DE10227500A1 - Use of cationic polymers in cosmetic formulations, especially shampoos and other hair-care preparations, involves using polymers obtained by polymerisation of quaternary nitrogen monomers in presence of polyether compounds - Google Patents

Abstract

Cationic polymers for use in cosmetic formulations are obtained by polymerisation of quaternised nitrogen-containing monomers in presence of polyether-containing compounds in a reaction mixture with a water content of less than 20 wt%. Cationic polymers (CP) are used in cosmetic preparations, where CP are obtained by the polymerisation of (a) 3-30 wt% quaternary nitrogen-containing radically-polymerizable monomer(s) (a1) and/or direct precursor(s) thereof (a2) in the presence of (b) 70-97 wt% polyether-containing compound(s), (c) optionally 0-15 wt% other comonomers with a water solubility of more than 60 g/l at 25[deg]C and (d) optionally 0-15 wt% other comonomers with a water solubility of less than 60 g/l at 25[deg]C. The water content of the reaction mixture during polymerisation is less than 20 wt%, compounds (a2) (if used) are converted into compounds with quaternary N (a2') during or after polymerisation, and the mol ratio of (a1 + a2' + c) to monomers (d) is at least 2:1. Independent claims are also included for: (1) the inventive cationic polymers (CP); (2) a method as described above for the production of CP; and (3) cosmetic hair formulations containing (A) 0.05-20 wt% CP, 20-99.95 wt% water and/or alcohol and 0-79.05 wt% other components (OC), or (B) 0.1-10 wt% CP, 20-99.9 wt% water and/or alcohol, 0-70 wt% propellant and 0-20 wt% OC, or (C) 0.1-10 wt% CP, 55-94.8 wt% water and/or alcohol, 5-20 wt% propellant, 0.1-5 wt% emulsifier and 0-10 wt% OC, or (D) 0.1-10 wt% CP, 60-99.85 wt% water and/or alcohol, 0.05-10 wt% gel-former and 0-20 wt% OC, or (E) 0.05-10 wt% CP, 25-94.95 wt% water, 5-50 wt% surfactant, 0-5 wt% other conditioning agent and 0-10 wt% OC.

Description

The present invention relates to cationic polymers, processes for their preparation, and their use in cosmetic formulations. The cationic Graft polymers are available through polymerization of quaternized cationic, radical polymerizable monomers and optionally other radically copolymerizable Monomers in the presence of a polyether-containing compound with the proviso that the implementation in the presence of small amounts of water from below 20 wt .-% of the total reaction mixture takes place.

DE 197 14 714 A1 describes linear block polymers of polyethylene glycol and cationic monomers, which are synthesized using macroinitiators. The compounds are used as polymeric surfactants. Grafting reactions which lead to branched polymers are not described and, according to the inventors, can be neglected in the described method (Lieske A and Jaeger W (1998) Macromol Chem Phys 199: 255-260; see in particular p. 256; left column, last paragraph: "Side reactions, particularly grafting onto the PEG chain and transfer reactions leading to DADMAC homopolymer, are neglectable").

DE-A 29 24 663 and US 4,380,600 describe the radical polymerization of ethylenically unsaturated monomers in aqueous solution using water-soluble polymers as dispersants. Polyethylene glycol is used as the water-soluble polymer. Quaternary ammonium compounds are also used as the ethylenically unsaturated monomer. The process described is a water-in-water ("W / W") emulsion polymerization, which has significant proportions of water. The ethylenically unsaturated monomers are used in a weight ratio of 3 to 150 parts to 100 parts of water. The weight ratio of ethylenically unsaturated monomer to the water-soluble polymer (for example polyethylene glycol) is 1: 5 to 5: 1. The high proportion of water means that, in this procedure, there is no or only a very small proportion of the grafting of the ethylenically unsaturated monomers onto the water-soluble polymer. The water-soluble polymer (for example polyethylene glycol) has the function of a dispersant for the aqueous dispersion.

EP-A 0 183 466 describes processes for the polymerization of water-soluble monomers in aqueous solution in the presence of a dispersant and a salt. Polyethylene glycol can be used as a dispersing agent. Water soluble monomers include certain cationic monomers. The high water content typical of a "W / W" emulsion polymerization means that no or only a very small amount of grafting of the ethylenically unsaturated monomers onto the water-soluble polymer takes place in this process. The water-soluble polymer (eg polyethylene glycol) has the function of a dispersing agent. Grafting of the monomers onto the dispersant is not mentioned. The compounds obtained are used as flocculants for wastewater treatment or in the paper industry. Use in cosmetic preparations is not described.

EP-A1 0 880 548 and DE 195 21 096 A1 describe processes for the preparation of dispersions of water-soluble vinyl polymers and stabilizers for carrying out the process. Graft polymers consisting of a backbone made of polyethylene oxide and graft branches made of cationic, preferably quaternary, vinyl polymers are described as stabilizers. The stabilizer is synthesized as described in Example 1 in aqueous solution. The weight ratio of ethylenically unsaturated monomer: polyethylene glycol: water is 24: 30: 270. The use of these stabilizers in cosmetic preparations is not mentioned. A disadvantage of the process described is the high proportion of water in the reaction mixture. With this procedure, there is no or only a very small proportion of grafting of the ethylenically unsaturated monomers onto the water-soluble polymer, i.e. polymers from the cationic monomer and polyethylene glycol are present to a considerable extent individually without grafting (see statement in Lieske A & Jaeger W (1998) Macromol Chem Phys 199: 255-260; see above). This affects the quality of the product, especially its suitability in cosmetics. Here, polyethylene glycol acts as a dispersing agent.

EP-A 1 123 942 describes the polymerization of anionic (carboxylic) ethylenically unsaturated monomers in a melt of polyethylene glycol. The carboxyl groups contained in the polymer are then at least partially reacted by adding an alkyleneimine. Primary amino groups are preferably obtained. Secondaries may also be possible. Tertiary or quaternary are not described and are also not accessible by the claimed method.

DD 117 326 describes the production of quaternized graft polymers using a two-stage process. There is first a polymerization of nonionic ethylenically unsaturated monomers (3-chloro-2-hydroxypropyl acrylate or vinylimidazole) in a melt of polyethylene glycol. The quaternization takes place starting from the polymer obtained in a second step by conversion with triethylamine or methyl iodide. The polymers are used in the production of photographic gelatin-halosilver emulsion layers. Use in the field of cosmetics is not described. The described method has disadvantages from an economic and procedural point of view. On the one hand is the process control tion due to the two-stage process. On the other hand, the method - for example as a result of an incomplete second reaction step - can lead to polymers with non-reproducible properties. The second implementation step also requires, in some cases, toxic compounds which further complicate manufacture and - particularly when the polymer is used in, for example, the cosmetic field of application - force cleaning.

WO 00/49998 describes polymerization processes of vinyl esters in polyether-containing compounds such as polyethylene glycol. In addition - optionally - other monomers such as cationic monomers can be used. The process includes the subsequent saponification of the polymer. In the case of the polymers described, the proportion of optionally additionally used monomers is limited to a maximum of 50% (see p. 9 / line 32 ff.). It is preferably 0 to 20%.

US 3,990,459 describes cosmetic compositions containing grafted cationic polymers. Said grafted cationic polymers are obtained by copolymerization of 3 to 95% by weight of dimethylaminoethyl methacrylate, 2 to 50% by weight of polyethylene glycol and 3 to 95% by weight of a further monomer such as N-vinylpyrrolidone. A quaternization of dimethylaminoethyl methacrylate can be carried out, for example, with dimethyl sulfate. In the polymers described here, the proportion of polyethylene glycol according to the claim is not greater than 50% by weight. In the examples according to the invention, it is even significantly lower, namely 10% by weight.

US 4,408,301 describes shampoo compositions containing grafted cationic polymers. Said grafted cationic polymers are obtained by copolymerization of 3 to 95% by weight of N-vinylpyrrolidone, 3 to 95% by weight of dimethylaminoethyl methacrylate and 2 to 50% by weight of polyethylene glycol. A quaternization of dimethylaminoethyl methacrylate can be carried out, for example, with dimethyl sulfate. In the polymers described here, the proportion of polyethylene glycol according to the claim is not greater than 50% by weight. In the examples according to the invention, it is even significantly lower, namely 8.15 and 8.81% by weight.

DE 2 623 692 describes hair dyes that contain grafted cationic polymers. Said grafted cationic polymers are obtained by copolymerization of N-vinylpyrrolidone, dimethylaminoethyl methacrylate and polyethylene glycol. A quaternization of dimethylaminoethyl methacrylate can be carried out, for example, with dimethyl sulfate. The graft polymers are preferably obtained by copolymerization of 3 to 95% by weight of N-vinylpyrrolidone, 3 to 95% by weight of dimethylaminoethyl methacrylate and 2 to 50% by weight of polyethylene glycol. In the polymers described here, the proportion of polyethylene glycol according to the claim is not greater than 50% by weight. In the examples according to the invention, it is even significantly lower, namely 8.15 and 8.81% by weight.

For the conditioning and strengthening of keratinous substances such as hair, nails and For years, synthetic polymers have also been used on skin. conditions hair conditioning agents are e.g. a strong reduction in the required combing force in wet as well as dry hair, good detangling the first time Scouring (English "Detangling") and good tolerance with other formulation components. Requirements for hair setting resins are e.g. a strong consolidation with high humidity, elasticity, washability of hair and tolerance with other formulation components. Creates difficulties the combination of different properties. So show polymers with good strength properties often low elasticities, see above that with mechanical stress on the hairstyle the strengthening effect damage the polymer film is often significantly affected. In addition, synthetic Polymers in cosmetic formulations, the pigments or cosmetic contain effective active components as a compatibility agent to achieve a homogeneous, stable formulation.

Despite the extensive effort, there is there is still a need for improvement in polymers to produce elastic Hairstyles with strong strengthening even at high humidity, good washability and good grip of the hair. The need for improvement also exists with polymers for the production of easily combable detangled hair and for conditioning skin and hair in their properties that can be sensed such as handle, volume, manageability etc. Also clear are watery Preparations of these polymers are desirable which therefore has good compatibility with other formulation components distinguished.

The task was to create new ones Polymers for in particular to provide hair cosmetic formulations that on the one hand the hairstyle a strong consolidation with a high one elasticity and on the other hand the hair is easy to comb at the same time voluminous Give appearance and make clear preparations with water.

The task is through the deployment of the polymers according to the invention solved.

• 3 bis 30 Gew.-% mindestens eines quaternären Stickstoff enthaltenden radikalisch polymerisierbaren Monomers (a1) und/oder eines direkten Vorproduktes (a2) desselben,
• in Gegenwart von 70 bis 97 Gew.-% mindestens einer polyetherhaltigen Verbindung (b) und
• gegebenenfalls 0 bis 15 Gew.-% eines oder mehrerer weiterer radikalisch polymerisierbarer Monomere (c) mit einer Wasserlöslichkeit oberhalb 60 g/l bei 25°C und
• gegebenenfalls 0 bis 15 Gew.-% eines oder mehrerer weiterer radikalisch polymerisierbarer Monomeren (d) mit einer Wasserlöslichkeit unterhalb 60 g/l bei 25°C
• wobei der Wassergehalt im Reaktionsgemisch während der Polymerisation weniger als 20 Gew.-% beträgt, und wobei bei Verwendung eines Vorproduktes (a2) dieses im Anschluss an oder während der Polymerisation zumindest teilweise in eine Verbindung mit quaternärem Stickstoff (a2') umgesetzt wird, wobei das molare Verhältnis der Summe der Monomeren (a1), (a2') und (c) zu der Summe der Monomeren (d) mindestens 2 zu 1 beträgt, und wobei sich die Gew.-% der einzelnen Komponenten a1 und/oder a2, b und gegebenenfalls c und d auf jeweils 100 Gew.-% addieren,
• in kosmetischen Zubereitungen.

A first object of the invention relates to the use of cationic polymers, obtainable by polymerizing

• 3 to 30% by weight of at least one quaternary nitrogen-containing free-radically polymerizable monomer (a1) and / or a direct precursor (a2) thereof,
• in the presence of 70 to 97% by weight of at least one polyether-containing compound (b) and
• optionally 0 to 15% by weight of one or more further radically polymerizable monomers (c) with a water solubility above 60 g / l at 25 ° C. and
• optionally 0 to 15% by weight of one or more further radically polymerizable monomers (d) with a water solubility below 60 g / l at 25 ° C.
• wherein the water content in the reaction mixture during the polymerization is less than 20% by weight, and wherein if a preliminary product (a2) is used, this is at least partially converted into a compound with quaternary nitrogen (a2 ') after or during the polymerization, wherein the molar ratio of the sum of the monomers (a1), (a2 ') and (c) to the sum of the monomers (d) is at least 2 to 1, and the weight% of the individual components a1 and / or a2, add b and optionally c and d to 100% by weight,
• in cosmetic preparations.

• 3 bis 30 Gew.-% mindestens eines kationischen, quarternären radikalisch polymerisierbaren Monomers (a1) und
• in Gegenwart von 70 bis 97 Gew.-% mindestens einer polyetherhaltigen Verbindung (b) und
• gegebenenfalls 0 bis 15 Gew.-% eines oder mehrerer weiterer radikalisch polymerisierbarer Monomere (c) mit einer Wasser löslichkeit oberhalb 60 g/l bei 25°C und
• gegebenenfalls 0 bis 15 Gew.-% eines oder mehrerer weiterer radikalisch polymerisierbarer Monomere (d) mit einer Wasserlöslichkeit unterhalb 60 g/l bei 25°C,
• wobei das molare Verhältnis der Summe der Monomeren (a1) und (c) zu der Summe der Monomeren (d) mindestens 2 zu 1 beträgt, wobei der Wassergehalt im Reaktionsgemisch während der Polymerisation weniger als 20 Gew.-% beträgt, und wobei sich die Gew.-% der einzelnen Komponenten a1, b und gegebenenfalls c und d auf jeweils 100 Gew.-% addieren.

Another object of the invention relates to polymers, obtainable by polymerization of

• 3 to 30% by weight of at least one cationic, quaternary free-radically polymerizable monomer (a1) and
• in the presence of 70 to 97% by weight of at least one polyether-containing compound (b) and
• optionally 0 to 15% by weight of one or more further radically polymerizable monomers (c) with a water solubility above 60 g / l at 25 ° C. and
• optionally 0 to 15% by weight of one or more further free-radically polymerizable monomers (d) with a water solubility below 60 g / l at 25 ° C.,
• wherein the molar ratio of the sum of the monomers (a1) and (c) to the sum of the monomers (d) is at least 2 to 1, the water content in the reaction mixture during the polymerization being less than 20% by weight, and the Add% by weight of the individual components a1, b and optionally c and d to 100% by weight.

