DE10219889A1 - Preparation containing a water soluble or water dispersible copolymer obtainable by radical copolymerization useful as a cosmetic or pharmaceutical preparation, a protective colloid, and in the textile-, paper-, or printing industries - Google Patents

Abstract

A cosmetic or pharmaceutical preparation containing a water soluble or water dispersible copolymer (A) obtainable by radical copolymerization of: (1) (meth)acrylic acid amide; (2) alpha-beta-ethylenically unsaturated amide group containing compounds starch, starch derivatives and their mixtures; and (3) at least one cosmetically acceptable carrier is new. A cosmetic or pharmaceutical preparation containing: (1) at least one water soluble of water dispersible copolymer (A) obtainable by radical copolymerization of (wt.%): (a) (meth)acrylic acid amide (5-90); (b) at least one alpha-beta-ethylenically unsaturated amide group containing compounds of formula R1-C(O)-NR2R3 (I) (0-85): (c) at least one component different from (a) and (b) with a copolymerisable unsaturated water soluble compound (0-40), where the sum of (b) and (c) is at least 5 wt.%, optionally in the presence of up to 25 wt.% on the total weight of components (a) and (b) of at least one water soluble component (d) selected from: (i) polyether containing compounds; (ii) polymers having at least one 50 wt.% repeating units derived from vinyl alcohol; and (iii) starch and starch derivatives and their mixtures; and (2) at least one cosmetically acceptable carrier. R1, R2 = CH2=CR4; R4 = H or 1-4C alkyl; R1, R2, R3 = H, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl; provided that: (1) either R1 is CH2=CR4 and R2 is H, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl or joined with R3 or R2 is C=R4 and R1 is H, alkyl, cycloalkyl, heterocycloalkyl, aryl or heteroaryl or joined with R3; and (2) both of R2 and R3 are not H. An Independent claim is also included for a copolymer A obtainable by radical polymerization of (wt.%)::(a) methacrylic acid amide (10-45) and (b) vinylpyrrolidone and/or vinylcaprolacatam (60-90), (c) at least one different from (a) and (b) copolymerisable unsaturated water soluble compound (0-25), optionally in the presence of up to 25 wt.% on the total weight of (a)-(d) of polymers (d2) and/or starch or starch derivatives.

Description

The present invention relates to a cosmetic agent, which contains at least one water-soluble copolymer which by radical copolymerization of acrylic acid amide and / or Methacrylic acid amide and other copolymerizable therewith water-soluble α, β-ethylenically unsaturated compounds, optionally in Presence of a water-soluble polymeric graft base, is available.

Cosmetically and pharmaceutically acceptable water-soluble polymers are widely used in cosmetics and medicine. In soaps, For example, they usually serve as creams and lotions Formulating agents, e.g. B. as a thickener, foam stabilizer or Water absorbent or the irritating effects of others Mitigate ingredients or dermal application of To improve active ingredients. Your job is in hair cosmetics in influencing the properties of the hair. In the Pharmaceuticals, for example, serve as coating agents or Binder for solid pharmaceutical forms.

For hair cosmetics, for example, film-forming polymers used as a conditioner to dry and Improve wet combability, feel, gloss and appearance and to give the hair antistatic properties. Prefers become water-soluble polymers with polar, often cationic Functionalities that have a greater affinity for structurally caused negatively charged surface of the hair exhibit. Structure and mode of operation of various Hair treatment polymers are described in Cosmetic & Toiletries 103 (1988) 23. Commercially available conditioner polymers are e.g. B. cationic Hydroxyethyl cellulose, cationic polymers based on N-vinyl pyrrolidone, e.g. B. copolymers of N-vinylpyrrolidone and quaternized N-vinylimidazole, acrylamide and Diallyldimethylammonium chloride or silicone.

To set hairstyles, for example, vinyl lactam Homopolymers and copolymers and carboxylate group-containing polymers used. For example, there are requirements for hair setting resins a strong consolidation with high humidity, elasticity, Washability of the hair, compatibility in the formulation and a pleasant grip on the hair treated with it.

The provision of products often presents difficulties a complex property profile. So there is a need for Polymers for cosmetic products that are essential for formation smooth, tack-free films that are capable of hair and Give skin a pleasant grip and at the same time a good one Have conditioning effect or strengthening effect. moreover are sent to cosmetic and pharmaceutical products by the consumer increasingly aesthetic demands. So at such products currently have a preference for clear, opaque Formulations in the form of gels were observed.

US 5,478,553 and US 5,632,977 describe Hair setting compositions, the hono- or copolymers of N-vinylformamide contain. As a suitable comonomer u. A. also acrylamide called.

From US-A-5,334,287 graft polymers are known which by radical initiated polymerization of N-vinyl carboxamides, preferably N-vinyl formamide, and optionally others Monomers in the presence of monosaccharides, oligosaccharides and Polysaccharides are available. As additional monomers in addition to a large number of others, also acrylamide and methacrylamide called. A suitability of these graft copolymers as an active ingredient in cosmetic formulations is not mentioned.

WO 02/15854 describes the use of Graft copolymers which are obtainable by free radicals Graft copolymerization of at least one open-chain N-vinylamide compound and possibly at least one more with it copolymerizable monomers on a polymeric graft base, for cosmetic applications.

The present invention is based on the object cosmetic and pharmaceutical agents with good application technology To provide properties. These are intended for education be capable of tack-free smooth films. You should in particular have a good strengthening effect and become Manufacture products in the form of gels.

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

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

The invention therefore relates to a cosmetic or pharmaceutical composition containing

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

In the context of the present invention, the expression alkyl includes straight-chain and branched alkyl groups. Suitable short chain alkyl groups are e.g. B. straight-chain or branched C ₁ -C ₇ alkyl, preferably C ₁ -C ₆ alkyl and particularly preferably C ₁ -C ₄ alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec.-butyl, tert.-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl , 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 , 3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl - 2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl etc.

Suitable longer-chain C ₈ -C ₃₀ alkyl or C ₈ -C ₃₀ alkenyl groups are straight-chain and branched alkyl or alkenyl groups. Preferably, these are predominantly linear alkyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols, which may optionally also be mono-, di- or polyunsaturated. These include e.g. B. n-hexyl (en), n-heptyl (en), n-octyl (en), n-nonyl (en), n-decyl (en), n-undecyl (en), n-dodecyl (en) , n-tridecyl (en), n-tetradecyl (en), n-pentadecyl (en), n-hexadecyl (en), n-heptadecyl (en), n-octadecyl (en), n-nonadecyl (en) etc ,

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

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

Aryl includes unsubstituted and substituted aryl groups and preferably represents phenyl, tolyl, xylyl, mesityl, naphthyl, Fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and especially for 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 preferably represents pyrrolyl, pyrazolyl, imidazolyl, Indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, Pyrimidinyl or pyrazinyl.

