1 Luviskol ^™ K90 2 Luviskol ^TM K30 0.20 panthenol qs perfume oil qs preservative ad 100 water A27) Hair-setting gel % 0.5 Polymer 1 (Q) 2 Luviskol ^™ K90 1 Luviskol ^TM VA 64 0.20 panthenol qs perfume oil qs preservative ad 100 water A28) hair fixer gel % 2 Polymer 1 (Q) 0.20 panthenol qs perfume oil qs preservative ad 100 water

These examples are repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). In each case a hair fixative gel with very good properties is obtained. A29) Hair conditioner gel % 1 Polymer 1 (Q) 0.20 panthenol qs perfume oil qs preservative ad 100 water A30) Hair conditioner gel % 1.5 Polymer 1 (Q) 0.20 panthenol qs perfume oil qs preservative ad 100 water A31) Hair conditioner gel % 0.5 Polymer 1 (Q) 0.20 panthenol qs perfume oil qs preservative ad 100 water

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

Gelcreme

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

O/W-Sonnenschutzformulierung

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

Hydrodispersionen

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

W/O-Sonnenschutzformulierungen

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

Feststoffstabilisierte Emulsionen

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

Stifte

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

PIT-Emulsionen

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

Kosmetische after-sun Formulierungen:

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

Kosmetische Formulierungen für die dekorative Kosmetik:

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

Peeling-Creme, Typ O/W Phase A 3,00 Ceteareth-6 1,50 Ceteareth-25 3,00 Glycerylstearat 5,00 Cetearylalkohol, Sodium Cetearyl Sulfate 6,00 Cetearyloctanoat 6,00 Mineralöl 0,20 Bisabolol Phase B 2,00 Propylenglykol 0,10 Dinatrium-EDTA 1,50 Polymer 1(Q) q.s. Konservierungsmittel 59,70 dest. Wasser Phase C 0,50 Tocopherylacetat q.s. Parfümöl Phase D 10,00 Polyethylen These examples are repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q). In each case a hair conditioner gel with very good properties is obtained. II) skin cosmetic preparations

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

Gel Cream

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

O / W sun protection formulation

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

hydrodispersions

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

W / O sunscreen formulations

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

Solid-stabilized emulsions

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

pencils

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

PIT emulsions

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

Cosmetic after-sun formulations:

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

Cosmetic formulations for decorative cosmetics:

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

Exfoliating cream, type O / W Phase A 3.00 Ceteareth-6 1.50 Ceteareth-25 3.00 glyceryl stearate 5.00 Cetearyl Alcohol, Sodium Cetearyl Sulfate 6.00 cetearyl 6.00 mineral oil 0.20 bisabolol Phase B 2.00 propylene glycol 0.10 Disodium EDTA 1.50 Polymer 1 (Q) qs preservative 59.70 least. water Phase C 0.50 tocopheryl acetate qs perfume oil Phase D 10.00 polyethylene

production:

The Heat phases A and B separately to approx. 80 ° C. Stir phase B into phase A and homogenize. cooling down to about 40 ° C, Add phase C and homogenize briefly again. Then phase D mix in

analog Preparations are also with the polymers 1 to 54 or the quaternized Derivatives 2 (Q) to 54 (Q).

Lip Care Cream

phase A 10.00 cetearyl 5.00 polybutene 1.40 polymer 1 (Q) phase C 2.00 Ceteareth-6 2.00 Ceteareth-25 2.00 glyceryl stearate 2.00 cetyl alcohol 1.00 dimethicone 1.00 Benzophenone-3 0.20 bisabolol 6.00 mineral oil phase D 3.00 panthenol 3.00 propylene glycol q.s. preservative 54,00 least. water phase e 0.10 triethanolamine phase F 0.50 tocopheryl acetate 0.10 tocopherol q.s. perfume oil

production:

phase Solve A and homogenize. Add phase C and melt at 80 ° C. phase Heat D to 80 ° C. phase Add D to phase ABC and homogenize. Cool to about 40 ° C, phase Add E and phase F, homogenize again.

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

Kosmetische W/O-Formulierungen:

• Analoge Zubereitungen werden auch mit den Polymeren 1 bis 54 bzw. den quaternierten Derivaten 2(Q) bis 54(Q) hergestellt.

Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively. Cosmetic O / W Formulations:

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

Cosmetic W / O Formulations:

• Analogous formulations are also prepared with the polymers 1 to 54 and the quaternized derivatives 2 (Q) to 54 (Q), respectively.

Claims (16)