The use of said is also included polymers according to the invention in the applications listed below, especially in cosmetic preparations.

• 3 bis 30 Gew.-% mindestens eines kationischen, quarternären radikalisch polymerisierbaren Monomers (a1)
• in Gegenwart von 70 bis 97 Gew.-% mindestens einer polyetherhaltigen Verbindung (b) und
• gegebenenfalls 0 bis 15 Gew.-% eines oder mehrerer weiterer radikalisch polymerisierbarer Monomere (c) mit einer Wasserlöslichkeit oberhalb 60 g/l bei 25°C und
• gegebenenfalls 0 bis 15 Gew.-% eines oder mehrerer weiterer radikalisch polymerisierbarer Monomere (d) mit einer Wasserlöslichkeit unterhalb 60 g/l bei 25°C,
• polymerisiert wird, wobei das molare Verhältnis der Summe der Monomeren (a1) und (c) zu der Summe der Monomeren (d) mindestens 2 zu 1 beträgt, wobei der Wassergehalt im Reaktionsgemisch während der Polymerisation weniger als 20 Gew.-% beträgt, und wobei sich die Gew.-% der einzelnen Komponenten a1, b und gegebenenfalls c und d auf jeweils 100 Gew.-% addieren.

Another object of the invention relates to processes for the preparation of the polymers according to the invention, characterized in that

• 3 to 30% by weight of at least one cationic, quaternary free-radically polymerizable monomer (a1)
• in the presence of 70 to 97% by weight of at least one polyether-containing compound (b) and
• optionally 0 to 15% by weight of one or more further radically polymerizable monomers (c) with a water solubility above 60 g / l at 25 ° C. and
• optionally 0 to 15% by weight of one or more further free-radically polymerizable monomers (d) with a water solubility below 60 g / l at 25 ° C.,
• is polymerized, the molar ratio of the sum of the monomers (a1) and (c) to the sum of the monomers (d) being at least 2 to 1, the water content in the reaction mixture during the polymerization being less than 20% by weight, and where the wt .-% of the individual components a1, b and optionally c and d add up to 100 wt .-%.

The polymers according to the invention have a excellent dry and wet combability of the hair treated with them. Other benefits are below among other things the soft feel and the antistatic properties of the surfaces treated with it such as textiles, hair, skin, paper, fiber and non-woven materials, but also other surfaces. Pigments or preparations with cosmetically active components are stabilized by the polymers. Another advantage is that with the polymers according to the invention aqueous Compositions such as hair shampoos and washing gels are clearly formulated can be. Furthermore can the polymers are used in the form of aqueous or aqueous / alcoholic Solutions, as watery Emulsion, microemulsion, dispersion, opaque or transparent gels or aerosols.

Of essential importance for the excellent conditioning properties is a proportion of at least 70% by weight of polyether-containing compounds in the polymers according to the invention, which are different from those in US 3,990,459 . US 4,048,301 and DE 26 23 692 the polymers disclosed stand out clearly.

In the preparation of the polymers used according to the invention, grafting onto the polyether-containing compounds (b) can occur during the polymerization, which can lead to the advantageous properties of the polymers. Depending on the degree of grafting, the polymers used according to the invention include both pure graft polymers and mixtures of the above graft polymers with ungrafted polyether-containing compounds and homo- or copolymers of the monomers (a1) and, if appropriate, (a2), (c) and (d). The properties of the polymers according to the invention stand out clearly from mixtures in which the polymerization is carried out in the presence of relatively amounts is realized (see comparative experiment 1) or in which the polyether component is added only after the polymerization of the monomers (see comparative experiment 2). However, mechanisms other than grafting are also conceivable that can cause these changed, advantageous properties.

Both polyalkylene oxides based on ethylene oxide, propylene oxide, butylene oxide and other alkylene oxides and polyglycerol can be used as the polyether-containing compounds (b). Depending on the type of monomer building blocks, the polymers contain the following structural units. - (CH ₂ ) ₂ -O-, - (CH ₂ ) ₃ -O-, (CH ₂ ) ₄ -O-, -CH ₂ -CH (R ⁶ ) -O-, -CH ₂ -CHOR ⁷ -CH ₂ -O- With
R ⁶ C ₁ -C ₂₄ alkyl;
R ^{7 is} hydrogen, C ₁ -C ₂₄ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -.

This can be the case with the structural units both homopolymers and statistical copolymers and block copolymers act.

in der die Variablen unabhängig voneinander folgende Bedeutung haben:
R¹ Wasserstoff, C₁-C₂₄-Alkyl, R⁶-C(=O)-, R⁶-NH-C(=O)-, Polyalkoholrest;
R⁵ Wasserstoff, C₁-C₂₄-Alkyl, R⁶-C(=O)-, R⁶-NH-C(=O)-;
R² bis R⁴
unabhängig voneinander für -(CH₂)₂-, -(CH₂)₃-, -(CH₂)₄-, -CH₂-CH(R⁶)-, -CH₂-CHOR⁷-CH₂-;
R⁶ C₁-C₂₄-Alkyl;
R⁷ Wasserstoff, C₁-C₂₄-Alkyl, R⁶-C(=O)-, R⁶-NH-C(=O)-;
A -C(=O)-O, -C(=O)-B-C(=O)-O, -CH₂-CH(-OH)-B-CH(-OH)-CH₂-O, -C(=O)-NH-B-NH-C(=O)-O,

B -(CH₂)_t-, Arylen, ggf. substituiert;
R³⁰, R³¹
unabhängig voneinander für Wasserstoff, C₁-C₂₄-Alkyl, C₁-C₂₄-Hydroxyalkyl, Benzyl oder Phenyl;
n 1 wenn R¹ kein Polyalkoholrest ist oder
n 1 bis 1000 wenn R¹ ein Polyakoholrest ist
s 0 bis 1000;
t 1 bis 12;
u 1 bis 5000;
v 0 bis 5000;
w 0 bis 5000:
x 0 bis 5000;
y 0 bis 5000;
z 0 bis 5000.Polymers of the general formula I are preferably used as polyether (b),

in which the variables have the following meaning independently of one another:
R ^{1 is} hydrogen, C ₁ -C ₂₄ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -, polyalcohol radical;
R ^{5 is} hydrogen, C ₁ -C ₂₄ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -;
R ² to R ⁴
independently for - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH ₂ -CH (R ⁶ ) -, -CH ₂ -CHOR ⁷ -CH ₂ -;
R ⁶ C ₁ -C ₂₄ alkyl;
R ^{7 is} hydrogen, C ₁ -C ₂₄ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -;
A -C (= O) -O, -C (= O) -BC (= O) -O, -CH ₂ -CH (-OH) -B-CH (-OH) -CH ₂ -O, -C (= O) -NH-B-NH-C (= O) -O,

B - (CH ₂ ) _t -, arylene, optionally substituted;
R ³⁰ , R ³¹
independently of one another for hydrogen, C ₁ -C ₂₄ -alkyl, C ₁ -C ₂₄ -hydroxyalkyl, benzyl or phenyl;
n 1 if R ^{1 is} not a polyalcohol radical or
n 1 to 1000 if R ^{1 is} a polyalcohol radical
s 0 to 1000;
t 1 to 12;
u 1 to 5000;
v 0 to 5000;
w 0 to 5000:
x 0 to 5000;
y 0 to 5000;
z 0 to 5000.

The terminal primary or secondary hydroxyl groups of the polyethers prepared on the basis of polyalkylene oxides and the secondary OH groups of polyglycerol can be freely available both in unprotected form and with a chain length C with alcohols, such as mono-, di-, tri- or polyalcohols ₁ -C ₂₄ or with carboxylic acids with a chain length of C ₁ -C _{24 are} etherified or esterified and optionally crosslinked or reacted with isocyanates, diisocyanates or triisocyanates to form urethanes and optionally crosslinked.

As alkyl radicals for R ¹ and R ⁵ to R ⁷ are branched or unbranched C ₁ -C ₂₄ alkyl chains, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1- Ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-ethylhexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n- Called nonadecyl or n-eicosyl.

Preferred representatives of the above-mentioned alkyl radicals are branched or unbranched C ₁ to C ₁₂ , particularly preferably C ₁ to C _6, alkyl chains.

The molecular weight of the polyether is in the range less than 1,000,000 (by number average), preferably in Range from 300 to 100,000, particularly preferably in the range from 500 to 50,000, very particularly preferably in the range from 600 to 20,000.

Homopolymers from ethylene oxide or Copolymers of ethylene oxide and propylene oxide are particularly preferred being the molar ratio from ethylene oxide to propylene oxide preferably in a range from 1: 9 to 9: 1 lies. It is advantageous to use homopolymers of Ethylene oxide or copolymers, with an ethylene oxide content of 9 to 99 mol%. For the preferred ethylene oxide polymers to use the proportion of copolymerized ethylene oxide 10 to 100 mol%. As Comonomer for these copolymers come with propylene oxide, butylene oxide and / or isobutylene oxide into consideration. Copolymers of ethylene oxide are suitable, for example and propylene oxide, copolymers of ethylene oxide and butylene oxide and copolymers of ethylene oxide, propylene oxide and at least a butylene oxide. The ethylene oxide content of the copolymers is preferably 10 to 99 mol%, the propylene oxide proportion 1 to 90 mol% and the proportion Butylene oxide in the copolymers 1 to 30 mol%. In addition to straight chain can also branched homopolymers or copolymers as polyether-containing compounds (b) can be used.

Branched polymers can be produced by, for example, polyalcohol residues, e.g. to pentaerythritol, Glycerin or on sugar alcohols like D-sorbitol and D-mannitol also on polysaccharides such as cellulose and starch, ethylene oxide and optionally nor propylene oxide and / or butylene oxides. The alkylene oxide units can be statistically distributed in the polymer or in the form of blocks.

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

Particularly preferred polyethers (b) are polymers of the general formula I with an average molecular weight of 300 to 100,000 (by number average), in which the variables have the following meaning independently of one another:
R ¹ is hydrogen, C ₁ -C1 ₂ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -, polyalcohol radical;
R ^{5 is} hydrogen, C ₁ -C ₁₂ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -;
R ² to R ⁴ - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH ₂ -CH (R ⁶ ) -, -CH ₂ -CHOR ⁷ -CH ₂ - ;
R ⁶ C ₁ -C ₁₂ alkyl;
R ^{7 is} hydrogen, C ₁ -C ₁₂ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -;
n 1 if R ^{1 is} not a polyalcohol radical or
n 1 to 8 when R ^{1 is} a polyalcohol radical
s 0;
u 2 to 2000;
v 0 to 2000;
w 0 to 2000.

Polymers i of general formula I with an average molecular weight of 600 to 20,000 (based on the number average), in which the variables have the following meaning independently of one another, are very particularly preferred as polyether (b):
R ^{1 is} hydrogen, C ₁ -C ₆ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -;
R ^{5 is} hydrogen, C ₁ -C ₆ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -;
R ² to R ⁹ - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH ₂ -CH (R ⁶ ) -, -CH ₂ -CHOR ⁷ -CH ₂ - ;
R ⁶ C ₁ -C ₆ alkyl;
R ^{7 is} hydrogen, C ₁ -C ₆ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -;
n 1;
s 0;
u 5 to 500;
v 0 to 500;
w 0 to 500.

However, silicone derivatives can also be used as the polyether. Suitable silicone derivatives are those known under the INCI name of Dimethicone copolyols or silicone surfactants such as those available under the trade names Abil ^® (Fa. T. Goldschmidt), Alkasil ^® (Fa. Rhône-Poulenc), Silicone Polyol Copolymer ^® (Fa Genesee), Belsil ^® (from Wacker), Silwet ^® (from Witco, Greenwich, CT, USA) or Dow Corning (from Dow Corning). These include compounds with the CAS numbers 64365-23-7; 68937-54-2; 68938-54-5; 68937-55-3.

Silicones are used in hair cosmetics generally used to improve the grip. The usage of polyether-containing silicone derivatives as polyether (b) in the polymers of the invention therefore additionally lead to an improvement in the grip of the hair.

wobei
R⁹ =CH₃ oder

R¹⁰ = CH₃ oder R⁹ R¹¹ = H, CH₃,

Preferred representatives of such polyether-containing silicone derivatives are those which contain the following structural elements:

in which
R ⁹ = CH ₃ or

R ¹⁰ = CH ₃ or R ⁹ R ¹¹ = H, CH ₃ ,

mit der Maßgabe, daß mindestens einer der Reste R⁸, R⁹ oder R¹⁰ ein polyalkylenoxidhaltiger Rest nach obengenannter Definition ist, und
f eine ganze Zahl von 1 bis 6 ist,
a und b ganze Zahlen derart sind, dass das Molekulargewicht des Polysiloxan-Blocks zwischen 300 und 30000 liegt,
c und d ganze Zahlen zwischen 0 und 50 sein können mit der Maßgabe, dass die Summe aus c und d größer als 0 ist, und e 0 oder 1 ist.R ^{13 is} an organic radical of 1 to 40 carbon atoms, which may contain amino, carboxylic acid or sulfonate groups or, if e = 0, also means the anion of an inorganic acid,
and wherein the radicals R ^{8 can be} identical or different and either come from the group of aliphatic hydrocarbons with 1 to 20 carbon atoms, are cyclic aliphatic hydrocarbons with 3 to 20 C atoms, are aromatic in nature or are equal to R ¹² , where:

with the proviso that at least one of the radicals R ⁸ , R ⁹ or R ^{10 is} a polyalkylene oxide-containing radical as defined above, and
f is an integer from 1 to 6,
a and b are integers such that the molecular weight of the polysiloxane block is between 300 and 30000,
c and d can be integers between 0 and 50, with the proviso that the sum of c and d is greater than 0 and e is 0 or 1.

Preferred radicals R ⁹ and R ¹² are those in which the sum of c + d is between 5 and 30.

The groups R ⁸ are preferably selected from the following group: methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl, dodecyl and octadecyl, cycloaliphatic radicals, especially cyclohexyl, aromatic groups, especially phenyl or naphthyl, mixed aromatic-aliphatic radicals such as benzyl or phenylethyl as well as tolyl and xylyl and R ¹² , particularly suitable radicals R ¹¹ are those in which in the case of R ¹¹ = - (CO) _e -R ¹³ R ¹³ any alkyl, cycloalkyl or Aryl residue means between 1 and 40 C atoms and which can carry further ionogenic groups such as NH ₂ , COOH, SO ₃ H.