The following are compounds that differ from acrylic acid and Deriving methacrylic acid can sometimes be shortened by insertion the syllable "(meth)" into that derived from acrylic acid Called connection.

The agents according to the invention can be used under normal conditions (20 ° C) advantageously formulated as gels. "Gel-like consistency" show agents that have a higher viscosity than a liquid have and which are self-supporting, d. H. one of them Retain the shape lent without a shape-stabilizing covering. in the In contrast to solid formulations, they can be gel-like However, slightly deform formulations using shear forces. The viscosity of the gel-like compositions is preferably in a range from greater than 600 to about 60,000 mPas.

Among water-soluble monomers and polymers are in the frame of the present invention understood monomers and polymers that dissolve at least 1 g / l in water at 20 ° C. Under water-dispersible polymers are understood to mean polymers which are referred to as Application of shear forces, for example, by stirring in dispersible particles disintegrate.

The invention and for the production of the invention copolymers A) used in cosmetic compositions preferably no copolymerized monomers containing acid groups.

Is the free radical copolymerization of components a) and optionally b) and / or c) in the presence of at least one Compounds of component d) are copolymers A) with get advantageous properties. This can, for example, from a at least partial grafting on component d) as Graft base result. However, there are mechanisms other than a graft imaginable. Component A) comprises entirely generally the process products of radical copolymerization including z. B. pure graft polymers, mixtures of Graft polymers with ungrafted compounds of component d), Homopolymers and copolymers of monomers a) and optionally b) and / or c) and any mixtures. shares of ungrafted compounds of component d) can, depending on Use of the copolymers A) be advantageous. You can for example an effect as an emulsifier or protective colloid get.

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

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

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

Preferred monomers b) are N-vinyl lactams and their derivatives, which, for. B. may have one or more C ₁ -C ₆ alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. These include e.g. B. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, etc. N-vinylpyrrolidone and N-vinylcaprolactam are preferably used.

Examples of suitable N-vinylamides as monomers b) are N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide, N-vinyl-butyramide and mixtures from that. N-vinylformamide is preferably used.

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

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

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

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

The cationogenic and / or cationic groups of component c) are preferably nitrogen-containing groups, such as primary, secondary and tertiary amino groups and quaternary ammonium groups. The nitrogen-containing groups are preferably tertiary amino groups or quaternary ammonium groups. Charged cationic groups can be derived from the amine nitrogen either by protonation, e.g. B. with carboxylic acids, such as lactic acid, or mineral acids, such as phosphoric acid, sulfuric acid and hydrochloric acid, or by quaternization, for. B. with alkylating agents such as C ₁ -C ₄ alkyl halides or sulfates. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Protonation or quaternization can generally take place both before and after the polymerization.

Suitable compounds c) are e.g. B. the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, preferably C ₂ -C ₁₂ amino alcohols. These can preferably be C ₁ -C ₈ monoalkylated or dialkylated on the amine nitrogen. As an acid component of these esters are, for. As acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Acrylic acid, methacrylic acid and mixtures thereof are preferably used. Are preferred
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. are preferred
N, N-dimethylaminoethyl (meth) acrylate and
N, N-dimethylaminopropyl (meth) acrylate used.

Suitable esters of vinyl alcohol as monomers c) Examples of monocarboxylic acids are vinyl formate, vinyl acetate and Propionate.

Suitable vinyl and allyl-substituted monomers c) heteroaromatic compounds are, for example, N-vinylimidazole, N-vinyl-2-methylimidazole etc.

Suitable monomers c) are also the amides of the above with α, β-ethylenically unsaturated mono- and dicarboxylic acids Diamines that are a tertiary and a primary or secondary Have amino group. These include e.g. B. N- [2- (dimethylamino) ethyl] - acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) - butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] methacrylamide etc. are preferred N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide used.

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


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

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

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

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

Y in formula II is preferably O or NH.

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

Suitable polyether acrylates are also urethane (meth) acrylates Alkylene oxide. Such compounds are in DE 198 38 851 (Component e2)) described, whereupon in full Scope is referred to.

The copolymers A) can, if desired, at least one Crosslinker, d. H. a compound with 2 or more than 2 ethylenic polymerized unsaturated double bonds. Crosslinkers are preferably used in an amount of 0.01 to 10% by weight, particularly preferably 0.1 to 3 wt .-% based on the Total weight of components a) to d) used.

Crosslinking monomers include compounds with at least two ethylenically unsaturated double bonds are used, such as for example esters of ethylenically unsaturated carboxylic acids, such as acrylic acid or methacrylic acid and polyhydric alcohols, Ethers of at least dihydric alcohols, such as Vinyl ether or allyl ether.

Examples of the underlying alcohols are dihydric Alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, But-2-en-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, Neopentyl glycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-bis (hydroxymethyl) cyclohexane, Hydroxypivalic acid neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) - propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane, Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, Tripropylene glycol, tetrapropylene glycol, 3-thio-pentane-1,5-diol, as well as polyethylene glycols, polypropylene glycols and Polytetrahydrofurans with molecular weights of 200 to 10,000 each. Except the homopolymers of ethylene oxide or propylene oxide also block copolymers of ethylene oxide or propylene oxide or Copolymers containing ethylene oxide and propylene oxide groups built-in included. Examples of underlying Alcohols with more than two OH groups are trimethylolpropane, Glycerin, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, Triethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, Mannose. The polyhydric alcohols can of course also after reaction with ethylene oxide or propylene oxide as that corresponding ethoxylates or propoxylates are used. The Polyhydric alcohols can also be initially reacted with Epichlorohydrin converted into the corresponding glycidyl ether become.

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

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

Straight-chain or branched, linear or cyclic aliphatic or aromatic hydrocarbons, the have at least two double bonds, which in the aliphatic hydrocarbons must not be conjugated, z. B. divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes with Molecular weights from 200 to 20,000.

Amides of unsaturated carboxylic acids are also suitable, such as B., acrylic and methacrylic acid, itaconic acid, maleic acid, and N-allylamines of at least divalent amines, such as Example 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, Piperazine, diethylene triamine or isophoronediamine. Likewise the amides of allylamine and unsaturated are suitable Carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, Maleic acid, or at least dibasic carboxylic acids as described above have been described.

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

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

Other suitable crosslinkers are divinyl dioxane, tetraallylsilane or tetravinylsilane.

Particularly preferred crosslinkers are, for example Methylenebisacrylamide, divinylbenzene, triallylamine and triallylammonium salts, Divinylimidazole, N, N'-divinylethylene urea, reaction products polyhydric alcohols with acrylic acid or methacrylic acid, Methacrylic acid esters and acrylic acid esters of polyalkylene oxides or polyhydric alcohols with ethylene oxide and / or propylene oxide and / or epichlorohydrin have been implemented, and allyl or Vinyl ethers of polyhydric alcohols, for example 1,2-ethanediol, 1,4-butanediol, diethylene glycol, trimethylolpropane, Glycerin, pentaerythritol, sorbitan and sugar such as sucrose, Glucose, mannose.