Use of a water-soluble or water-dispersible polymer obtainable by polymerization of a mixture comprising a) 99.99 to 10% by weight of at least one α, β-ethylenically unsaturated compound having at least one cationogenic and / or cationic group per molecule, b) 0 to 90% by weight % of at least one of a) different monoethylenically unsaturated amide group-containing compound, c) 0.01 to 5 wt .-% of a crosslinking agent, d) 0 to 15 wt .-% of at least one monoethylenically unsaturated compound d1) containing at least one group selected from the group consisting of optionally substituted, C5-C30-alkyl, C5-C30-alkenyl, C5-C8-cycloalkyl, aryl, arylalkyl and hetaryl and / or a reactive precursor d2), e) 0 to 30 wt .-% further , from a) to d) of various monoethylenically unsaturated compounds, in the presence of f) 0 to 70% by weight, based on the sum of the components a) to e) of a polyether-containing compound, with the proviso, that the amounts of components a) to e) add up to 100 wt .-%, wherein the polymerization in the presence of less than 69 wt .-% cyclohexane and less than 12 wt .-% water, based on the total amount of all during the Polymerization of current components, and in the absence of supercritical carbon dioxide is carried out to modify the rheology of aqueous Compositions. Use according to claim 1, wherein a) is selected out ai) esters α, β-ethylenic unsaturated Mono- and dicarboxylic acids with amino alcohols which mono- or dialkylates on the amine nitrogen could be, aii) Amides α, β-ethylenic unsaturated Mono- and dicarboxylic acids with diamines containing at least one primary or secondary amino group exhibit, aiii) N, N-diallylamines, aiv) vinyl and allyl substituted Nitrogen heterocycles, av) vinyl- and allyl-substituted heteroaromatic compounds and avi) mixtures thereof. Use according to claim 2, wherein a) is selected from 2.aiv), in particular vinylimidazoles of the general formula (I), wherein R ¹ to R ^{3 is} hydrogen, C ₁ -C ₄ -alkyl or phenyl.

Use according to claim 3, wherein R ¹ to R ^{3 are} hydrogen. Use according to one of claims 1 to 4, wherein at least one further component b) is selected from α, β-ethylenically unsaturated amide group-containing compounds of general formula IV

wherein R ^{1 is} a group of the formula CH ₂ = CR ⁴ - with R ⁴ = H or C ₁ -C ₄ alkyl and R ² and R ^{3 are} independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or R ² and R ³ together with the nitrogen atom to which they are attached represent a five- to eight-membered nitrogen heterocycle or R ^{2 represents} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ³ independently of one another H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or R ¹ and R ³ together with the amide group to which they are attached represent a lactam having 5 to 8 ring atoms. Use according to claim 5, wherein in formula IV R ^{2 represents} CH ₂ = CH- and R ¹ and R ³ together with the amide group to which they are attached represent a lactam having 5 ring atoms. Use according to one of claims 1 to 6, wherein as polyether-containing component f) compounds of the general formulas Va or Vb are used

wherein: R ^{7 is} hydroxy, amino, C ₁ -C ₂₄ alkoxy, R ^{13 is} -COO-, R ^{13 is} -NH-COO- or a polyalcohol radical, R ⁸ , R ⁹ and R ¹⁰ are each independently - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH ₂ -CH (CH ₃ ) -, -CH ₂ -CH (CH ₂ -CH ₃ ) - or -CH ₂ -CHOR ¹⁴ -CH ₂ - stand, R ^{11 is} hydrogen, amino-C ₁ -C ₆ -alkyl, C ₁ -C ₂₄ -alkyl, R ¹³ -C (= O) - or R ¹³ -NH-C (= O) -, R ^{12 is} a C ₁ -C ₂₀ -alkylene group whose carbon chain may be interrupted by 1 to 10 non-adjacent oxygen atoms; R ^{13 is} C ₁ -C ₂₄ -alkyl, R ^{14 is} hydrogen, C ₁ -C ₂₄ -alkyl or R ¹³ -CO-, A is -C (= O) -O-, -C (= O) -BC (= O) -O- or -C (= O) -NH-B-NH-C (= O) -O-, B is - (CH ₂ ) _t -, optionally substituted cycloalkylene, optionally substituted heterocycloalkylene or, if desired, substituted arylene, n is 1 or, when R ^{7 is} a polyalcohol radical, 1 to 8, s is 0 to 500, preferably 0 to 100, t is 1 to 12, preferably 2 to 6, u is independently each from 1 to 5000, preferably 1 to 1000, is, v is independently each 0 to 5000, preferably 1 to 1000, w independently of each other for 0 to 5000, preferably 1 to 1000, stands. Use according to claim 7, wherein as polyether-containing component f) homopolymers and copolymers of ethylene oxide and / or propylene oxide having a weight-average molecular weight M _w in the range of 1000 to 100,000, preferably from 5000 to 50,000 g / mol are used, which end-capped on one side or on both sides could be. Use according to any one of claims 1 to 8, wherein the polyether-containing Component f) in the polymerization in an amount in the range of 5 to 70, preferably from 10 to 50 wt .-%, based on the total amount of components a) to e) is present. Use according to any one of claims 1 to 9, wherein the crosslinker c) selected is selected from the group consisting of pentaerythritol triallyl ether, methylenebisacrylamide, N, N'-Divinylethylenharnstoff, Triallylamine and triallylmonoalkylammonium salts, acrylic esters of ethylene glycol, butanediol, trimethylolpropane or glycerol or acrylate of glycol reacted with ethylene oxide and / or epichlorohydrin, Butanediol, trimethylolpropane or glycerol. Use according to any one of claims 1 to 10, wherein the polymerizing mixture 0.05 to 2 wt .-% of Vrnetzers c). Use according to any one of claims 1 to 11 wherein compound d) is selected from the group consisting of C ₁₈ -C ₃₀ alkyl (meth) acrylates and C ₁₈ -C ₃₀ alkyl vinyl ethers. Use according to any one of claims 1 to 12, wherein the polymer after or during the polymerization partially or completely protonated or in the field from 20 to 99 mol% is quaternized, if as component a) an unprotected or partially protonated or quaternized monomer is used for polymerization. A polymer as defined in any one of claims 1 to 13. Contains cosmetic or pharmaceutical agent at least one polymer according to claim 14th Composition according to claim 15, containing at least one Polymer according to claim 14 in an amount in the range of 0.01 to 5 wt .-%.