Preferred inorganic radicals R ¹³ are, for the case e = 0, phosphate and sulfate.

Particularly preferred polyether-containing silicone derivatives are those of the general structure:

Furthermore, as polyether (b) Homopolymers and copolymers of polyalkylene oxide-containing ethylenically unsaturated Monomers such as polyalkylene oxide (meth) acrylates, polyalkylene oxide vinyl ethers, Polyalkylene oxide (meth) acrylamides, polyalkylene oxide allylamides or Polyalkylene oxide vinyl amides can be used. Of course you can too Copolymers of such monomers with other ethylenically unsaturated Monomers are used.

As polyether-containing compounds b) can but also reaction products of polyethyleneimines with alkylene oxides be used. In this case, preferred alkylene oxides are preferred Ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, particularly preferably used ethylene oxide. As polyethyleneimines can Polymers with number average molecular weights from 300 to 20,000, preferably 500 to 10,000, very particularly preferably 500 to 5000, be used. The weight ratio between inserted Alkylene oxide and polyethyleneimine range from 100: 1 to 0.1: 1, preferably in the range 50: 1 to 0.5: 1, very particularly preferably in the range 20: 1 to 0.5: 1.

The polyether (b) is most preferably a homopolymer of ethylene oxide or to a block copolymer of ethylene oxide / propylene oxide with a Molecular weight below 100,000 g / mol, preferably below 20,000 g / mol. The blocks can in the form A-B or A-B-A or B-A-B or other combinations available.

• 1) Quaternäre Vinylamine der allgemeinen Formeln (IIIa) und (IIIb) sowie deren Salze: W-(CH₂)_n-CR¹⁵=CHR¹⁴ (IIIa)
  
  wobei gilt: R¹⁴ und R¹⁵ sind unabhängig voneinander ausgewählt 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, n ist 0, 1 oder 2, W ist -N +(R¹⁶ )₃/x^– oder
  
  , X^– wobei die Reste R¹⁶ identisch oder verschieden ausgewählt werden können aus der Gruppe bestehend aus C₁-C₄₀ linear- oder verzweigtkettige Alkylreste, Formyl, C₁-C₁₀ linear- oder verzweigtkettige Acyl, N,N-Dimethylaminoethyl, 2-Hydroxyethyl, 2-Methoxyethyl, 2-Ethoxyethyl, Hydroxypropyl, Methoxypropyl, Ethoxypropyl oder Benzyl, bevorzugt sind Methyl, Ethyl und n-Propyl, X^– ist ein Anion, bevorzugt ein Anion das kosmetisch verträglich ist. Bevorzugt sind als Anion Acetat, Methylsulfat oder Halogenid wie insbesondere Chlorid oder Bromid.
• 2) Quaternäre N,N,N-Trialkylaminoalkylacrylate und -methacrylate und quaternäre N,N,N-Trialkylaminoalkylacrylamide und -methacrylamide der allgemeinen Formel (IV) sowie deren Salze.
  
  wobei R¹⁴, R¹⁵ und W die gleiche Bedeutung wie in der allgemeinen Formel IIIa und IIIb haben, und R¹⁷ = Wasserstoff oder Methyl, R¹⁸ = Alkylen oder Hydroxyalkylen mit 1 bis 24 C-Atomen, optional substituiert durch Alkyl, bevorzugt C₂H₄, C₃H₆, C₄H₈, CH₂-CH(OH)-CH₂ g = 0 oder 1 Z = Stickstoff für g = 1 oder Sauerstoff für g = 0 Die erfindungsgemäß umfassten Amide können unsubstituiert, N-Alkyl oder N-Alkylamino monosubstituiert oder N,N-dialkylsubstituiert oder N,N-dialkylaminodisubstituiert vorliegen, worin die Alkyl- oder Alkylaminogruppen von C₁-C₄₀ linearen, C₃-C₄₀ verzweigtkettigen, oder C₃-C₄₀ carbocyclischen Einheiten abgeleitet sind. Bevorzugte Monomere der Formel (IV) sind die Salze von N,N,N-Trimethylaminomethyl(meth)acrylat, N,N,N-Triethylaminomethyl(meth)acrylat, N,N,N-Trimethylaminoethyl(meth)acrylat, N,N,N-Triethylaminoethyl-(meth)acrylat, N,N,N-Trimethylaminobutyl(meth)acrylat, N,N,N-Triethylaminobutyl(meth)acrylat, N,N,N-Trimethylaminohexyl(meth)acrylat, N,N,N-Trimethylaminooctyl(meth)acrylat, N,N,N-Trimethylaminododecyl(meth)acrylat. Ferner sind bevorzugt die Salze von N-[3-(Trimethylamino)propyl]methacrylamid und N-[3-(Trimethylamino)propyl]acrylamid, N-[3-(Dimethylamino)butyl]methacrylamid, N-[8-(Trimethylamino)octyl]methacrylamid, N-[12-(Trimethylamino)dodecyl]methacrylamid, N-(3-(Triethylamino)propyl]methacrylamid und N-(3-(Triethylamino)propyl]acrylamid. Weiterhin bevorzugt sind (Meth)acryloyloxyhydroxypropyltrimethylammoniumchlorid und (Meth)acryloyloxyhydroxypropyltriethylammoniumchlorid. Ganz besonders bevorzugt sind N,N,N-Trimethylaminoethylmethacrylat und N-[3-(Trimethylamino)propyl]methacrylamid.
• 3) Quaternäre N-Vinylimidazole der allgemeinen Formel (V) sowie deren Salze,
  
  wobei R¹⁹ bis R²¹ unabhängig voneinander für Wasserstoff, C₁-C₄-Alkyl, C₁-C₄-Hydroxyalkyl oder Phenyl; und R²² für C₁-C₄-Alkyl, C₁-C₄-Hydroxyalkyl oder Phenyl; und und X^– für ein Anion steht, bevorzugt ein Anion das kosmetisch verträglich ist. Bevorzugt sind als Anion Acetat, Methylsulfat oder Halogenid wie insbesondere Chlorid oder Bromid. Besonders bevorzugt sind 3-Methyl-1-vinylimidazoliumchlorid, 3-Methyl-1-vinylimidazoliummethylsulfat.
• 4) Quaternäre Vinylpyridine der allgemeinen Formel (VI) sowie deren Salze, R²¹, R²² und X^– die gleiche Bedeutung wie in der allgemeinen Formel V haben.
  
• 5) Weitere geeignete Monomere sind Diallylamine der allgemeinen Formel (VII) sowie deren Salze
  
  wobei R²³ und R²⁴ jeweils und unabhängig voneinander C₁- bis C₂₄-Alkyl sein können und X^– die gleiche Bedeutung wie in Formel (V) hat. Besonders bevorzugt ist N,N-Dimethyl-N,N-diallylammoniumchlorid.

For the polymerization in the presence of the polyether (b), component (a1) uses radically polymerizable monomers with at least one quaternary nitrogen. In the context of this invention, quaternary nitrogen means nitrogen to which four organic radicals are covalently bound. Examples of suitable monomers with a quaternary nitrogen are:

• 1) Quaternary vinylamines of the general formulas (IIIa) and (IIIb) and their salts: W- (CH ₂ ) _n -CR ¹⁵ = CHR ¹⁴ (IIIa)
  
  where: 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. Hydrogen, methyl or ethyl are preferred, n is 0, 1 or 2, W is -N + (R ¹⁶ ) ₃ / x ^- or
  
  , X ^- where the radicals R ¹⁶ can be selected identically or differently from the group consisting of C ₁ -C ₄₀ linear or branched chain alkyl radicals, formyl, C ₁ -C ₁₀ linear or branched chain acyl, N, N-dimethylaminoethyl, 2 -Hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl, ethoxypropyl or benzyl, preferably methyl, ethyl and n-propyl, X ^- is an anion, preferably an anion that is cosmetically compatible. Acetate, methyl sulfate or halide such as, in particular, chloride or bromide are preferred as the anion.
• 2) Quaternary N, N, N-trialkylaminoalkyl acrylates and methacrylates and quaternary N, N, N-trialkylaminoalkylacrylamides and methacrylamides of the general formula (IV) and their salts.
  
  where R ¹⁴ , R ¹⁵ and W have the same meaning as in the general formula IIIa and IIIb, and R ¹⁷ = hydrogen or methyl, R ¹⁸ = alkylene or hydroxyalkylene with 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 = 0 or 1 Z = nitrogen for g = 1 or oxygen for g = 0 The amides included according to the invention can be unsubstituted, N -Alkyl or N-alkylamino monosubstituted or N, N-dialkyl-substituted or N, N-dialkylaminodisubstituted, wherein the alkyl or alkylamino groups of C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched chain, or C ₃ -C ₄₀ carbocyclic units are derived. Preferred monomers of the formula (IV) are the salts of N, N, N-trimethylaminomethyl (meth) acrylate, N, N, N-triethylaminomethyl (meth) acrylate, N, N, N-trimethylaminoethyl (meth) acrylate, N, N , N-triethylaminoethyl (meth) acrylate, N, N, N-trimethylaminobutyl (meth) acrylate, N, N, N-triethylaminobutyl (meth) acrylate, N, N, N-trimethylaminohexyl (meth) acrylate, N, N, N-trimethylaminooctyl (meth) acrylate, N, N, N-trimethylaminododecyl (meth) acrylate. Also preferred are the salts of N- [3- (trimethylamino) propyl] methacrylamide and N- [3- (trimethylamino) propyl] acrylamide, N- [3- (dimethylamino) butyl] methacrylamide, N- [8- (trimethylamino) octyl] methacrylamide, N- [12- (trimethylamino) dodecyl] methacrylamide, N- (3- (triethylamino) propyl] methacrylamide and N- (3- (triethylamino) propyl] acrylamide. (Meth) acryloyloxyhydroxypropyltrimethylammonium chloride and (meth ) Acryloyloxyhydroxypropyltriethylammonium chloride, N, N, N-trimethylaminoethyl methacrylate and N- [3- (trimethylamino) propyl] methacrylamide are very particularly preferred.
• 3) quaternary N-vinylimidazoles of the general formula (V) and their salts,
  
  where R ¹⁹ to R ^{21 are} independently hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl or phenyl; and R ^{22 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl or phenyl; and and X ^{- represents} an anion, preferably an anion that is cosmetically compatible. Acetate, methyl sulfate or halide such as, in particular, chloride or bromide are preferred as the anion. 3-Methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate are particularly preferred.
• 4) Quaternary vinylpyridines of the general formula (VI) and their salts, R ²¹ , R ²² and X ^{- have} the same meaning as in the general formula V.
  
• 5) Other suitable monomers are diallylamines of the general formula (VII) and their salts
  
  where R ²³ and R ^{24 can} each, independently of one another, be C ₁ -C ₂₄ -alkyl and X ^{- has} the same meaning as in formula (V). N, N-Dimethyl-N, N-diallylammonium chloride is particularly preferred.

Of course, mixtures of the different Monomers (a1) from the groups mentioned above together (and, if appropriate, other monomers) are polymerized.

3-Methyl-1-vinylimidazolium chloride is particularly preferred, 3-methyl-1-vinylimidazolium methyl sulfate and N, N-dimethyl-N, Ndiallyl ammonium chloride, and mixtures of the aforementioned. Are very particularly preferred for (a1) Mixtures of 3-methyl-1-vinylimidazolium methyl sulfate and N, N-dimethyl-N, N-diallylammonium chloride.

• 1) Ungesättigte primäre, sekundäre oder tertiäre Amine Die zu den erfindungsgemäßen Polymerisaten führende Quaternisierung der Amine kann beispielsweise durch Umsetzung der in den Monomeren (a2) enthaltenen Aminogruppen mit Alkylhalogenide mit vorzugsweise 1 bis 24 C-Atomen in der Alkylgruppe realisiert werden. Besonders bevorzugt werden eingesetzt Methylchlorid, Methylbromid, Methyliodid, Ethylchlorid, Ethylbromid, Propylchlorid, Hexylchlorid, Dodecylchlorid, Laurylchlorid und Benzylhalogenide, wie insbesondere Benzylchlorid und Benzylbromid. Andere zur Quaternisierung geeignete Agentien umfassen Dialkylsulfate wie insbesondere Dimethylsulfat oder Diethylsulfat. Eine Quaternisierung basischer Aminogruppen kann ferner mit Alkylenoxiden wie Ethylenoxide oder Propylenoxide in Gegenwart von Säuren realisiert werden. Am meisten werden als Agentien für die Quaternisierung eingesetzt: Methylchlorid, Dimethylsulfat oder Diethylsulfat. Ferner ist eine Umsetzung mit quaternisierten Epichlorhydrin der allgemeinen Formel (XII) möglich (s.u.) Beispielhaft jedoch nicht einschränkend seien für die als Monomere (a2) geeigneten Amine zu nennen:
• a) Aminoalkylacrylate- und -methacrylate und Aminoalkylacryl- und -methacrylamide der allgemeinen Formel (VIII)
  
  wobei für R¹⁴ bis R¹⁸ die für Formel (IV) gegebenen Definitionen gelten und 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. Die Amide können unsubstituiert, N-Alkyl oder N-Alkylamino monosubstituiert oder N,N-dialkylsubstituiert oder N,N-dialkylaminodisubstituiert vorliegen, worin die Alkyl- oder Alkylaminogruppen von C₁-C₄₀ linearen, C₃-C₄₀ verzweigtkettigen, oder C₃-C₄₀ carbocyclischen Einheiten abgeleitet sind. Zusätzlich können die Alkylaminogruppen quaternisiert werden. Bevorzugte Comonomere der Formel (VIII) sind N,N-Dimethylaminomethyl(meth)acrylat, N,N-Diethylaminomethyl(meth)acrylat, N,N-Dimethylaminoethyl(meth)acrylat, N,N-Diethylaminoethyl(meth)acrylat, N,N-Dimethylaminobutyl(meth)acrylat, N,N-Diethylaminobutyl(meth)acrylat, N,N-Dimethylaminohexyl(meth)acrylat, N,N-dimethylamino octyl(meth)acrylat, N,N-Dimethylaminododecyl(meth)acrylat. Ferner sind bevorzugt N-[3-(dimethylamino)propyl]methacrylamid, N-[3-(dimethylamino)propyl]acrylamid, N-[3-(Dimethylamino)butyl]methacrylamid, N-[8-(Dimethylamino)octyl]methacrylamid, N-[12-(Dimethylamino)dodecyl]methacrylamid, N-[3-(Diethylamino)propyl]methacrylamid und N-[3-(Diethylamino)propyl]acrylamide. Ganz besonders bevorzugt sind N,N-Dimethylaminoethylmethacrylat, N-[3-(dimethylamino)propyl]methacrylamid, N-Methylaminoethylmethacrylat, N-[3-(Methylamino)propyl]methacrylamid, Aminoethylmethacrylat und N-[3-aminopropyl]methacrylamid. Bevorzugt erfolgt bei den obengenannten Monomeren eine Quaternisierung unter Verwendung Methylchlorid, Methylsulfat oder Diethylsulfat.
• b) N-Vinylimidazole der allgemeinen Formel IX, wobei für R¹⁹ bis R²¹ unabhängig voneinander die für Formel (V) gegebenen Definitionen gelten.
  