Are particularly preferred as crosslinkers Pentaerythritol triallyl ether, allyl ether of sugars such as sucrose, glucose, mannose, Divinylbenzene, N, N'-methylenebisacrylamide, N, N'-divinylethylene urea, and (meth) acrylic acid esters of glycol, butanediol, Trimethylolpropane or glycerin or (meth) acrylic acid ester from with Ethylene oxide and / or epichlorohydrin reacted glycol, Butanediol, trimethylolpropane or glycerin. Very particularly preferred are N, N'-methylenebisacrylamide, diallyltartaric acid diamide, Diallyl phthalate, diallyl urea, glycol di (meth) acrylate, Allyl (meth) acrylate and polyallyl ether.

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

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

The compounds of component d) used according to the invention contain essentially none Carbon-carbon double bonds. According to a suitable embodiment, the Compounds of component d) do not contain silicon atoms Groups.

Suitable polyether-containing compounds d1) are in general water-soluble or water-dispersible, nonionic polymers, which have polyalkylene glycol groups. The is preferably The proportion of polyalkylene glycol groups is at least 40% by weight on the total weight of the connection d1). As a polyether Compound d1) can, for example, be those mentioned above Polyalkylene glycols, polyesters based on polyalkylene glycols as well Polyether urethanes are used.

Depending on the type of monomer building blocks used for their preparation, the polyether-containing compounds d1) contain the following structural units:
- (CH ₂ ) ₂ -O-, - (CH ₂ ) ₃ -O-, - (CH ₂ ) ₄ -O-, -CH ₂ -CH (R ⁸ ) -O-, wherein
R ^{8 represents} C ₁ -C ₂₄ alkyl, preferably C ₁ -C ₄ alkyl.

The compounds d1) can additionally have bridging groups which are selected, for example, from:
-C (= O) -O-, -OC (= O) -O-, -C (= O) -NR ^a -, -OC (= O) -NR ^a -, -NR ^b - (C = O ) -NR ^a -
wherein R ^a and R ^{b are} independently hydrogen, C ₁ -C ₃₀ alkyl, preferably C ₁ -C ₄ alkyl or cycloalkyl.

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


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

The terminal primary hydroxyl groups of the polyethers produced on the basis of polyalkylene oxides and the secondary OH groups of polyglycerol can both be freely available in unprotected form and etherified with alcohols with a chain length of C ₁ -C ₂₄ or with carboxylic acids with a chain length of C ₁ -C ₂₄ or are esterified or reacted with isocyanates to form urethanes. Polyether urethanes are preferably used.

Branched or unbranched C ₁ -C ₁₂ -, particularly preferably C ₁ -C ₆ -alkyl chains may be mentioned as preferred representatives of the above-mentioned alkyl radicals.

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

It is advantageous to use homopolymers of Ethylene oxide or copolymers with an ethylene oxide content of 40 up to 99% by weight. For those who prefer to be used Ethylene oxide polymers is thus the proportion of polymerized Ethylene oxide 40 to 100 mol%. As a comonomer for these copolymers come in propylene oxide, butylene oxide and / or isobutylene oxide Consideration. Copolymers of, for example, are suitable Ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide and copolymers of ethylene oxide, Propylene oxide and at least one butylene oxide. The ethylene oxide content the copolymer is preferably 40 to 99 mol%, the Propylene oxide proportion 1 to 60 mol% and the proportion of butylene oxide in the copolymers 1 to 30 mol%. In addition to straight chain also branched homopolymers or copolymers as polyether-containing ones Compounds d1) are used.

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

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

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

Suitable polyether urethanes are the condensation products of Polyether polyols, such as polyether diols, with polyisocyanates, such as Diisocyanates. Suitable polyether polyols are those previously mentioned polyalkylene glycols, for example, from the Polymerization of cyclic ethers, such as tetrahydrofuran, or from the Reaction of one or more alkylene oxides with one Starter molecule that has two or more active hydrogen atoms, are available.

Suitable polyisocyanates are selected from compounds with 2 up to 5 isocyanate groups, isocyanate prepolymers with a medium Number of 2 to 5 isocyanate groups, and mixtures thereof. To count z. B. aliphatic, cycloaliphatic and aromatic di-, Tri and polyisocyanates. Suitable diisocyanates are e.g. B. Tetramethylene diisocyanate, hexamethylene diisocyanate, 2,3,3-trimethylhexamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, Isophorone diisocyanate, 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and its isomer mixtures (e.g. 80% 2,4- and 20% 2,6-isomer), 1,5-naphthylene diisocyanate, 2,4- and 4,4'-diphenylmethane diisocyanate. A suitable triisocyanate is e.g. B. Triphenylmethane-4,4 ', 4 "-triisocyanate. Also suitable Isocyanate prepolymers and polyisocyanates by adding the previously mentioned isocyanates on polyfunctional hydroxyl or compounds containing amine groups are available. Are also suitable Polyisocyanates resulting from the formation of biurets or isocyanurates. Hexamethylene diisocyanate, trimerized are preferred Hexamethylene diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and mixtures thereof.

Also suitable as graft base are polymers d2) which have at least 50% by weight of vinyl alcohol units. These polymers preferably contain at least 70% by weight, very particularly preferably 80% by weight, of polyvinyl alcohol units. Such polymers are usually produced by polymerization of a vinyl ester and subsequent at least partial alcoholysis, aminolysis or hydrolysis. Vinyl esters of linear and branched C ₁ -C ₁₂ carboxylic acids are preferred, and vinyl acetate is very particularly preferred. The vinyl esters can of course also be used in a mixture.

As comonomers of the vinyl ester for the synthesis of the graft base d2) come, for example, N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate, diallyl ammonium chloride, Styrene, alkylstyrenes in question.

Other suitable comonomers for the preparation of the graft base d2) are, for example, monoethylenically unsaturated C ₃ -C ₆ -carboxylic acids such as, for. As acrylic acid, methacrylic acid, crotonic acid, fumaric acid, and their esters, amides and nitriles such as. As methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, stearyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, Hydroxyisobutylacrylat, Hydroxyisobutylmethacrylat, monomethyl maleate, dimethyl maleate, monoethyl maleate, Maleinsäureiethylester, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, maleic anhydride and its Halbester, alkylene glycol (meth ) acrylates, acrylamide, methacrylamide, N-dimethylacrylamide, N-tert-butylacrylamide, acrylonitrile, methacrylonitrile, vinyl ethers such as e.g. B. methyl, ethyl, butyl or dodecyl vinyl ether, cationic monomers such as dialkylaminoalkyl (meth) acrylates and dialkylaminoalkyl (meth) acrylamides such as dimethylaminothylacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and the salts of the latter monomers with carboxylic acids or mineral acids and the quar.