  Besonders bevorzugt sind N-Vinylimidazol, 1-Vinyl-2-methylvinylimidazol und eine Quaternisierung mit Methylchlorid, Methylsulfat oder Diethylsulfat.
• c) Diallylamine der allgemeinen Formel (X)
  
  mit R²⁷ = Wasserstoff oder C₁- bis C₂₄-Alkyl. Besonders bevorzugt ist N,N-Diallylamin und eine Quaternisierung mit Methylchlorid oder Methylsulfat.
• d) Ferner kann (a2) ausgewählt sein aus Verbindungen wie 1,3-Divinylimidazolid-2-on oder N-Disubstituierte Vinylaminen der allgemeinen Formel (XI): (R²⁸)₂N-(CH₂)_n-CR¹⁵=CHR¹⁴ (XI) wobei R¹⁴, R¹⁵ und n die gleich Bedeutung wie in den Formeln (IIIa) und (IIIb) haben, und die Reste R²⁸ ausgewählt seien können aus der Gruppe bestehend aus Wasserstoff C₁-C₄₀ linear- oder verzweigtkettige Alkylreste, Formyl, C₁-C₁₀ linear- oder verzweigtkettige Acyl, N,N-Dimethylaminoethyl, 2-Hydroxyethyl, 2-Methoxyethyl, 2-Ethoxyethyl, Hydroxypropyl, Methoxypropyl, Ethoxypropyl oder Benzyl. Bevorzugt sind Methyl, Ethyl, n-Propyl und Benzyl. Dabei gilt, wenn n = 0, dass nicht beide Reste R²⁸ gleichzeitig Wasserstoff sind.
• 2) Ungesättigte Säuren Quaternäre Amine können durch Umsetzung von Säuren, wie sie beispielsweise durch Verwendung von ungesättigten Säuren wie z.B. Acrylsäure oder Methacrylsäure als Ausgangsverbindung (a2) eingebracht würden, mit einem quaternisierten Epichlorhydrin der allgemeinen Formel (XII) erhalten werden.
  
  Dabei ist R²⁹ bevorzugt C₁- bis C₄₀-Alkyl. Bevorzugt wird 2,3-Epoxypropyl-trimethylammoniumchlorid bzw. 3-Chlor-2-hydroxypropyl-trimethylammoniumchlorid eingesetzt. Die Epoxide der Formel XI können auch in situ durch Umsetzung der entsprechenden Chlorhydrine mit Basen, beispielsweise Natriumhydroxid, erzeugt werden. Entsprechend können auch Hydroxy- und/oder Aminogruppen enthaltende Monomere (a2) umgesetzt werden. Bevorzugt sind Hydroxylgruppen der Polyvinylalkohol-Einheiten und Vinylamin-Einheiten, entstanden durch Hydrolyse von Vinylformamid.
• 3) Halogenide radikalisch polymerisierbarer Monomere, wie beispielsweise Halogenalkylacrylate oder Halogenalkylmethacrylate. Bevorzugt sind Chlor-, Brom- oder Iodverbindungen. Beispielhaft jedoch nicht einschränkend sei zu nennen 3-Chlor-2-hydroxypropylacrylat. Die Umsetzung zu quaternären Aminen erfolgt durch Reaktion mit Aminen z.B. Trialkylaminen wie beispielsweise Trimethylamin oder Triethylamin.

Direct precursors (a2) for component (a1) generally include all those free-radically polymerizable monomers which can be converted into a free-radically polymerizable monomer with a quaternary nitrogen. The same definitions as given above for (a1) apply to the compounds (a2 ') obtained as a result. The following free-radically polymerizable monomers are preferred for component (a2) as a direct precursor for (a1):

• 1) Unsaturated primary, secondary or tertiary amines The quaternization of the amines leading to the polymers according to the invention can be achieved, for example, by reacting the amino groups contained in the monomers (a2) with alkyl halides having preferably 1 to 24 carbon atoms in the alkyl group. Methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and benzyl halides, such as in particular benzyl chloride and benzyl bromide, are particularly preferably used. Other agents suitable for quaternization include dialkyl sulfates such as especially dimethyl sulfate or diethyl sulfate. A quaternization of basic amino groups can also be achieved with alkylene oxides such as ethylene oxides or propylene oxides in the presence of acids. Most commonly used as agents for quaternization: methyl chloride, dimethyl sulfate or diethyl sulfate. A reaction with quaternized epichlorohydrin of the general formula (XII) is also possible (see below). The following are examples of non-limiting examples of the amines suitable as monomers (a2):
• a) aminoalkyl acrylates and methacrylates and aminoalkyl acrylates and methacrylamides of the general formula (VIII)
  
  where for R ¹⁴ to R ¹⁸ the definitions given for formula (IV) apply and R ²⁵ and R ²⁶ are each selected independently of one another 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. Hydrogen, methyl, ethyl, n-propyl and benzyl are preferred. The amides can be unsubstituted, N-alkyl or N-alkylamino monosubstituted or N, N-dialkyl-substituted or N, N-dialkylaminodisubstituted, in which the alkyl or alkylamino groups of C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched, or C ₃ -C ₄₀ carbocyclic units are derived. In addition, the alkylamino groups can be quaternized. Preferred comonomers of the formula (VIII) are N, N-dimethylaminomethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, N, N-dimethylamino octyl (meth) acrylate, N, N-dimethylaminododecyl (meth) acrylate. Also preferred are N- [3- (dimethylamino) propyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) butyl] methacrylamide, N- [8- (dimethylamino) octyl] methacrylamide , N- [12- (dimethylamino) dodecyl] methacrylamide, N- [3- (diethylamino) propyl] methacrylamide and N- [3- (diethylamino) propyl] acrylamide. N, N-Dimethylaminoethyl methacrylate, N- [3- (dimethylamino) propyl] methacrylamide, N-methylaminoethyl methacrylate, N- [3- (methylamino) propyl] methacrylamide, aminoethyl methacrylate and N- [3-aminopropyl] methacrylamide are very particularly preferred. The above-mentioned monomers are preferably quaternized using methyl chloride, methyl sulfate or diethyl sulfate.
• b) N-vinylimidazoles of the general formula IX, where the definitions given for formula (V) apply independently of one another for R ¹⁹ to R ²¹ .
  
  N-vinylimidazole, 1-vinyl-2-methylvinylimidazole and quaternization with methyl chloride, methyl sulfate or diethyl sulfate are particularly preferred.
• c) diallylamines of the general formula (X)
  
  with R ²⁷ = hydrogen or C ₁ - to C ₂₄ -alkyl. N, N-diallylamine and quaternization with methyl chloride or methyl sulfate are particularly preferred.
• d) Furthermore, (a2) can be selected from compounds such as 1,3-divinylimidazolid-2-one or N-disubstituted vinylamines of the general formula (XI): (R ²⁸ ) ₂ N- (CH ₂ ) _n -CR ¹⁵ = CHR ¹⁴ (XI) where R ¹⁴ , R ¹⁵ and n have the same meaning as in the formulas (IIIa) and (IIIb), and the radicals R ²⁸ can be selected from the group consisting of hydrogen C ₁ -C ₄₀ linear or branched chain alkyl radicals, formyl , C ₁ -C ₁₀ linear or branched chain acyl, N, N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl, ethoxypropyl or benzyl. Methyl, ethyl, n-propyl and benzyl are preferred. If n = 0, it applies that both radicals R ²⁸ are not hydrogen at the same time.
• 2) Unsaturated acids Quaternary amines can be obtained by reacting acids, such as would be introduced, for example, by using unsaturated acids such as acrylic acid or methacrylic acid as starting compound (a2), with a quaternized epichlorohydrin of the general formula (XII).
  
  R ^{29 is} preferably C ₁ -C ₄₀ -alkyl. 2,3-Epoxypropyl-trimethylammonium chloride or 3-chloro-2-hydroxypropyl-trimethylammonium chloride is preferably used. The epoxides of the formula XI can also be generated in situ by reacting the corresponding chlorohydrins with bases, for example sodium hydroxide. Monomers (a2) containing hydroxyl and / or amino groups can also be reacted accordingly. Hydroxyl groups of the polyvinyl alcohol units and vinylamine units, formed by hydrolysis of vinylformamide, are preferred.
• 3) Halides of radically polymerizable monomers, such as, for example, haloalkyl acrylates or haloalkyl methacrylates. Chlorine, bromine or iodine compounds are preferred. 3-Chloro-2-hydroxypropyl acrylate may be mentioned by way of example but not by way of limitation. The conversion to quaternary amines is carried out by reaction with amines, for example trialkylamines such as trimethylamine or triethylamine.

Of course, mixtures of the respective Monomers from group (a2) are polymerized. Most preferred Monomers (a2) include N-vinylimidazole, N, N-diallylamine and aminoethyl methacrylate.

The implementation of the compounds (a2) to quaternary Amines (as a result of a2 ') can during or after the reaction. In a subsequent implementation can the intermediate Polymer first isolated or - preferably - immediate be implemented. The implementation can be complete or partial. there are preferably at least 10%, particularly preferably at least 50%, most preferably at least 80% of compound (a2) quaternary Amines (a2 ') transferred. The Share of implementation to quaternary Amines are preferably the higher, the lower the water solubility of the monomer (a2). Is the water solubility of the monomer (a2) below 60 g / l the reaction is carried out so that the ratio of Sum of monomers (a2 ') and optionally (a1) and (c) to the sum of the monomers (a2) and (d) at least Is 2 to 1, preferably 4 to 1, particularly preferably 10 to 1.

Those containing the quaternary nitrogen Polymerizable monomer (a1) and / or their precursors (a2) can also also in a mixture with one or more, ethylenically unsaturated copolymerizable comonomers (c) and / or (d) are used, the molar ratio of the sum of the monomers in the end product Units a1 and / or a2 and possibly c to the sum of the monomers d is at least 2 to 1. Is preferably The relationship at least 4 to 1, very particularly preferably at least 10 to 1, most preferably at least 20 to 1.

Basically, all come as monomers (c) hydrophilic monomers with a water solubility above 60 g / l at 25 ° C in question, which is copolymerizable with the monomers (a1) and optionally (a2) and (d) are. They are preferably ethylenically unsaturated monomers. Various monomers suitable as monomers (c) include described in Ullmann's Encyclopedia of Industrial Chemistry, vol. A21, chapter "Polyacrylates", pp. 157-178, 5. Edition, 1992, VCH Verlagsgesellschaft mbH, Weinheim, Germany.

The term ethylenically unsaturated means that the Monomers at least one radically polymerizable carbon-carbon Have double bond which is mono-, di-, tri- or tetrasubstituted can be.

• i) N-Vinyllactame, bevorzugt mit einem 5 bis 7-Ring, wie z.B. N-Vinylpyrrolidon, N-Vinylpiperidon, N-Vinylcaprolactam,
• ii) acyclische N-Vinylcarbonsäureamide, bevorzugt mit 2 bis 6 C-Atomen, wie z.B. N-Vinylformamid, N-Ethyl-N-vinylacetamid oder N-Methyl-N-vinylacetamid,
• iii) Hydroxyalkylacrylate, bevorzugt mit 2 bis 6 C-Atomen, wie z.B. 2-Hydroxyethylacrylat, 2-Hydroxyethylmethacrylat, 2-Hydroxypropylmethacrylat, Butandiolmonoacrylat,
• iv) ethylenisch ungesättigte Amide, wie beispielsweise Acrylamid oder Methacrylamid,
• v) N-Vinylimidazol,
• vi) Ungesättigte Säuren, bevorzugt Carbon- oder Sulfonsäuren, wie beispielsweise Acrylsäure, Maleinsäure, Methacrylsäure, 2-Acrylamido-2-methylpropansulfonsäure.
• vii) Ungesättigte Amine wie Dimethylaminoethylacrylat, Dimethylaminomethacrylat.

The monomers (c) are preferably

• i) N-vinyl lactams, preferably having a 5 to 7 ring, such as, for example, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam,
• ii) acyclic N-vinylcarboxamides, preferably having 2 to 6 C atoms, such as, for example, N-vinylformamide, N-ethyl-N-vinylacetamide or N-methyl-N-vinylacetamide,
• iii) hydroxyalkyl acrylates, preferably having 2 to 6 carbon atoms, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butanediol monoacrylate,
• iv) ethylenically unsaturated amides, such as, for example, acrylamide or methacrylamide,
• v) N-vinylimidazole,
• vi) Unsaturated acids, preferably carboxylic or sulfonic acids, such as acrylic acid, maleic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid.
• vii) Unsaturated amines such as dimethylaminoethyl acrylate, dimethylaminomethacrylate.

Furthermore, any mixture of different ones Monomers (c) are used. Particularly preferred monomers (c) are N-vinyl lactams and N-vinyl imidazole. Very particularly preferred is N-vinyl pyrrolidone.

Basically, all come as monomers (d) hydrophobic monomers with water solubility below 60 g / l at 25 ° C in question, which is copolymerizable with the monomers (a1) and optionally (a2) and (c) are. They are preferably ethylenically unsaturated monomers. Various monomers suitable as monomers (d) include described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A21, chapter "Polyacrylates", pp. 157-178, p. Edition, 1992, VCH Verlagsgesellschaft mbH, Weinheim, Germany.