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

The graft base d2) is produced in accordance with known methods Processes, for example the solution, precipitation, suspension or emulsion polymerization using compounds, which form radicals under the polymerization conditions. The Polymerization temperatures are usually in the range from 30 to 200 ° C, preferably 40 to 110 ° C. Suitable initiators are, for example, azo and peroxy compounds and usual redox initiator systems, such as combinations of Hydrogen peroxide and reducing compounds, for example Sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and Hydrazine. If necessary, these systems can additionally contain small amounts of a heavy metal salt.

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

Particularly preferred graft bases d2) are polymers which by homopolymerizing vinyl acetate and subsequent at least partial saponification can be produced. Such Polymers containing polyvinyl alcohol units are available under the name Mowiol® available.

Starch and / or starch derivatives are preferred as component d) d3) used. These include substances that have saccharide structures contain. Such natural substances are, for example Saccharides of vegetable or animal origin or products that have arisen through metabolism by microorganisms, as well as their degradation products. Suitable graft bases d3) are for example oligosaccharides, polysaccharides, oxidative, enzymatically or hydrolytically degraded polysaccharides, oxidative hydrolytically degraded or oxidatively enzymatically degraded Polysaccharides, chemically modified oligosaccharides or polysaccharides and Mixtures of these. Preferred products are those in US 5,334,287 in Column 4, line 20 to column 5, line 45 compounds mentioned.

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

If desired, mixtures of compounds of the component d) are used. Z are advantageous. B. Mixtures that at least one connection d2) and at least one connection d3) contain.

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

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

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

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

• a) 30 bis 40 Gew.-% Methacrylsäureamid,
• b) 30 bis 60 Gew.-% Vinylpyrrolidon,

in Gegenwart von 1 bis 20 Gew.-% Polymeren d2) und/oder Stärke und Stärkederivaten d3). The copolymer A) is particularly preferably obtainable by free-radical polymerization of

• a) 30 to 40% by weight of methacrylic acid amide,
• b) 30 to 60% by weight of vinyl pyrrolidone,

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

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

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

• a) 30 to 40% by weight of methacrylic acid amide,
• b) 20 to 60% by weight vinyl pyrrolidone and 1 to 20% by weight vinyl caprolactam.

• a) 30 bis 40 Gew.-% Methacrylsäureamid,
• b) 20 bis 60 Gew.-% Vinylpyrrolidon und
• c) 1 bis 20 Gew.-% wenigstens einer von a) und b) verschiedenen, damit copolymerisierbaren wasserlöslichen Verbindung.

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

• a) 30 to 40% by weight of methacrylic acid amide,
• b) 20 to 60 wt .-% vinyl pyrrolidone and
• c) 1 to 20 wt .-% of at least one of a) and b) different, copolymerizable therewith water-soluble compound.

The copolymers A) are prepared in accordance with the usual Methods known to those skilled in the art, preferably by Solution polymerization.

The polymerization temperatures are preferably in one Range from about 30 to 120 ° C, particularly preferably 40 to 100 ° C. The Polymerization usually takes place under atmospheric pressure, however, it can also be used under reduced or increased pressure expire. A suitable pressure range is between 1 and 5 bar.

The monomers can be used to prepare the polymers optionally in the presence of component d) using both Free radical initiators as well as by action high energy radiation, including exposure to high energy Electrons to be understood are polymerized.

As initiators for radical polymerization, the Peroxo and / or azo compounds customary for this are used are, for example alkali or ammonium peroxydisulfates, Diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, Di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permaleinate, cumene hydroperoxide, Diisopropyl peroxidicarbamate, bis (o-toluoyl) peroxide, Didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl 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-methylbutyronitrile). Are also suitable Initiator mixtures or redox initiator systems, such as. B. Ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate.

The polymerization can also be caused by exposure to ultraviolet Radiation, optionally in the presence of UV initiators, be performed. For polymerizing under the influence of UV Rays are used for those that are usually considered Photoinitiators or sensitizers. This is what it is about are compounds such as benzoin and benzoin ether, α-methylbenzoin or α-phenylbenzoin. Also known as triplet Sensitizers such as benzyl diketals can be used. In addition, for example, serve as UV radiation sources high-energy UV lamps, such as carbon arc lamps, mercury vapor lamps or xenon lamps also low-UV light sources, such as fluorescent tubes with a high proportion of blue.

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

The polymerization can take place, for example, in bulk. at bulk polymerization using a Graft base d) can be in at least one monomer and possibly further comonomers dissolved and after adding a The mixture can be polymerized out of the polymerization initiator. The Polymerization can also be carried out semi-continuously by you start with a part, e.g. B. 10% of the polymerized Mixture from the graft base d), at least one monomer of Group a), possibly presenting further comonomers and initiators, the mixture is heated to the polymerization temperature and after Starting the polymerization the rest of the to be polymerized Mixture is added as the polymerization progresses. The Polymers can also be obtained by the Gopfgrundlage d) in a reactor, on the Heated polymerization temperature and at least one monomer from group a), possibly further comonomers and polymerization initiator either all at once, batchwise or preferably continuously adds and polymerizes.

Polymerization in a solvent is preferred. suitable Solvents are water and mixtures of water with water-miscible solvents, for example alcohols, such as methanol, Ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol as well as glycols, such as Ethylene glycol, propylene glycol and butylene glycol as well as the methyl or Ethyl ether of dihydric alcohols, diethylene glycol, Triethylene glycol, glycerin and dioxane.

To adjust the molecular weight, the polymerization in Presence of at least one controller. Can as a controller the usual compounds known to the person skilled in the art, such as, for. B. Sulfur compounds, e.g. B. mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid or dodecyl mercaptan and Tribromochloromethane or other compounds that regulate that Molecular weight of the polymers obtained act, are used. Silicon-free controllers are preferably used.

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

Is an organic in the manufacture of the polymers Solvent used, this can by usual, the expert known methods, e.g. B. by distillation at reduced pressure, be removed.

The polymer solutions can be different Drying processes such as B. spray drying, fluidized spray drying, Roller drying or freeze drying can be transferred in powder form. Spray drying is preferably used. The so obtained Polymer dry powder can advantageously be dissolved or redispersing in water again in an aqueous solution or Transfer dispersion. Powdery copolymers have the advantage better shelf life, easier Possibility of transportation and usually show a lower inclination for Microbial attack.

The invention also relates to copolymers A).

• a) Wasser,
• b) wassermischbaren organischen Lösungsmitteln, vorzugsweise C₁-C₄-Alkanolen,
• c) Ölen, Fetten, Wachsen,
• d) von iii) verschiedenen Estern von C₆-C₃₀-Monocarbonsäuren mit ein-, zwei- oder dreiwertigen Alkoholen,
• e) gesättigten acyclischen und cyclischen Kohlenwasserstoffen,
• f) Fettsäuren,
• g) Fettalkoholen

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

• a) water,
• b) water-miscible organic solvents, preferably C ₁ -C ₄ -alkanols,
• c) oils, fats, waxes,
• d) esters of C ₆ -C ₃₀ monocarboxylic acids with mono-, di- or trihydric alcohols which are different from iii),
• e) saturated acyclic and cyclic hydrocarbons,
• f) fatty acids,
• g) fatty alcohols

and mixtures thereof.

The agents according to the invention have, for. B. an oil or fat component B), which is selected from: hydrocarbons of low polarity, such as mineral oils; linear saturated hydrocarbons, preferably with more than 8 carbon atoms, such as 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. B. the esters of C ₁ -C ₂₄ monoalcohols with C ₁ -C ₂₂ monocarboxylic acids, such as isopropyl isostearate, n-propyl myristate, iso-propyl myristate, n-propyl palmitate, iso-propyl palmitate, hexacosanyl palmitate, octacosanyl palmitate, triacontanyl palmitate, tiacontanyl palmitate, Hexancosanyl stearate, octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, tetratriacontanyl stearate; Salicylates such as C ₁ -C ₁₀ salicylates, e.g. B. 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 e.g. B. linear polydimethylsiloxanes, Poly (methylphenylsiloxanes), cyclic siloxanes and mixtures from that. The number average molecular weight of the polydimethylsiloxanes and poly (methylphenylsiloxane) is preferably in one Range from about 1000 to 150,000 g / mol. Preferred cyclic Siloxanes have 4- to 8-membered rings. Suitable cyclic Siloxanes are e.g. B. commercially under the name Cyclomethicone available.

Preferred oil or fat components B) are selected from Paraffin and paraffin oils; Petroleum jelly; natural fats and oils, such as castor oil, soybean oil, peanut oil, olive oil, sunflower oil, Sesame oil, avocado oil, cocoa butter, almond oil, peach seed oil, Castor oil, cod liver oil, pork lard, walnut, spermacet 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 like Myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid, Linolenic acid and various saturated, unsaturated and substituted fatty acids; Waxing like beeswax, carnauba wax, Candililla wax, walrus and mixtures of the aforementioned oil or fat components.

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

Suitable hydrophilic carriers B) are selected from water, 1-, 2- or polyhydric alcohols, preferably 1 to 8 Carbon atoms, such as ethanol, n-propanol, iso-propanol, Propylene glycol, glycerin, sorbitol, etc.

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

The agents according to the invention are preferably in the form of a Gels, foams, sprays, an ointment, cream, emulsion, suspension, Lotion, milk or paste. If desired, you can also Liposomes or microspheres can be used.

The cosmetically or pharmaceutically active according to the invention Agents can additionally be cosmetically and / or dermatologically active Contain active substances and auxiliary substances.

Suitable cosmetically and / or dermatologically active ingredients are z. B. coloring agents, skin and Hair pigmentation, tinting, tanning, bleaching, Keratin-curing substances, antimicrobial substances, light filter substances, Repellent agents, hyperemising substances, substances with keratolytic and keratoplastic effects, Anti-dandruff agents, anti-inflammatory agents, keratinizing substances, antioxidant or active as a radical scavenger, skin moisturizing or moisturizing substances, moisturizing agents, anti-inflammatory or anti-allergic active ingredients and mixtures from that.

Artificially tanning agents that are suitable for the skin without natural or artificial radiation with UV rays too tan, are z. B. dihydroxyacetone, alloxan and Walnut shell extract. Suitable keratin-curing substances are usually Active ingredients such as those used in antiperspirants, such as z. B. potassium aluminum sulfate, aluminum hydroxychloride, Aluminum lactate, etc. Antimicrobial agents are used to To destroy microorganisms or to inhibit and serve their growth thus both as a preservative and as a deodorant acting substance, which the emergence or the intensity of Body odor reduced. These include e.g. B. usual, the expert known preservatives, such as p-hydroxybenzoic acid esters, Imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, Salicylic acid, etc. Such substances are deodorant z. B. zinc ricinoleate, triclosan, undecylenic acid alkylolamides, Citric acid triethyl ester, chlorhexidine etc. Suitable Light filter active ingredients are substances that emit UV rays in UV-B and / or UV Absorb A area. Suitable UV filters are e.g. B. 2,4,6-triaryl-1,3,5-triazines, in which the aryl groups in each case at least can carry a substituent, which is preferably selected is under hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and mixtures thereof. Also suitable are p-aminobenzoic acid esters, cinnamic acid esters, Benzophenones, camphor derivatives and UV rays Pigments such as titanium dioxide, talc and zinc oxide. suitable Repellent agents are compounds that are capable of certain Keep animals, especially insects, away from humans to evict. This includes e.g. B. 2-ethyl-1,3-hexanediol, N, N-diethyl- m-toluamide etc. Suitable hyperemising substances, which stimulate the blood circulation in the skin, e.g. B. essential oils, such as Mountain pine, lavender, rosemary, juniper berries, Horse chestnut extract, birch leaf extract, hay flower extract, ethyl acetate, Camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil, etc. Suitable keratolytic and keratoplastic materials are z. B. salicylic acid, calcium thioglycolate, thioglycolic acid and their salts, sulfur, etc. are suitable antidandruff agents z. B. sulfur, sulfur polyethylene glycol sorbitan monooleate, Sulfur ricinol polyethoxylate, zinc pyrithione, aluminum pyrithione, etc. Suitable anti-inflammatory drugs that counteract skin irritation are z. B. allantoin, bisabolol, dragosantol, chamomile extract, Panthenol, etc.

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

Examples of anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes, e.g. B. Luviset PUR® from BASF, and polyureas. Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (e.g. Luvimer® 100P), copolymers of ethyl acrylate and methacrylic acid (e.g. Luviumer® MAE), copolymers of N-tert.-butyl acrylamide, ethyl acrylate, acrylic acid (Ultrahold® 8, strong), copolymers of vinyl acetate, crotonic acid and optionally further vinyl esters (e.g. Luviset® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, e.g. B. carboxy-functional, t-butyl acrylate, methacrylic acid (z. B. Luviskol® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as. B. C ₄ -C ₃₀ alkyl esters of meth (acrylic acid), C ₄ -C ₃₀ alkyl vinyl esters, C ₄ -C ₃₀ alkyl vinyl ether and hyaluronic acid. Examples of anionic polymers are also vinyl acetate / crotonic acid copolymers, such as are commercially available under the names Resyn® (National Starch) and Gafset® (GAF), and vinylpyrrolidone / vinyl acrylate copolymers, available, for example, under the trademark Luviflex® (BASF) , Other suitable polymers are the vinyl pyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF) and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyester.

Other suitable polymers are cationic polymers with the Designation polyquaternium according to INCI, e.g. B. copolymers Vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat O MS, Luviquat® Care), copolymers N-vinyl pyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ 11), copolymers from N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold); cationic Cellulose derivatives (Polyquaternium-4 and -10), acrylamido copolymers (Polyquaternium-7) and chitosan. Suitable cationic (Quaternized) polymers are also Merquat® (polymer based on Dimethyldiallylammonium chloride), Gafquat® (quaternary polymers that by reaction of polyvinylpyrrolidone with quaternary Ammonium compounds are formed), polymer JR (with hydroxyethyl cellulose cationic groups) and cationic polymers on vegetable Base, e.g. B. guar polymers, such as the Jaguar® brands from Rhodia.