• 1) C₁-C₁₀-Alkylester monoethylenisch ungesättigter C₃-C₆-Carbonsäuren, insbesondere die Ester der Acrylsäure und der Methacrylsäure. Die Ester können abgeleitet sein von C₁-C₄₀ linearen, C₃-C₄₀ verzweigtkettigen oder C₃-C₄₀ carbocyclischen Alkoholen, wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, 2-Butanol, tert.-Butanol, n-Pentanol, n-Hexanol, 2-Ethylhexan-1-ol, n-Octanol, n-Decanol, 2-Propylheptan-1-ol, Cyclohexanol, 4-tert.-Butylhexanol oder 2,3,5-Trimethylcyclohexanol. Besonders bevorzugt sind Methylacrylat, Ethylacrylat, Propylacrylat, n-Butylacrylat, iso-Butylacrylat, t-Butylacrylat, 2-Ethylhexylacrylat, Decylacrylat, Methylmethacrylat, Ethylmethacrylat, Propylmethacrylat, n-Butylmethacrylat, iso-Butylmethacrylat, t-Butylmethacrylat, 2-Ethylhexylmethacrylat, Decylmethacrylat, Methylethacrylat, Ethylethacrylat, n-Butylethacrylat, iso-Butylethacrylat, t-Butyl-ethacrylat, 2-Ethylhexylethacrylat, Decylethacrylat, Stearylacrylat, Stearyl(meth)acrylat. Ester können auch von mehrfachfunktionellen Alkoholen mit 2 bis etwa 8 Hydroxylgruppen abgeleitet sein, so lange sie die Löslichkeitsanforderungen für Monomere (d) genügen. Beispielhaft seien Ester von Ethylenglycol, Hexylenglycol, Glycerin und 1,2,6-Hexantriol, von Aminoalkoholen oder von Alkoholethern wie Methoxyethanol und Ethoxyethanol, (Alkyl)Polyethylenglykolen, (Alkyl)Polypropylenglykolen oder ethoxylierten Fettalkoholen, beispielsweise C₁₂-C₂₄-Fettalkoholen umgesetzt mit 1 bis 200 Ethylenoxid-Einheiten zu nennen.
• 2) Di-C₁-C₁₀-alkylester ethylenisch ungesättigter Dicarbonsäuren wie Maleinsäure, Fumarsäure oder Itaconsäure mit den oben unter 1) genannten C₁-C₁₀-Alkanolen oder C₁-C₁₀-Cycloalkanolen, z.B. Maleinsäuredimethylester oder Maleinsäuredin-butylester.
• 3) Kohlenwasserstoffe mit mindestens einer radikalisch polymerisierbaren Kohlenstoff-Kohlenstoff Doppelbindung, bevorzugt Styrol, alpha-Methylstyrol, tert.-Butylstyrol, Butadien, Isopren, Cyclohexadien, Ethylen, Propylen, 1-Buten, 2-Buten, Isobutylen, Vinyltoluol, sowie Mischungen dieser Monomere. Besonders bevorzugt sind vinylaromatische Verbindungen wie Styrol und α-Methylstyrol, die gegebenenfalls am aromatischen Ring einen oder mehrere Substituenten aufweisen können, die bevorzugt ausgewählt sind unter C₁-C₄-Alkyl, Halogenatomen, insbesondere Chlor, und/oder Hydroxylgruppen.
• 4) Vinyl-, Vinyliden- oder Allylhalogenide, bevorzugt Vinylchlorid, Vinylidenchlorid und Allylchlorid.
• 5) Vinyl-, Allyl- und Methallylester von C₁-C₄₀ linearen, C₃-C₄₀ verzweigtkettigen oder C₃-C₄₀ carbocyclische Carbonsäuren aliphatischer, gesättigter oder ungesättigter Natur. Als Carbonsäuren bevorzugt sind z.B. Ameisensäure, Essigsäure, Propionsäure, Buttersäure, Valeriansäure, Isovaleriansäure, Capronsäure, Caprylsäure, Caprinsäure, Undecylensäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmitoleinsäure, Stearinsäure, Ölsäure, Arachinsäure, Behensäure, Lignocerinsäure, Cerotinsäure sowie Melissensäure. Bevorzugt werden Vinylester der oben genannten C₁-C₁₂-Carbonsäuren, insbesondere der C₁-C₆-Carbonsäuren, verwendet. Ganz besonders bevorzugt sind Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylvalerat, Vinylhexanoat, Vinyl-2-ethylhexanoat, Vinyldecanoat, Vinyllaurat und Vinylstearat sowie die entsprechenden Allyl- und Methallylester. Am meisten bevorzugt ist Vinylacetat.
• 6) Vinyl-, Allyl- und Methallylether linearer oder verzweigter, aliphatischer Alkohole mit 2 bis 20 C-Atomen, z.B. Vinylmethylether, Vinylethylether, Vinyldodecylether, Vinylhexadecylether und Vinylstearylether.
• 7) Monoethylenisch ungesättigter Monocarbonsäuren, sofern sie eine Löslichkeit in Wasser von unter 60 g/l bei 25°C aufweisen, wie beispielsweise Acrylamidoglycolsäure, Fumarsäure oder Crotonsäure.

This is in particular:

• 1) C ₁ -C ₁₀ alkyl esters of monoethylenically unsaturated C ₃ -C ₆ carboxylic acids, in particular the esters of acrylic acid and methacrylic acid. The esters can be derived from C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched or C ₃ -C ₄₀ carbocyclic alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, tert .-Butanol, n-pentanol, n-hexanol, 2-ethylhexan-1-ol, n-octanol, n-decanol, 2-propylheptan-1-ol, cyclohexanol, 4-tert-butylhexanol or 2,3,5 -Trimethylcyclohexanol. Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, methacrylate, methacrylate, methacrylate, t-butyl methacrylate , Methylethacrylate, ethylethacrylate, n-butylethacrylate, iso-butylethacrylate, t-butylethacrylate, 2-ethylhexylethacrylate, decylethacrylate, stearyl acrylate, stearyl (meth) acrylate. Esters can also be derived from polyfunctional alcohols with 2 to about 8 hydroxyl groups, as long as they meet the solubility requirements for monomers (d). Examples include esters of ethylene glycol, hexylene glycol, glycerol and 1,2,6-hexanetriol, of amino alcohols or of alcohol ethers such as methoxyethanol and ethoxyethanol, (alkyl) polyethylene Lenglycols, (alkyl) polypropylene glycols or ethoxylated fatty alcohols, for example C ₁₂ -C ₂₄ fatty alcohols reacted with 1 to 200 ethylene oxide units.
• 2) Di-C ₁ -C ₁₀ alkyl esters of ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with the C ₁ -C ₁₀ alkanols mentioned above under 1) or C ₁ -C ₁₀ cycloalkanols, for example dimethyl maleate or din-butyl maleate.
• 3) hydrocarbons with at least one radically polymerizable carbon-carbon double bond, preferably styrene, alpha-methylstyrene, tert-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene, vinyl toluene, and mixtures thereof monomers. Vinylaromatic compounds such as styrene and .alpha.-methylstyrene are particularly preferred, which may optionally have one or more substituents on the aromatic ring, which are preferably selected from C ₁ -C ₄ alkyl, halogen atoms, in particular chlorine, and / or hydroxyl groups.
• 4) vinyl, vinylidene or allyl halides, preferably vinyl chloride, vinylidene chloride and allyl chloride.
• 5) vinyl, allyl and methallyl esters of C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched chain or C ₃ -C ₄₀ carbocyclic carboxylic acids of an aliphatic, saturated or unsaturated nature. Preferred carboxylic acids are, for example, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, isovaleric acid, caproic acid, caprylic acid, capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, arachic acid, behenic acid, melissinic acid, lignocenoic acid. Vinyl esters of the abovementioned C ₁ -C ₁₂ carboxylic acids, in particular the C ₁ -C ₆ carboxylic acids, are preferably used. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl decanoate, vinyl laurate and vinyl stearate and the corresponding allyl and methallyl esters are very particularly preferred. Most preferred is vinyl acetate.
• 6) vinyl, allyl and methallyl ethers of linear or branched, aliphatic alcohols having 2 to 20 carbon atoms, for example vinyl methyl ether, vinyl ethyl ether, vinyl dodecyl ether, vinyl hexadecyl ether and vinyl stearyl ether.
• 7) Monoethylenically unsaturated monocarboxylic acids, provided that they have a solubility in water of less than 60 g / l at 25 ° C., such as, for example, acrylamidoglycolic acid, fumaric acid or crotonic acid.

Furthermore, any mixture of different ones Monomers (d) are used. Particularly preferred monomers (d) are vinyl acetate, methyl methacrylate, methyl acrylate and ethyl acrylate.

In addition to the above-mentioned comonomers, so-called macromonomers such as, for example, silicone-containing macromonomers with one or more radical-polymerizable groups or alkyloxazoline macromonomers, as described, for example, in, can be used as comonomers (c) or (d) EP 408 311 are described. Furthermore, fluorine-containing monomers, such as those in the EP 558423 are described, crosslinking or regulating the molecular weight compounds are used in combination or alone. The assignment to groups (c) or (d) is based on their solubility.

The skilled worker is aware that a Monomer (a2) can fall into the group of monomers (c) or (d), as long as (a2) has not been converted into a quaternary amine (a2 ').

The basic monomers (c) or (d) can can also be cationized by mixing with mineral acids, e.g. Sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or Nitric acid, or with organic acids, such as. formic acid, Acetic acid, Lactic acid, or citric acid, be neutralized.

The usual ones known to the person skilled in the art can be used as regulators Compounds, such as sulfur compounds (e.g. mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid or dodecyl mercaptan), as well as tribromochloromethane or other compounds that regulate the molecular weight of the polymers obtained are used become.

It may also contain thiol groups Silicone compounds are used.

Silicone-free controllers are preferred used.

As monomers (a1), (a2), (c) or (d) can crosslinking monomers are also used, for example compounds with at least two ethylenically unsaturated double bonds, such as for example esters of ethylenically unsaturated carboxylic acids, such as acrylic acid or methacrylic acid and polyhydric alcohols, ethers of at least dihydric alcohols, such as vinyl ether or allyl ether. Straight-chain are also suitable or branched, linear or cyclic aliphatic or aromatic Hydrocarbons over have at least two double bonds, which in the aliphatic Hydrocarbons must not be conjugated. Are also suitable Amides of acrylic and methacrylic acid and N-allylamines of at least divalent amines, such as 1,2-diaminoethane, 1,3-diaminopropane. Also triallylamine, N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes. Other suitable crosslinkers are divinyl dioxane, Tetraallylsilane or tetravinylsilane.

Particularly preferred crosslinkers are, for example, methylenebisacrylamide, triallylamine and triallylammonium salts, divinylimidazole, N, N'-divinylethyleneurea, reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic acid esters and acrylic acid esters of polyalkylene oxides or more valuable alcohols that have been reacted with ethylene oxide and / or propylene oxide and / or epichlorohydrin.

A very particularly preferred crosslinker is divinylethylene urea.

The crosslinking monomers are used in an amount of less than 5% by weight, based on the sum of the starting materials a) to d). Less than 3% by weight and very particularly preferably less than 1% by weight of crosslinking monomer are particularly preferably used. In the polymerization for the preparation of the polymers according to the invention, other polymers, such as polyamides, polyurethanes, polyesters, homo- and Copolymers of ethylenically unsaturated monomers. Examples of such polymers, some of which are also used in cosmetics, are the polymers Amerhold ^TM , Ultrahold ^TM , Ultrahold Strong ^TM , Luviflex ^TM VBM, Luvimer ^TM , Acronal ^TM , Acudyne ^TM , Stepanhold ^TM , Lovocryl ^TM , Versatyl ^TM , known under the trade names. Amphomer ^TM or Eastma AQ ^TM . Cationic guar derivatives such as guar hydroxypropyltrimonium chloride (INCI) can also be used.

The comonomers (c) and / or (d) can if they contain ionizable groups, before or after the polymerization, partially or completely with acids or bases are neutralized, for example the water solubility adjust or dispersibility to a desired level.

As a neutralizing agent for acid groups supporting monomers can for example mineral bases such as sodium carbonate, alkali hydroxides as well 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 can be used.

For the preparation of the polymers can the monomers of component a1) both in the presence of the polyether with the help of initiators which form free radicals and also by action high energy radiation, including exposure to high energy Electrons to be understood are polymerized.

As initiators for radical polymerization can the usual ones for this Peroxo and / or azo compounds are used, for example Alkali or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, Succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl 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, Azobis-isobutyronitrile, azo-bis (2-amidonopropane) dihydrochloride or 2-2'-azo-bis- (2-methylbutyronitrile). Initiator mixtures or redox initiator systems are also suitable, such as. Ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate.

Organic peroxides are preferred used.

The amounts of initiator used or initiator mixtures based on the radically polymerizable used Monomers (a1, a2, c, d) are between 0.01 and 100% by weight, preferably between 0.1 and 40% by weight, particularly preferably between 1 and 15 Wt .-%.

The polymerization takes place in the temperature range from 40 to 200 ° C, preferably in the range from 50 to 140 ° C., particularly preferably in the range from 60 to 110 ° C. It usually becomes under atmospheric pressure carried out, can, however, also under reduced or elevated pressure, preferably between 1 and 5 bar. The reaction temperature is preferred in this way selected that it is at least the melting temperature of the polyether-containing compound (b) under the respective reaction conditions, so that the reaction can be carried out in a melt of (b).

The polymerization can, for example as solution polymerization, Bulk polymerization, emulsion polymerization, reverse Emulsion polymerization, suspension polymerization, reverse suspension polymerization or precipitation polymerization carried out be without the usable methods are limited to this. The is preferred Bulk polymerization, the polymerization of a1 and optionally a2, c and / or d is carried out in the presence of b. The water content in the reaction mixture during the Polymerization less than 20% by weight, preferably less than 15%, particularly preferably less than 10% by weight, most preferred less than 5% by weight. Preference is given to essentially anhydrous Conditions worked and carried out a polymerization in bulk. "Essentially anhydrous" means in this Connection that in addition to the water contained in the raw materials no additional Water is introduced into the reaction mixture. "During the polymerization" means in this Context that the radical polymerization of the radical polymerizable monomers is not yet complete. Doing so a polymerization is considered to be incomplete as long as as long as the content of residual monomers compared to the starting amount of monomers is even larger than 50%, preferably greater than 30%, particularly preferably greater than 10%, very particularly preferably greater than 5% most preferably greater than 2%. After completion of the polymerization as defined above, it is possible the reaction mixture water also in larger amounts (i.e. more than 20% by weight of the reaction mixture).

With the particularly preferred bulk polymerization, one can proceed in such a way that at least one at least one monomer from group (a1) and / or (a2) and / or possibly further comonomers from groups (c) and / or (d) dissolves in the polyether-containing compound (b) and the mixture is polymerized out after addition of a polymerization initiator. The polymerization can also be carried out semicontinuously by firstly removing part, for example 10%, of the mixture to be polymerized from the polyether-containing compound (b), at least one monomer from group (a1) and / or (a2), possibly further comonomers from the groups ( c) and / or (d) and initiator, the mixture is heated to the polymerization temperature and, after the polymerization has started, the rest of the mixture to be polymerized is added as the polymerization progresses. The polymers can - most preferably - also be obtained by placing the polyether-containing compounds of group (b) in a reactor, heating to the polymerization temperature and at least one monomer from group (a1) and / or (a2), possibly further Comonomers of groups (c) and / or (d) and polymerization initiator are added and polymerized either all at once, batchwise or, preferably, continuously.

For the polymerization can Emulsifiers can be added.

One uses, for example, as emulsifiers ionic or nonionic surfactants, whose HLB value is in the range of 3 to 18. The definition of the HLB value is based on the publication by Griffin WC (1954) J Soc Cosmetic Chem Volume 5, p. 249. The amount of surfactants, based on the polymer, is 0 to 10% by weight. Preferably be for no surfactants were added to the polymerization.

The polymerizations for production of the polymers according to the invention can in the presence of at least one non-aqueous, organic solvent or in mixtures of at least one organic solvent and performed water become. Is preferably used per 100 parts by weight of the sum of Educts (a1 and / or a2, b, and optionally c and d) 5 to 2000, preferably 10 to 500 parts by weight of the organic solvent or the solvent mixture. 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 the divalent Alcohols, diethylene glycol, triethylene glycol, glycerin and dioxane.

• 1) 3 bis 30 Gew.-% mindestens eines Monomers mit quaternären Aminogruppen (a1) und
• 2) 0 bis 15 Gew.-% eines oder mehreren weiteren copolymerisierbaren Monomeren (c) und
• 3) 0 bis 15 Gew.-% eines oder mehreren weiteren copolymerisierbaren Monomeren (d) in Gegenwart von
• 4) 70 bis 97 Gew.-% mindestens einer polyetherhaltigen Verbindung,

wobei sich für eine definierte Polymerisation die Gew.-% der einzelnen Komponenten a1 – d auf jeweils 100 Gew.-% addieren.Polymers which are obtainable by free-radical polymerization of

• 1) 3 to 30% by weight of at least one monomer with quaternary amino groups (a1) and
• 2) 0 to 15% by weight of one or more further copolymerizable monomers (c) and
• 3) 0 to 15% by weight of one or more further copolymerizable monomers (d) in the presence of
• 4) 70 to 97% by weight of at least one polyether-containing compound,

the weight percent of the individual components a1-d adding up to 100 weight percent for a defined polymerization.

• 1) 4 bis 12 Gew.-% mindestens eines Monomers mit quaternären Aminogruppen (a1) und
• 2) 0 Gew.-% eines oder mehreren weiteren copolymerisierbaren Monomeren (c)
• 3) 0 Gew.-% eines oder mehreren weiteren copolymerisierbaren Monomeren in (d) Gegenwart von
• 4) 88 bis 96 Gew.-% mindestens einer polyetherhaltigen Verbindung,

wobei sich für eine definierte Polymerisation die Gew.-% der einzelnen Komponenten a1 und b auf jeweils 100 Gew.-% addieren.Polymers which are obtainable by free-radical polymerization of

• 1) 4 to 12% by weight of at least one monomer with quaternary amino groups (a1) and
• 2) 0% by weight of one or more further copolymerizable monomers (c)
• 3) 0% by weight of one or more further copolymerizable monomers in (d) the presence of
• 4) 88 to 96% by weight of at least one polyether-containing compound,

the weight percent of the individual components a1 and b adding up to 100 weight percent for a defined polymerization.

The K values of the polymers should in the range from 10 to 300, preferably 11 to 100, particularly preferred 15 to 60 are. The K value desired in each case can be in a manner known per se through the composition of the starting materials to adjust. The K values are determined according to Fikentscher, cellulose chemistry, Vol. 13, pp. 58 to 64, and 71 to 74 (1932) in N-methylpyrrolidone at 25 ° C and polymer concentrations, depending on the K value range between 0.1% by weight and 5% by weight. Other solvents instead of N-methylpyrrolidone can be used. Ethanol is particularly preferred. The limits given above preferably refer to the determination of 1% polymer solutions in Ethanol.

After implementation, the polymer solutions Steam distilled to remove residual monomers, for example become. After steam distillation, depending on the amount of quaternized Amino groups and the type of polyether (b) aqueous solutions or dispersions. The Obtaining watery solutions is preferred. The polymers according to the invention are advantageously used for the sake of one better handling after completion of the water polymerization added. It is the polymer content is preferably 20 to 60% by weight.

The polymers can by various drying processes such as Spray drying, fluidized spray Drying, roller drying or freeze drying can be transferred to powder form. Spray drying is preferably used as the drying process. Out The polymer dry powder thus obtained can be dissolved or Redisperse in water again to produce an aqueous solution or dispersion. The transfer to Powder form has the advantage of a better shelf life, a simpler one of transportation as well as a lower tendency for Microbial attack.

• a) in kosmetischen Zubereitungen
• b) in Arzneimitteln und anderen therapeutisch-medizinischen Zubereitungen
• c) in Formulierungen für Reinigungsmittel, Desinfektionsmitteln oder Geschirrspülmittel.
• d) in Textil- und/oder Teppichpflegemitteln z.B. in Weichspülern oder in Wasch- und Pflegemitteln
• e) als Stabilisatoren für beispielsweise Dispersionen z.B. bei der Durchführung von Polymerisationen in wässriger Lösung oder Emulsion
• f) als Stabilisator für die Herstellung fotografischer Emulsionen
• g) als Flockungsmittel beispielsweise bei der Abwasserbehandlung
• h) als Hilfsmittel zur Papierherstellung insbesondere zur Herstellung von Papieren für die Verwendung in "Ink Jet" Verfahren
• i) in der Färbeindustrie als Zusatz zu Farben oder Tinten
• j) als Feuchthaltemittel oder Gelbildner
• k) als Gelantineersatzstoff
• l) als Verdickungsmittel
• m) als Dehydrierungsmittel

The water-soluble or water-dispersible polyether-containing polymers according to the invention can advantageously be used for numerous purposes. One example is a use

• a) in cosmetic preparations
• b) in medicinal products and other therapeutic-medical preparations
• c) in formulations for cleaning agents, disinfectants or dishwashing detergents.
• d) in textile and / or carpet care products, for example in fabric softeners or in detergents and care products
• e) as stabilizers for, for example, dispersions, for example when carrying out polymerizations in aqueous solution or emulsion
• f) as a stabilizer for the production of photographic emulsions
• g) as a flocculant, for example in waste water treatment
• h) as an aid to paper manufacture, in particular for the manufacture of papers for use in "ink jet" processes
• i) in the dyeing industry as an additive to paints or inks
• j) as a humectant or gelling agent
• k) as a gelatin substitute
• l) as a thickener
• m) as a dehydrating agent

The water-soluble or water-dispersible according to the invention Polymers containing polyalkylene oxide or polyglycerol are suitable are particularly suitable for use in cosmetic formulations, especially hair cosmetic formulations.

The concept of cosmetic formulations is to be understood broadly and means all such preparations that are suitable for application to skin and / or hair and / or nails and another as one exclusively pursue medical-therapeutic purpose.

 Includes hair cosmetic formulations in particular styling agents and / or conditioning agents in hair cosmetics Preparations such as hair treatments, hair foams (English Mousses), (hair) gels or hair sprays, hair lotions, hair rinses, hair shampoos, hair emulsions, Top fluids, leveling agents for perms, hair dyeing and bleaching agents, "hot oil treatment" preparations, Conditioners, setting lotions or hair sprays. Depending on the area of application can the hair cosmetic preparations as (aerosol) spray, (aerosol) foam, Gel, gel spray, cream, lotion or wax can be applied.

Other cosmetic preparations include, for example, skin conditioners, e.g. in skin or Personal care products, Foam and shower baths. It also includes use in oral hygiene and others Hygiene formulations, in anti-acne products, in sunscreens, in tanning agents, in pigment-containing formulations of decorative cosmetics, in anti-wrinkle agents, in skin tightening agents, in deodorants.

• a) 0,05 – 20 Gew.-% des erfindungsgemäßen Polymerisates
• b) 20 – 99,95 Gew.-% Wasser und/oder Alkohol
• c) 0 – 79,5 Gew.-% weitere Bestandteile

In a preferred embodiment, the hair cosmetic formulations according to the invention contain

• a) 0.05-20% by weight of the polymer according to the invention
• b) 20-99.95% by weight of water and / or alcohol
• c) 0 - 79.5% by weight of other constituents

Under alcohol are all common in cosmetics Understand alcohols, e.g. Ethanol, isopropanol, n-propanol.

Among other components are the ones common in cosmetics additions to understand, for example blowing agents, defoamers, surfactants Connections, i.e. Surfactants, emulsifiers, foaming agents and solubilizers. The surfactants used Connections can be anionic, cationic, amphoteric or neutral. Other common ingredients can further be e.g. Preservatives, perfume oils, opacifiers, active ingredients, UV filters, Care substances such as panthenol, collagen, vitamins, protein hydrolyzates, 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.

Furthermore, this includes all in cosmetics well-known styling and conditioner polymers, which in combination with the polymers according to the invention can be used if very special properties are to be set.

Anionic polymers, for example, are suitable as conventional hair cosmetic polymers. Such 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 (Luviset ^® PUR) and polyureas. Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example, Luvimer 100P ^®), copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold ^® 8, strong), copolymers from vinyl acetate, crotonic acid and optionally further vinyl esters (eg Luviset ^® brands), maleic anhydride copolymers, if appropriate reacted with alcohols, anionic polysiloxanes, eg carboxy-functional, copolymers from vinylpyrrolidone, t-butyl acrylate, methacrylic acid (eg Luviskol ^® VBM).

The group of polymers suitable for combination with the polymers according to the invention further includes, for example, Balance ^® CR (National Starch; acrylate copolymer), Balance ^® 0/55 (National Starch; acrylate copolymer), Balance ^® 47 (National Starch; octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer) ), Aquaflex ^® FX 64 (ISP; isobutylene / ethylmaleimide / hydroxyethylmaleimide copolymer), Aquaflex ^® SF-40 (ISP / National Starch; VP / Vinyl Caprolactam / DMAPA acrylate copolymer), Allianz ^® LT-120 (ISP / Rohm &Haas; Acrylate / C1-2 succinate / hydroxyacrylate copolymer), Aquarez ^® HS (Eastman; Polyester-1), Diaformer ^® Z-400 (Clariant; methacryloyl ethyl betaine / 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 (National Starch; Octyl-acrylamide / acrylate / butylaminoethyl methacrylate copolymer), Advantage ^® HC 37 (ISP; terpolymer made of vinyl caprolactam / vinyl pyrrolidone / dimethylaminoethyl methacrylate), Acudyne ^® 258 (Rohm &Haas; acrylate / hydroxy ester acrylate copolymer), Luviset ^® PUR (BASF, polyurethanes -1), Luviflex Silk ^® (BASF), Eastman ^® AQ48 (Eastman).

Are very particularly preferred as anionic polymers Acrylates with an acid number greater than or equal to 120 and copolymers from t-butyl acrylate, ethyl acrylate, methacrylic acid.

Other suitable hair cosmetic polymers are cationic polymers having the INCI name Polyquaternium, eg 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).

Cationic guar derivatives can also be used such as guar hydroxypropyltrimonium chloride (INCI) can be used.

As further hair cosmetic polymers neutral polymers are also suitable, such as polyvinylpyrrolidones, copolymers from N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, Polyvinyl caprolactam and copolymers with N-vinyl pyrrolidone, polyethylene imines and their salts, polyvinylamines and their salts, cellulose derivatives, polyaspartic and derivatives.

For setting certain properties can the preparations additionally also conditioning substances based on silicone compounds contain. Suitable silicone compounds are, for example, polyalkylsiloxanes, Polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes, silicone resins or Dimethicon Copolyole (CTFA) and amino functional silicone compounds like Amodimethicone (CTFA).

• a) 0,1 – 10 Gew.-% des erfindungsgemäßen Polymerisates
• b) 20 – 99,9 Gew.-% Wasser und/oder Alkohol
• c) 0 – 70 Gew.-% eines Treibmittel
• d) 0 – 20 Gew.-% weitere Bestandteile

The polymers according to the invention are particularly suitable as setting agents in hair styling preparations, in particular hair sprays (aerosol sprays and pump sprays without propellant gas) and hair foams (aerosol foams and pump foams without propellant gas). In a preferred embodiment, these preparations contain

• a) 0.1-10% by weight of the polymer according to the invention
• b) 20-99.9% by weight of water and / or alcohol
• c) 0 - 70 wt .-% of a blowing agent
• d) 0-20% by weight of further constituents

Blowing agents are those for hair sprays or aerosol foams commonly used Propellant. Mixtures of propane / butane, pentane, Dimethyl ether, 1,1-difluoroethane (HFC-152 a), carbon dioxide, nitrogen or compressed air.

• a) 0,1 – 10 Gew.-% des erfindungsgemäßen Polymerisates
• b) 55 – 94,8 Gew.-% Wasser und/oder Alkohol
• c) 5 – 20 Gew.-% eines Treibmittel
• d) 0,1 – 5 Gew.-% eines Emulgators
• e) 0 – 10 Gew.-% weitere Bestandteile

A formulation according to the invention for aerosol hair foams contains

• a) 0.1-10% by weight of the polymer according to the invention
• b) 55-94.8% by weight of water and / or alcohol
• c) 5-20% by weight of a blowing agent
• d) 0.1-5% by weight of an emulsifier
• e) 0-10% by weight of other constituents

As emulsifiers, all of them can usually be found in hair foams emulsifiers used are used. Suitable emulsifiers can be non-ionic, cationic or anionic or amphoteric.

Examples of nonionic emulsifiers (INCI nomenclature) are Laurethe, e.g. Laureth-4; Cethethe, e.g. Cetheth-1, polyethylene glycol cetyl ether; Cethearethe, e.g. Cetheareth-25, Polyglycol fatty acid glycerides, hydroxylated Lecithin, lactyl ester of fatty acids, Alkylpolyglycosides.