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

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

Suitable polymers are also amphoteric or zwitterionic Polymers, such as those under the names Amphomer® (National Starch) available Octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers as well zwitterionic polymers, such as those found in German Patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 are disclosed. Acrylamidopropyltrimethylammoniumchlorid / acrylic acid or methacrylic acid copolymers and their Alkali and ammonium salts are preferred zwitterionic Polymers. Suitable zwitterionic polymers are also Methacroylethylbetaine / methacrylate copolymers, which under the Name Amersette® (AMERCHOL) are commercially available, and Copolymers of hydroxyethyl methacrylate, methyl methacrylate, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon®).

Suitable polymers are also nonionic, siloxane-containing, water-soluble or -dispersible polymers, e.g. B. Polyether siloxanes, such as Tegopren® (from Goldschmidt) or Belsil® (from Wacker).

The formulation basis of pharmaceutical according to the invention Agent preferably contains pharmaceutically acceptable excipients. Those in the field of pharmacy are pharmaceutically acceptable Food technology and related fields are known usable auxiliaries, in particular those in relevant Pharmacopoeia (e.g. DAB Ph. Eur. BP NF) listed as well as others Excipients, their properties of a physiological application don't stand in the way.

Suitable auxiliaries can be: lubricants, wetting agents, emulsifying and suspending agents, preservatives, Antioxidants, anti-irritants, chelating agents, Emulsion stabilizers, film formers, gel formers, odor masking agents, resins, Hydrocolloids, solvents, solubilizers, Neutralizing agents, permeation accelerators, pigments, quaternary Ammonium compounds, refatting and superfatting agents, ointments, Cream or oil base materials, silicone derivatives, stabilizers, Sterilants, blowing agents, drying agents, opacifiers, Thickeners, waxes, plasticizers, white oils. A related one Design is based on professional knowledge like them for example in Fiedler, H. P. Lexicon of auxiliaries for Pharmacy, cosmetics and related areas, 4th ed., Aulendorf: ECV- Editio-Kantor-Verlag, 1996.

For the production of the dermatological agents according to the invention the active ingredients with a suitable excipient (excipient) can be mixed or diluted. Excipients can be solid, semi be solid or liquid materials used as vehicles, carriers or medium can serve for the active ingredient. The admixture If desired, further auxiliaries are carried out in the skilled person known way.

According to a first preferred embodiment, it is the inventive agents around a skin cleanser.

Preferred skin cleansers are soaps from liquid to gel-like consistency, such as transparent soaps, luxury soaps, Deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, paste soaps, soft soaps and washing pastes, liquid washing, showering and bathing preparations, such as washing lotions, Shower baths and gels, bubble baths, oil baths and scrub preparations.

According to a further preferred embodiment, it is in the inventive agents to cosmetic agents Care and protection of the skin, nail care products or Preparations for decorative cosmetics.

It is particularly preferably skin care products, Intimate hygiene products, foot care products, light stabilizers, repellents, Shaving, hair removal, anti-acne, make-up, Mascara, lipsticks, eye shadows, eye pencils, eyeliner, blushes and eyebrow pencils.

The skin care products according to the invention are especially 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 care lotions and Moisturizing lotions.

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

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

Especially have light stabilizers based on copolymers A) the property, the residence time of the UV absorbing Ingredients compared to common aids such as Increase polyvinyl pyrrolidone.

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

In addition to the polymers A), the skin cosmetic preparations can and suitable carriers are still more common in skin cosmetics Active substances and auxiliary substances, as described above, contain. These preferably include emulsifiers, preservatives, Perfume oils, cosmetic ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, Bleaching agents, coloring agents, tinting agents, tanning agents, collagen, Protein hydrolyzates, stabilizers, pH regulators, dyes, Salts, thickeners, gelling agents, consistency agents, silicones, Humectants, moisturizers and other common additives.

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

The polymers of the invention can also be used with conventional ones Mix polymers if special properties are set should be.

To set certain properties such. B. Improvement of feeling, of spreading behavior, of water resistance and / or the binding of active substances and auxiliary substances, such as pigments, can use the skin cosmetic and dermatological preparations also conditioning substances based on Contain silicone compounds. Suitable silicone compounds are for example polyalkylsiloxanes, polyarylsiloxanes, Polyarylalkylsiloxanes, polyether siloxanes or silicone resins.

The production of cosmetic or dermatological Preparations are carried out by customary methods known to those skilled in the art.

The cosmetic and dermatological agents are preferably in Form of emulsions especially as water-in-oil (W / O) or oil in water (O / W) emulsions. But it is also possible for others To choose types of formulation, for example hydrodispersions, Gels, oils, oleogels, multiple emulsions, for example in the form of W / O / W or O / W / O emulsions, anhydrous ointments or Ointment bases, etc.

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

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

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

Preferred fat components, which are in the fat phase of the Emulsions that may be included are: hydrocarbon oils, such as Paraffin oil, Purcellinöl, Perhydrosqualen and solutions microcrystalline waxes in these oils; animal or vegetable oils, such as Sweet almond oil, avocado oil, calophylum oil, lanolin and derivatives thereof, Castor oil, sesame oil, olive oil, jojoba oil, shea oil, hoplostethus Oil; mineral oils, the distillation of which begins at Atmospheric pressure at approx. 250 ° C and their distillation end point at 410 ° C lies, such as B. Vaseline oil; More saturated or unsaturated esters 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 silicone oils soluble in other oils, such as Dimethylpolysiloxane, methylphenylpolysiloxane and that Contains silicone glycol copolymer, fatty acids and fatty alcohols.

To promote the retention of oils, in addition to the Polymers A) waxes are also used, such as. B. carnauba wax, Candililla wax, beeswax, microcrystalline wax, Ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and Stearates.

Generally, the water-in-oil emulsions are made that the fat phase and the emulsifier in a batch container are given. It is heated at a temperature of about 50 to 75 ° C, then gives the active ingredients soluble in oil and / or Add excipients and add water while stirring, which previously was heated to about the same temperature and in which one if necessary, has previously dissolved the water-soluble ingredients. The mixture is stirred until an emulsion of the desired fineness is obtained and then allowed to cool to room temperature, where appropriate is less stirred.

According to a further preferred embodiment, it is in the agents according to the invention a shower gel, a shampoo Formulation or a bath preparation.

Such formulations contain at least one polymer A) and usually anionic surfactants as base surfactants and amphoteric and / or nonionic surfactants as cosurfactants. More suitable Active substances and / or auxiliary substances are generally selected under lipids, perfume oils, dyes, organic acids, Preservatives and antioxidants as well Thickeners / gelling agents, skin conditioners and humectants.

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

In the washing, showering and bathing preparations, everyone can Body cleansers commonly used anionic, neutral, amphoteric or cationic surfactants can be used.

Suitable anionic surfactants are, for example, alkyl sulfates, Alkyl ether sulfates, alkyl sulfonates, alkyl aryl sulfonates, Alkyl succinates, alkyl sulfosuccinates, N-alkoylsarcosinates, acyl taurates, Acyl isothionates, alkyl phosphates, alkyl ether phosphates, Alkyl ether carboxylates, alpha olefin sulfonates, especially the alkali and Alkaline earth metal salts, e.g. B. sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, Alkyl ether phosphates and alkyl ether carboxylates can be between 1 up to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 Have ethylene oxide units in the molecule.

These include e.g. B. sodium lauryl sulfate, ammonium lauryl sulfate, Sodium lauryl ether sulfate, ammonium lauryl ether sulfate, Sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecyl benzene sulfonate, Triethanolamine.

Suitable amphoteric surfactants are e.g. B. alkyl betaines, Alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, Alkyl carboxyglycinates, alkyl amphoacetates or propionates, Alkyl amphodiacetates or dipropionates.

For example, cocodimethylsulfopropyl betaine, Lauryl betaine, cocamidopropyl betaine or sodium cocamphopropionate be used.

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

In addition, the washing, showering and bathing preparations can be usual contain cationic surfactants, such as. B. quaternary Ammonium compounds, for example cetyltrimethylammonium chloride.

In addition, other conventional cationic polymers can also be used are used, for. B. copolymers of acrylamide and Dimethyldiallylammonium chloride (Polyquaternium-7), cationic Cellulose derivatives (Polyquaternium-4, -10), Guar hydroxypropyltrimethylammonium chloride (INCI: hydroxylpropyl guar hydroxypropyltrimonium Chlorides), copolymers of N-vinylpyrrolidone and quaternized N-vinylimidazole (Polyquaterinium-16, -44, -46), copolymers of N-vinyl pyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (polyquaternium-11) and others.

Furthermore, the shower gel / shampoo formulations thickeners, such as B. Saline, PEG-55, Propylene Glycol Oleate, PEG-120 Methyl glucose dioleates and others, as well as preservatives, contain other active substances and auxiliary substances and water.

According to a further preferred embodiment, it is in the inventive agents around a hair treatment agent.

Hair treatment compositions according to the invention preferably contain at least one copolymer A) in an amount in the range of about 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, based on the Total weight of the product.

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

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

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

• a) 0.1 to 20% by weight, preferably 1 to 10% by weight, of at least one polymer A), as previously defined,
• b) 0 to 40% by weight of at least one carrier (solvent) which is selected from C ₂ -C ₅ alcohols, in particular ethanol,
• c) 0.01 to 5% by weight, preferably 0.2 to 3% by weight, of at least one thickener,
• d) 0 to 50% by weight of a blowing agent,
• e) 0 to 10% by weight, preferably 0.1 to 3% by weight, of at least one fixing polymer different from a), preferably a water-soluble nonionic polymer,
• f) 0 to 1% by weight of at least one refatting agent, preferably selected from glycerol and glycerol derivatives,
• g) 0 to 30% by weight of further active substances and / or auxiliaries, for. B. at least one silicone compound,
• h) water ad 100 wt .-%.

The hair treatment agents can continue in the form of hair sprays or hair foams. Include hair sprays and hair foams preferably predominantly or exclusively water-soluble or water dispersible components. Are they in the Hair sprays and hair foams used according to the invention water dispersible, they can be in the form of aqueous microdispersions with particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm, can be used. The The solids content of these preparations is usually in one Range from about 0.5 to 20% by weight. These microdispersions generally do not need any emulsifiers or surfactants for their Stabilization.

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

The hair treatment agents according to the invention can also be used in Contain generally customary cosmetic auxiliaries, for example plasticizers such as glycerin and glycol; emollients; perfumes; surfactants; UV absorbers; dyes; antistatic agents; Combing agents; Preservatives; and defoamers.

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

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

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

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

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

• a) 0.5 to 20% by weight, preferably 1 to 10% by weight, of at least one polymer A), as previously defined,
• b) 50 to 99.5% by weight, preferably 55 to 99% by weight, of a carrier (solvent) selected from water and water-miscible solvents, preferably C ₂ -C ₅ alcohols, in particular ethanol, and mixtures thereof,
• c) 0 to 70 wt .-%, preferably 0.1 to 50 wt .-%, of a blowing agent, preferably selected from dimethyl ether and alkanes, such as. B. propane / butane mixtures,
• d) 0 to 10% by weight, preferably 0.1 to 10% by weight, of at least one hair polymer different from a), preferably a water-soluble or dispersible polymer,
• e) 0 to 0.5% by weight, preferably 0.001 to 2% by weight, of at least one water-soluble or water-dispersible silicone compound,

and optionally further active substances and / or auxiliary substances, as previously defined.

The agent according to the invention can contain at least one as component e) nonionic, siloxane containing, water soluble or -Dispersible polymer, especially selected from those previously described polyether siloxanes contain. The share of this Component is then generally about 0.001 to 2% by weight, based on the total weight of the agent.

The copolymers A) are advantageously suitable as Pharmaceutical auxiliaries, preferably as or in Coating agent (s) for the textile, paper, printing and leather industries.

The invention is non-limiting based on the following Examples explained in more detail.

Examples General manufacturing instructions Solution polymerization (example 10)

Inlet 1:
Monomer mixture from:
240 g (50% aqueous solution) acrylamide and
533.4 g (15% aqueous solution) methacrylamide
Inlet 2:
Monomer mixture from:
120 g vinyl pyrrolidone and
80 g vinyl caprolactam
Inlet 3:
Initiator solution from:
20 g Wako V 50 [2,2'-azobis (2-amidinopropane) - dihydrochloride] and
180 g water
Inlet 4:
Initiator solution from:
10 g Wako V 50 [2,2'-azobis (2-amidinopropane) - dihydrochloride] and
90 g water

In a stirrer with reflux condenser, internal thermometer and four separate feed devices were 10% of feed 1, 20% of feed 2 and 10% of feed 3 in 490 g of water and the mixture was heated to about 60 ° C. with stirring. After this Polymerization, recognizable by the beginning of an increase in viscosity, the rest of feed 1 was at 65 ° C. within three hours, the rest of feed 2 within 1.5 hours and the rest of Feed 3 added within four hours. After the end of the Addition was continued at this temperature for two hours afterpolymerized. Subsequently, feed 4 added within 30 minutes at 65 ° C and after the end of the The addition was continued at this temperature for about two hours another two hours at a temperature of 80 to 90 ° C afterpolymerized. An approximately 30% aqueous microdispersion is obtained. To stabilize the solution with 100 ppm of Euxyl®K 100 der Schülke & Mayr (5-chloro-2-methyl-3- (2H) -isothiazolone / 2-methyl-3- (2H) -isothiazolone / benzyl alcohol). At the Use of water / ethanol mixtures can lead to the use of a Stabilizer are dispensed with.