Examples of cationic emulsifiers are Cetyidimethyl-2-hydroxyethylammonium dihydrogenphosphate, Cetyltrimonium chloride, cetyltrimmonium bromide, cocotrimonium methyl sulfate, 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, especially the alkali and alkaline earth metal salts, e.g. Sodium, potassium, magnesium, calcium, as well as ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can between 1 to 10 ethylene oxide or propylene oxide units, preferred Have 1 to 3 ethylene oxide units in the molecule.

• a) 0,1 – 10 Gew.-% des erfindungsgemäßen Polymerisates
• b) 60 – 99,85 Gew.-% Wasser und/oder Alkohol
• c) 0,05 – 10 Gew.-% eines Gelbildners
• d) 0 – 20 Gew.-% weitere Bestandteile

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

• a) 0.1-10% by weight of the polymer according to the invention
• b) 60-99.85% by weight of water and / or alcohol
• c) 0.05-10% by weight of a gel former
• d) 0-20% by weight of further constituents

All of the usual cosmetics can be used as gel formers Gel formers are used. These include slightly cross-linked polyacrylic acid, for example Carbomer (INCI), cellulose derivatives, e.g. Hydroxypropyl cellulose, hydroxyethyl cellulose, cationically modified celluloses, polysaccharides, e.g. Xanthum Rubber, caprylic / capric triglycerides, sodium acrylates copolymer, Polyquaternium-32 (and) Paraffinum Liquidum (INCI), Sodium Acrylates Copolymer (and) Paraffinum Liquidum (and) PPG-1 Trideceth-6, Acrylamidopropyl Trimonium Chloride / Acrylamide Copolymer, Steareth-10 Allyl Ether Acrylates Copolymer, Polyquaternium-37 (and) Paraffinum Liquidum (and) PPG-1 Trideceth-6, Polyquaternium 37 (and) Propylene Glycole Dicaprate dicaprylate (and) PPG-1 trideceth-6, polyquaternium-7, Polyquaternium-44th

• a) 0,05 – 10 Gew.-% des erfindungsgemäßen Polymerisates
• b) 25 – 94,95 Gew.-% Wasser
• c) 5 – 50 Gew.-% Tenside
• c) 0 – 5 Gew.-% eines weiteren Konditioniermittels
• d) 0 – 10 Gew.-% weitere kosmetische Bestandteile

The polymers according to the invention can also be used in shampoo formulations as setting and / or conditioning agents. Polymers with a cationic charge are particularly suitable as conditioning agents. Preferred shampoo formulations included

• a) 0.05-10% by weight of the polymer according to the invention
• b) 25-94.95% by weight water
• c) 5-50% by weight of surfactants
• c) 0-5% by weight of a further conditioning agent
• d) 0-10% by weight of further cosmetic ingredients

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

Suitable anionic surfactants are for example alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, Alkylarylsulfonates, alkylsuccinates, alkylsulfosuccinates, N-alkoylsarcosinates, Acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, Alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali and alkaline earth metal salts, e.g. Sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, Alkyl ether phosphates and alkyl ether carboxylates can contain between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule exhibit.

For example, sodium lauryl sulfate is suitable, Ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, Sodium lauroyl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, Sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.

Suitable amphoteric surfactants are for example alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, Alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or propionates, Alkyl amphodiacetates or dipropionates.

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

Examples of nonionic surfactants are suitable the reaction products of aliphatic alcohols or Alkylphenols with 6 to 20 carbon atoms in the alkyl chain that are linear or can be branched, with ethylene oxide and / or propylene oxide. The amount of alkylene oxide is about 6 to 60 moles to one mole of alcohol. Furthermore, alkylamine oxides, Mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, Alkyl polyglycosides or sorbitan ether esters are suitable.

In addition, the shampoo formulations can be conventional cationic Contain surfactants such as quaternary ammonium compounds, for example Cetyltrimethylammonium chloride.

In order to achieve certain effects, customary conditioning agents can be used in combination with the polymers according to the invention in the shampoo formulations. These include, for example, cationic polymers with the designation Polyquaternium according to INCI, in particular copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ^® FC, Luviquat ^® HM, Luviquat ^® MS, Luviquat ^® Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate (quaternized with 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). Protein hydrolyzates can also be used, and conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins. Other suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicone (CTFA). Cationic guar derivatives such as guar hydroxypropyltrimonium chloride (INCI) can also be used.

embodiments

The following examples demonstrate this improved properties of the polymers according to the invention in comparison to polymers in which either water in large amounts in the reaction mixture was present or the polyether component only after polymerization of individual monomers was added.

• a) Vinylimidazol quaternisiert mit Dimethylsulfat, 45%ige Lösung in Wasser (infolge "QVIXDMS")
• b) Diallyldimethylammoniumchlorid, 65%ige Lösung in Wasser (infolge "DADMAC")
• c) Pluronic^® PE 4300 Polyethylenglykol-Polypropylenglykol-Blockcopolymer (BASF Aktiengesellschaft)
• d) Pluriol^® E 600 Polyethylenglykol mit Molekulargewicht 600 (BASF Aktiengesellschaft)
• e) Wako V 50 Azostarter der Fa. Wako Chemicals GmbH

Were used:

• a) vinylimidazole quaternized with dimethyl sulfate, 45% solution in water (as a result of "QVIXDMS")
• b) Diallyldimethylammonium chloride, 65% solution in water (due to "DADMAC")
• c) Pluronic ^® PE 4300 polyethylene glycol-polypropylene glycol block copolymer (BASF Aktiengesellschaft)
• d) Pluriol ^® E 600 polyethylene glycol with molecular weight 600 (BASF Aktiengesellschaft)
• e) Wako V 50 azo starter from Wako Chemicals GmbH

Example 1: Production a cationic polymer by the process according to the invention.

A cationic was produced Polymer with the quantitative composition Pluronic PE 4300: QVIxDMS: DADMAC = 92: 7: 1. As monomers (a1) QVIxDMS and DADMAC were used in a 7: 1 ratio. The Water content during the polymerization was 7% by weight.

The reaction was carried out in a 2 1 glass apparatus (HWS) with anchor stirrer and temperature control (inside). The template was created with the liquid Product Pluronic PE 4300 and a portion of feed 1 filled and then to 85 ° C heated. At 80 ° C 8 g of feed 2 were added, followed by a wait of 4 minutes. Then became the inlets 1 and 2 started simultaneously. Feed 1 was over 6 h, the inlet 2 in parallel also over 6 h added. The mixture was then polymerized at 85 ° C for 2 h. Then was on Cooled at room temperature and diluted with feed 3. See property assessment below.

Comparative Example 1: Production of a cationic polymer by polymerization in watery solution

A cationic was manufactured Polymer with the quantitative composition Pluronic PE 4300: QVIxDMS: DADMAC = 92: 7: 1. The quantitative composition was identical to that of Example 1. As monomers (a1), QVIxDMS and DADMAC in relation 7: 1 used. The water content during the polymerization was however, in contrast to Example 1, 50% by weight.

The polymerization was analogous to for example 1 described. The reaction was carried out in a 2 l glass apparatus (HWS) with anchor stirrer and Temperature control (inside) carried out. The template was created with the liquid Product Pluronic PE 4300, water and a portion of the inlet 1 filled and then to 85 ° C heated. At 80 ° C 8 g of feed 2 were added, followed by a wait of 4 minutes. Then were the inlets 1 and 2 started simultaneously. Feed 1 was over 6 h, the inlet 2 in parallel also over 6 h added. The mixture was then polymerized at 85 ° C for 2 h. Then was cooled to room temperature. See property assessment below.

Comparative Example 2: Preparation of a mixture of polyether and a cationic polymer

• a) A cationic polymer with the quantitative composition QVIxDMS: DADMAC = 92: 7: 1 was produced. This serves as a preliminary product for the production of a mixture with the polyether component. The quantitative composition was identical to that of the monomers (a1) in Example 1. QVIxDMS and DADMRC in a ratio of 7: 1 were used as monomers (a1).
  
  The reaction was carried out in a 2 l glass apparatus (HWS) with anchor stirrer and temperature control (inside). The template was filled with water and a portion of feed 1 and then heated to 75 ° C. At 70 ° C, 2 g of feed 2 were added and then waited for 3 minutes. Then feeds 1 and 2 were started simultaneously. Feed 1 was added over 2.5 h, feed 2 over 3 h. The mixture was then polymerized at 75 ° C for 3 h. The mixture was then cooled to room temperature. For an assessment of the properties of the cationic product, see below.
• b) A mixture of the aqueous, cationic polymeric precursor (see above) and Pluronic PE 4300 with the formal composition as in Example 1 or Comparative Example 1 was produced. The composition was Pluronic PE 4300: QVIxDMS: DADMAC = 92: 7: 1.
  
  The mixture was carried out in a 2-1 glass apparatus (HWS) with anchor stirrer and temperature control (inside). In addition to the products Pluronic PE 4300 and Pluriol E 600, the template was filled with the cationic preliminary product from the previous experiment. This template becomes intense with space mixed temperature. See property assessment below.

Example 2: Comparison the properties of the polymers according to the invention with the polymers Comparative Examples 1 and 2

The polymers were in a Surfactant formulation with the following composition:

• 40.0% Texapon NSO (Sodium Laureth Sulfate solution 28%; Cognis)
• 10.0% Tego betaine L7 (cocamidopropyl betaine solution 30%; Goldschmidt)
• 0.5% polymer (solids content)
• add 100% water

i) Determination of combability

The following instructions describe the procedure for determining the wet and dry combability of hair after treatment with conditioners. All measurements are carried out in a climate room at 65% relative humidity and 21 ° C.

Devices used
Wet combability: Frank Zug / pressure tester
Dry combability: Diastron force measuring system
Digital scales (upper pan scales)

Hair:

• a) European, bleached: hair tresses from Wernesgrün (bleaching see below)
• b) Asian, untreated: hair tresses from Wernesgrün with split sharpen

The following tests are carried out:

• - Wet combability after using shampoo on European bleached hair
• - Dry combability after using shampoo on Asian hair

Pretreatment / Cleansing The Hair:

Before using for the first time Asian hair tresses in a solvent mixture (ethanol / isopropanol / acetone / water 1: 1: 1: 1) cleaned until the hair is clean when dry (i.e. no longer glued). Then the hair with sodium lauryl ether sulfate washed.

The European hair is afterwards with a bleaching paste (7.00 g ammonium carbonate, 8.00 g calcium carbonate, 0.50 g Aerosil 200, 9.80 g hydrogen peroxide (30%), 9.80 g fully desalinated Water) treated. The hair tresses are completely immersed in the bleaching paste, so that extensive wetting of the entire hair surface is guaranteed is. Subsequently the strands between the fingers are stripped off around the excess bleaching paste to remove. The exposure time of the remaining bleach on the hair, is adjusted to the degree of damage required, in the Usually 15 to 30 minutes, but can fluctuate due to the quality of the hair. After that, the bleached hair tresses are under running tap water thoroughly (2 minutes) rinsed and washed with sodium lauryl ether sulfate. Then you should the hair short in one because of the so-called creeping bleach aqueous, acidic solution (e.g. citric acid) immersed and rinsed with tap water.

applications:

1 minute into the hair Dipped surfactant formulation to be tested, shampooed for 1 minute and then 1 minute under flowing Drinking water (lukewarm) rinsed out.

I) Wet combability

Determination of blank value for wet combability: The washed hair is dried overnight in a climatic room. Before the measurement, they are shampooed twice with Texapon NSO for a total of 1 minute and rinsed out for 1 minute so that they are defined wet, ie swollen. Before the start of the measurement, the braid is pre-combed until the hair is no longer hooked, so that constant force is required if the combing is repeated. The braid is then fixed to the holder and combed into the fine-toothed side of the test comb with the fine-toothed side of the comb. The insertion of the hair into the test comb must be carried out evenly and stress-free with every measurement. The measurement is started and evaluated using software (EGRA-NUDO program, Frank company). The single measurement is repeated 5 to 10 times. The calculated mean is noted.

Determination of the measuring value for wet combability: After determining the blank value, the hair becomes more depending on the desired Application treated. The combing force is measured analogously to Blank determination.

Evaluation: Decrease in combing force wet [%] = 100 - (measured value · 100 / blank value)

II) Dry combability

Determination of blank value for dry combability: The washed hair becomes over Dried at night in the climate room. Before the measurement begins, the braid so combed until there are no more tangles in the hair and thus at repeated combing constant effort is required. Then will the braid is fixed to the bracket and into the fine-toothed side of the test comb combed. The hair has been inserted into the test comb with each measurement evenly and to be stress-free. The measurement is started and by Software (mtt-win, DIASTRON) evaluated. The single measurement is repeated 5 to 10 times. The calculated mean is put together noted with the standard deviation.

Determination of dry combing value: After determining the blank value, the hair is treated according to the desired application and dried overnight. The combing force is measured analogously to the blank value determination. Evaluation: Decrease in combing force wet [%] = 100 - (measured value · 100 / blank value)

The polymer of the invention provides that dry combing, but especially wet combability regarding, excellent results. Another advantage is that with the polymer according to the invention clear (wash) formulations are also possible.