Powdery products can be obtained by spray drying or freeze drying. In analogy, all of the products in the list below were polymerized. Table 1

Application properties standard formulation

From 0.5% by weight of a commercially available polyacrylic acid thickener (Carbopol 940, BFGoodrich), neutralized with triethanolamine (TEA) a gel is formulated which, when applied to the hair in the Has essentially no conditioning or strengthening effect. The application properties are in Table 2, Comparative Example A reproduced.

Comparative Examples B-D

The gel formulation from the standard formulation are each 3% by weight a commercially available hair polymer (Example B: Polyacrylic acid amide, C: polyvinylformamide, D: polyvinylpyrrolidone) added. The application properties are shown in Table 2 played. The products are still sticky improvement.

According to the invention

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

B) viscosity grade viscosity 1 very firm (reference: gel made from 0.5% Carbopol 940 / TEA) 2 firmly 3 moderately firm 4 fluently 5 low viscosity

C) stickiness

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



Use in hair cosmetics 1) Hair gels with an anionic thickener: Examples No. 1-50

The components are weighed and homogenized to produce the hair gel. Phase 2 forms a clear, firm gel into which phase 1 is slowly stirred. 2) Hair gels with another setting polymer and anionic thickener Example No. 51-100


Production: Weighing in and homogenization. Phase 2 forms a clear, firm gel. Stir phase 1 slowly into phase 2. 3) Liquid hair gels Example No. 101-138



Preparation: Weigh in and slowly homogenize at room temperature. 4) Aqueous Hand Pump Sprays Examples No. 139-175

Preparation: Weigh in and slowly homogenize at room temperature. 5) VOC 55 hand pump spray Examples No. 176-194

6) VOC 55 aerosol hairspray Example No. 195-213

7) Foam strengthener Examples No. 214-232

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

Production: Weigh in and separate phases A) and B) with stirring and mix. Stir phase B) slowly into phase A). Use in skin cosmetics 9) Standard o / w cream Examples No. 273-290



Production: Weigh in and homogenize the oil phase and the water phase separately at a temperature of 80 ° C. Slowly stir the water phase into the oil phase. Cool slowly to room temperature while stirring. 10) Day Lotion Examples No. 291-308



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

Claims (14)

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


in which
R ^{1 represents} 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 independently of one another represent H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl the proviso that one of the radicals R ² and R ^{3 is} different from H, or R ² and R ³ together with the nitrogen atom to which they are attached represent a five- to eight-membered heterocycle,
or R ^{2 is} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ³ independently of one another are H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl, or R ¹ and R ³ together with the amide group to which they are bound for a lactam with 5 to 8 ring atoms, c) 0 to 40% by weight, based on the total weight of components a) to d), of at least one unsaturated water-soluble compound which is copolymerizable with components a) and b), the proportion by weight of the sum of components b) and c) being at least 5% by weight,
optionally in the presence of up to 25% by weight, based on the total weight of components a) to d), of at least one water-soluble component d) which is selected from 1. polyether-containing compounds, 2. Polymers which have at least 50% by weight of repeat units derived from vinyl alcohol, 3. starch and starch derivatives, and mixtures thereof, and B) at least one cosmetically acceptable carrier. 2. Composition according to claim 1, wherein component b) at least includes a compound selected from N-vinyl lactams, N-vinyl amides of saturated monocarboxylic acids, N-alkyl and N, N-dialkylamides α, β-ethylenically unsaturated Monocarboxylic acids and mixtures thereof. 3. Composition according to one of the preceding claims, wherein the Component c) comprises at least one compound which is selected from esters α, β-ethylenically unsaturated mono- and Dicarboxylic acids with amino alcohols, their N-alkyl and N, N dialkyl derivatives; Esters of ethanol with Monocarboxylic acids; vinyl and allyl substituted heteroaromatic Links; Amides α, β-ethylenically unsaturated mono- and Dicarboxylic acids with diamines, which are tertiary and primary or have secondary amino group; Polyether acrylates and Mixtures of these. 4. Composition according to one of the preceding claims, wherein component B) is selected from a) water, b) water-miscible organic solvents, preferably C ₁ -C ₄ -alkanols, c) oils, fats, waxes, d) esters of C ₆ -C ₃₀ monocarboxylic acids with mono-, di- or trihydric alcohols which are different from iii), e) saturated acyclic and cyclic hydrocarbons, f) fatty acids, g) fatty alcohols and mixtures thereof. 5. Composition according to one of the preceding claims in the form of a Gels, foams, sprays, an ointment, cream, emulsion, Suspension, lotion, milk or paste. 6. Copolymer A) as defined in any one of claims 1 to 4. 7. Copolymer A) according to claim 6, obtainable by radical copolymerization of a) 10 to 45% by weight, based on the total weight of components a) to d), of methacrylic acid amide, b) 60 to 90% by weight, based on the total weight of components a) to d), vinyl pyrrolidone and / or vinyl caprolactam, c) 0 to 25% by weight, based on the total weight of components a) to d) of at least one of a) and b) different and thus copolymerizable unsaturated water-soluble compound, optionally in the presence of up to 20% by weight, based on the total weight of components a) to d), polymers d2) and / or starch and starch derivatives d3). 8. Copolymer A) according to claim 7, obtainable by radical polymerization of a) 30 to 40% by weight of methacrylic acid amide, b) 30 to 60% by weight of vinyl pyrrolidone, in the presence of 1 to 20% by weight of polymers d2) and / or starch and starch derivatives d3). 9. Copolymer A) according to claim 7, obtainable by radical polymerization of a) 30 to 40% by weight of methacrylic acid amide, b) 20 to 60% by weight vinyl pyrrolidone and 1 to 20% by weight vinyl caprolactam. 10. Copolymer A) according to claim 7, obtainable by radical polymerization of a) 30 to 40% by weight of methacrylic acid amide, b) 20 to 60 wt .-% vinyl pyrrolidone and c) 1 to 20 wt .-% of at least one of a) and b) different, copolymerizable therewith water-soluble compound. 11. Use of a copolymer A), as in one of claims 1 defined up to 4, in skin cleansers, care products and to protect the skin, nail care products, preparations for decorative cosmetics and hair treatment products. 12. Use according to claim 11 in hair treatment compositions as Firming and / or as a conditioner. 13. Use according to claim 12, wherein the agent in the form of a Hair gels, shampoos, foaming agents, hair lotions, hair sprays or hair foam. 14. Use of a copolymer A) as in one of claims 1 defined to 4, as an aid in pharmacy, preferred as or in coating compositions for solid pharmaceutical forms as well as or in coating agent (s) for the textile, Paper, printing and leather industries.