Claims (33)

Use of cationic polymers, obtainable by polymerizing 3 to 30% by weight of at least one quaternary nitrogen-containing free-radically polymerizable monomer (a1) and / or a direct precursor (a2) thereof in the presence of 70 to 97% by weight of at least one polyether-containing one Compound (b) and optionally 0 to 15% by weight of one or more further radically polymerizable monomers (c) with a water solubility above 60 g / l at 25 ° C. and optionally 0 to 15% by weight of one or more further free radically polymerizable Monomers (d) with a water solubility below 60 g / l at 25 ° C., the water content in the reaction mixture during the polymerization being less than 20% by weight, and if a preliminary product (a2) is used, this after or during the polymerization is at least partially converted into a compound with quaternary nitrogen (a2 '), and wherein the molar ratio of the sum of the monomers (a1), (a2 ') and (c) to the sum of the monomers (d) is at least 2 to 1, and wherein the wt .-% of the individual components a1 and / or a2 , b and optionally add c and d to 100% by weight in cosmetic preparations. Use according to claim 1, wherein the monomer (a1) and / or the connection (a2 ') selected is from the group consisting of quaternary vinylamines, N, N, N-trialkylaminoalkylacrylates and methacrylates, N, N, N-trialkylaminoalkylacrylamides and methacrylamides, 3-alkyl-1-vinylimidazoles, 3-aryl-1-vinylimidazoles, quaternary vinyl pyridines and quaternary Diallylamines, as well as the salts. Use according to claim 1 or 2, wherein the monomer (a1) and / or the compound (a2 ') is selected from the group consisting of a) quaternary vinylamines of the general formulas (IIIa) or (IIIb) W- (CH ₂ ) _n -CR ¹⁵ = CHR ¹⁴ (IIIa)

wherein 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, and n is 0.1 or 2, and W is -N + (R ¹⁶ ) ₃ / X ^- or

where the radicals R ¹⁶ can be selected identically or differently from the group consisting of C ₁ -C ₄₀ linear or branched-chain alkyl radicals, formyl, C ₁ -C ₁₀ linear or branched-chain acyl, N, N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl, ethoxypropyl or benzyl, and where X ^{- is} an anion, b) N, N, N-trialkylaminoalkyl acrylates or methacrylates, N, N, N-trialkylaminoalkyl acrylamides or methacrylamides of the general formula (IV)

where R ¹⁴ , R ¹⁵ and W have the same meaning as in the general formula IIIa and IIIb in claim 3 a), and R ¹⁷ = hydrogen or methyl, R ¹⁸ = alkylene or hydroxyalkylene with 1 to 24 carbon atoms, Z = Nitrogen for g = 1 or oxygen for g = 0, c) quaternary N-vinylimidazoles of the general formula (V)

in which R ¹⁹ to R ²¹ independently of one another are hydrogen, C ₁ -C ₄ -alkyl, C1-C4-hydroxyalkyl or phenyl; and R ^{22 is} C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl or phenyl; and and X ^{- represents} an anion, d) quaternary vinyl pyridines of the general formula (VI)

where R ²¹ , R ²² and X ^{- have} the same meaning as in the general formula (V) in claim 3 c), e) quaternary diallylamines of the general formula (VII)

where R ²³ and R ^{24 can} each, independently of one another, be C ₁ - to C ₂₄ -alkyl and X ^{- stands} for an anion. Use according to any one of claims 1 to 3, wherein the monomer (a1) and / or the compound (a2 ') selected is made of N, N, N-trimethylaminomethyl (meth) acrylate, N, N, N-triethylaminomethyl (meth) acrylate, N, N, N-trimethylaminoethyl (meth) acrylate, N, N, N-triethylaminoethyl (meth) acrylate, N, N, N-trimethylaminobutyl (meth) acrylate, N, N, N-triethylaminobutyl (meth) acrylate, N, N, N-trimethylaminohexyl (meth) acrylate, N, N, N-trimethylaminooctyl (meth) acrylate, N, N, N-trimethylaminododecyl (meth) acrylate, N- [3- (trimethylamino) propyl] methacrylamide and N- [3- (trimethylamino) propyl] acrylamide, N- [3- (dimethylamino) butyl] methacrylamide, N- [8- (trimethylamino) octyl] methacrylamide, N- [12- (trimethylamino) dodecyl] methacrylamide, N- [3- (triethylamino) propyl] methacrylamide and N- [3- (triethylamino) propyl] acrylamide, (meth) acryloyloxyhydroxypropyltrimethylamine, (meth) acryloyloxyhydroxypropyltriethylamine, 3-methyl-1-vinylimidazole and N, N-dimethyl-N, N-diallylamine. Use according to one of claims 1 to 4, wherein the polymers starting from mixtures of 3-methyl-1-vinylimidazolium methyl sulfate and N, N-dimethyl-N, N-diallylammonium chloride as component (a1) available are. Use according to any one of claims 1 to 5, wherein the monomer (a2) selected is made of radically polymerizable unsaturated primary, secondary and tertiary Amines, unsaturated acids and unsaturated Halides. Use according to one of claims 1 to 6, wherein the monomer (a2) an amine is selected from the group of compounds consisting of a) aminoalkyl acrylates, aminoalkyl methacrylates, aminoalkyl acrylamides and aminoalkyl methacrylamides of the general formula (VIII)

where for R ¹⁴ to R ¹⁸ the definitions given for formula (IV) in claim 3 b) apply and 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, b) N-vinylimidazoles of the general formula IX , wherein for R ¹⁹ to R ²¹ independently of one another that for formula (V) the definitions given in claim 3 c) apply,

c) diallylamines of the general formula (X)

with R ²⁷ = hydrogen or C ₁ - to C ²⁴ -alkyl, d) 1,3-divinylimidazolid-2-one or N-disubstituted vinylamines of the general formula (XI): (R ²⁸ ) ₂ N- (CH ₂ ) _n -CR ¹⁵ = CHR ¹⁴ (XI) where R ¹⁴ R ¹⁵ and n have the same meaning as in the formulas (IIIa) and (IIIb), and the radicals R ²⁸ can be selected from the group consisting of hydrogen C ₁ -C ₄₀ linear or branched chain alkyl radicals, formyl, C ₁ -C ₁₀ linear or branched chain acyl, N, N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl, ethoxypropyl or benzyl, where if n = 0, not both radicals R ^{28 are} simultaneously hydrogen. Use according to one of claims 1 to 7, wherein the monomer (a2) selected is made of N, N-dimethylaminoethyl methacrylate, N- [3- (dimethylamino) propyl] methacrylamide, N-methylaminoethyl methacrylate, N- [3- (methylamino) propyl] methacrylamide, Aminoethyl methacrylate and N- [3-aminopropyl] methacrylamide, N-vinylimidazole, 1-vinyl-2-methylvinylimidazole and N, N-diallylamine. Use according to one of claims 6 to 8, wherein the quaternization with an alkyl halide with 1 to 24 carbon atoms, a dialkyl sulfate with 1 to 24 carbon atoms, an alkylene oxide or an epichlorohydrin he follows. Use according to claim 6, wherein the monomer (a2) is an unsaturated halide is selected from the haloalkyl acrylates or haloalkyl methacrylates. Use according to claim 10, wherein the quaternization with a Trialkylamine takes place. Use according to one of claims 1 to 11, wherein the monomer (c) selected is from the group consisting of N-vinyl lactams, N-vinyl carboxamides, Hydroxyalkyl acrylates, ethylenically unsaturated amides, vinylimidazoles, unsaturated acids and unsaturated Amines. Use according to one of claims 1 to 12, wherein the monomer (c) selected is from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylformamide, N-ethyl-N-vinylacetamide or N-methyl-N-vinyl acetamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butanediol monoacrylate, acrylamide, methacrylamide, N-vinylimidazole, acrylic acid, Maleic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, dimethylaminoethyl acrylate and dimethylaminomethacrylate. Use according to one of claims 1 to 13, wherein the monomer (d) is selected from the group consisting of C ₁ -C ₁₀ alkyl esters of monoethylenically unsaturated C ₃ -C ₆ carboxylic acids, di-C ₁ -C ₁₀ alkyl esters of ethylenically unsaturated Dicarboxylic acids, hydrocarbons with at least one radically polymerizable carbon-carbon double bond, vinyl, vinylidene or allyl halides, vinyl, allyl and methal Lyl esters of C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched chain or C ₃ -C ₄₀ carbocyclic carboxylic acids of aliphatic, saturated and unsaturated nature, vinyl, allyl and methallyl ethers of linear or branched, aliphatic alcohols with 2 to 20 C atoms , Use according to any one of claims 1 to 14, wherein the monomer (d) selected is from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, Ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, Ethyl ethacrylate, n-butyl ethacrylate, iso-butyl ethacrylate, t-butyl ethacrylate, 2-ethylhexylethacrylate, decylethacrylate, stearyl acrylate, stearyl (meth) acrylate, preferably styrene, alpha-methylstyrene, tert-butylstyrene, butadiene, Isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene, Vinyl toluene, vinyl chloride, vinylidene chloride, allyl chloride, vinyl acetate, Vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, vinyl 2-ethylhexanoate, Vinyl decanoate, vinyl laurate, vinyl stearate, vinyl methyl ether, vinyl ethyl ether, Vinyl dodecyl ether, vinyl hexadecyl ether, vinyl stearyl ether, acrylamidoglycolic acid, fumaric acid and Crotonic. Use according to one of claims 1 to 15, wherein the polyether-containing compound (b) is described by the general formula I,

in which the variables have the following meaning independently of one another: R ^{1 is} hydrogen, C ₁ -C ₂₄ -alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -, polyalcohol radical; R ^{5 is} hydrogen, C ₁ -C ₂₄ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -; R ² to R ⁴ - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH ₂ -CH (R ⁶ ) -, -CH ₂ -CHOR ⁷ -CH ₂ - ; R ⁶ C ₁ -C ₂₄ alkyl; R ^{7 is} hydrogen, C ₁ -C ₂₄ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -; A -C (= O) -O, -C (= O) -BC (= O) -O, -CH2-CH (-OH) -B-CH (-OH) -CH ₂ -O, -C ( = O) -NH-B-NH-C (= O) -O;

B - (CH ₂ ) _t -, arylene, optionally substituted; R ³⁰ R ^{31 is} hydrogen, C ₁ -C ₂₄ alkyl, C ₁ -C ₂₄ hydroxyalkyl, benzyl or phenyl; n 1 if R ^{1 is} not a polyalcohol radical or n 1 to 1000 if R ^{1 is} a polyalcohol radical s 0 to 1000; t 1 to 12; u 1 to 5000; v 0 to 5000; w 0 to 5000; x 0 to 5000; y 0 to 5000; z 0 to 5000. Use according to one of claims 1 to 16, wherein the polyether-containing compound (b) described by the general formula I has an average molecular weight of 500 to 50,000 (according to the number average) and the variables independently of one another have the following meanings: R ^{1 is} hydrogen, C ₁ -C ₆ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -; R ^{5 is} hydrogen, C ₁ -C ₆ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -; R ² to R ⁴ - (CH ₂ ) ₂ -, - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ -, -CH ₂ -CH (R ⁶ ) -, -CH ₂ -CHOR ⁷ -CH ₂ - ; R ⁶ C ₁ -C ₆ alkyl; R ^{7 is} hydrogen, C ₁ -C ₆ alkyl, R ⁶ -C (= O) -, R ⁶ -NH-C (= O) -; n 1; s 0; u 5 to 500; v 0 to 500; w 0 to 500. Use according to one of claims 1 to 17, wherein the polyether Compound a polymer, copolymer or block copolymer at least one compound selected from ethylene oxide and propylene oxide is. Use according to one of claims 1 to 15, wherein the polyether-containing Compound (b) is a polyether-containing silicone derivative. Use according to one of claims 1 to 15, wherein the polyether-containing Compound (b) by reacting polyethyleneimines with alkylene oxides is obtained. Use according to one of claims 1 to 15, wherein the polyether-containing Compound (b) by polymerizing ethylenically unsaturated alkylene oxide-containing monomers and optionally other copolymerizable Monomers available are. Use of polymers according to one of claims 1 to 21, the proportions a1) 3 - 30 Wt .-% b) 70-97 Wt .-% c) 0-15 Wt .-% d) 0-15 Wt .-% amount and the wt .-% of the individual components Add a1, b and optionally c and d to 100% by weight. Use of polymers according to one of claims 1 to 22, the proportions a1) 4 - 12 Wt .-% b) 88-96 Wt .-% c) 0% by weight d) 0% by weight amount and yourself the% by weight of the individual components a1 and b to 100% by weight in each case add. Cationic polymer, obtainable by polymerization of 3 to 30 wt .-% of at least one cationic, quaternary, radical polymerizable monomer (a1) in the presence of 70 to 97 % By weight of at least one polyether-containing compound (b) and possibly 0 to 15 wt .-% of one or more other radically polymerizable Monomers (c) with water solubility above 60 g / l at 25 ° C and optionally 0 to 15% by weight of one or more others radically polymerizable monomers (d) with water solubility below 60 g / l at 25 ° C, in which the molar ratio the sum of the monomers (a1) and (c) to the sum of the monomers (d) is at least 2 to 1, in which the water content in the reaction mixture during the polymerization is less than 20% by weight, and in which the% by weight of the individual components a1, b and possibly c and d add to 100% by weight. A cationic polymer according to claim 24, wherein i) the Monomers (a1) as in one of claims 2 to 5 ii) the polyether Compound (b) as in one of claims 16 to 21, iii) the Monomers (c) as in one of claims 12 or 13, and / or iv) the monomers (d) are as defined in one of claims 14 or 15. Cationic polymer according to one of claims 24 or 25, the composition of the polymer as in one of the Expectations 22 or 23 is defined. Process for the preparation of cationic polymers, according to any one of claims 24 to 26, characterized in that 3 to 30 wt .-% of at least one cationic, quaternary radically polymerizable monomer (a1) in the presence of 70 to 97 wt .-% of at least one polyether Compound (b) and optionally 0 to 15% by weight of one or more further radically polymerizable monomers (c) with a water solubility above 60 g / l at 25 ° C. and optionally 0 to 15% by weight of one or more further free-radically polymerizable Monomers (d) with a water solubility below 60 g / l at 25 ° C, is polymerized, the molar ratio of the sum of the monomers (a1) and (c) to the sum of Monomers (d) is at least 2 to 1, the water content in the reaction mixture during the polymerization being less than 20% by weight, and the weight% of the individual components a1, b and, if appropriate, c and d being 100 in each case Add% by weight. Hair cosmetic formulation composed as follows are: a) 0.05 - 20 % By weight of a cationic polymer according to one of claims 1 to 26 b) 20-99.95 % By weight of water and / or alcohol c) 0 - 79.05% by weight of further constituents Hair cosmetic formulation composed as follows are: a) 0.1-10 % By weight of a cationic polymer according to one of claims 1 to 26 b) 20-99.9 % By weight of water and / or alcohol c) 0 - 70 wt .-% of a blowing agent d) 0 - 20 % By weight of other constituents Hair cosmetic formulation composed as follows are: a) 0.1-10 % By weight of a cationic polymer according to one of claims 1 to 26 b) 55-94.8 % By weight of water and / or alcohol c) 5-20% by weight of a blowing agent d) 0.1 - 5 % By weight of an emulsifier e) 0-10% by weight of other constituents Hair cosmetic formulation composed as follows is. a) 0.1-10 % By weight of a cationic polymer according to one of claims 1 to 26 b) 60-99.85 % By weight of water and / or alcohol c) 0.05-10% by weight of a gel former d) 0 - 20 % By weight of other constituents Hair cosmetic formulation composed as follows is: a) 0.05-10 % By weight of a cationic polymer according to one of claims 1 to 26 b) 25-94.95 % By weight water c) 5 - 50 % By weight surfactants d) 0-5 % By weight of another conditioning agent e) 0-10% by weight other cosmetic ingredients