DE10212705A1 - 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 25degreesC and (d) optionally 0-15 wt% other comonomers with a water solubility of less than 60 g/l at 25degreesC. 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, Process for their preparation and their use in cosmetic formulations. The cationic graft polymers are obtainable by polymerizing quaternized-cationic, radically polymerizable monomers and optionally other radically copolymerizable monomers in the presence of a polyether compound with the proviso that the implementation in Presence of small amounts of water of less than 20% by weight on Total reaction mixture takes place.

DE 197 14 714 A1 describes linear block polymers Polyethylene glycol and cationic monomers using Macro initiators are synthesized. The connections are as polymeric surfactants used. Grafting reactions leading to branching Lead polymers are not described and in the described Process - according to the inventors - to be neglected (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 Dispersing. As a water-soluble polymer u. a. Polyethylene glycol used. As an ethylenically unsaturated monomer quaternary ammonium compounds are also used. In which described method is a water-in-water ("W / W") - emulsion polymerization, the significant water content having. So the ethylenically unsaturated monomers in a weight ratio of 3 to 150 parts to 100 parts of water used. The weight ratio of ethylenically unsaturated Monomer to the water-soluble polymer (e.g. polyethylene glycol) is 1: 5 to 5: 1. The high water content means that at no or only a very small proportion of this procedure Grafting of the ethylenically unsaturated monomers onto the water-soluble polymer takes place. The water-soluble polymer (e.g. Polyethylene glycol) has the function of a dispersing agent for the aqueous dispersion.

EP-A 0 183 466 describes processes for polymerization water soluble monomers in aqueous solution in the presence of a Dispersant and a salt. As a dispersant u. a. Polyethylene glycol can be used. Water soluble monomers include certain cationic monomers. The one "W / W" emulsion polymerization due to the typical high water content, that with this procedure no or very little Proportion of grafting of the ethylenically unsaturated monomers the water-soluble polymer takes place. The water-soluble polymer (e.g. polyethylene glycol) has the function of a Dispersant. A grafting of the monomers onto the Dispersant is not mentioned. The compounds obtained are called Flocculant for wastewater treatment or in the Paper industry used. Use in cosmetic preparations not described.

EP-A1 0 880 548 and DE 195 21 096 A1 describe methods for Production of dispersions of water-soluble vinyl polymers and Stabilizers to carry out the process. As Stabilizers are graft polymers consisting of a backbone Polyethylene oxide and graft from cationic, preferred quaternary vinyl polymers. The synthesis of the stabilizer as described in Example 1 takes place in aqueous solution. The Weight ratios of ethylenically unsaturated monomer:  Polyethylene glycol: water is 24: 30: 270. Use of this Stabilizers in cosmetic preparations are not mentioned. The disadvantage of the described method is the high water content in the Reaction mixture. With this procedure there is no or only a very small percentage of grafting the ethylenic unsaturated monomers on the water soluble polymer d. H. There are Polymers made from the cationic monomer and polyethylene glycol a significant proportion individually without grafting side by side before (see statement in Lieske A & Jaeger W (1998) Macromol Chem Phys 199: 255-260; s. O.). 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 1 made of polyethylene glycol. The contained in the polymer Carboxyl groups are then at least added by adding an Akylenimins partially implemented. Primary amino groups are preferred receive. Secondaries may also be possible. tertiary or quaternaries are not described and after the claimed method not accessible.

DD 117 326 describes the production of quaternized Graft polymers using a two-step process. It happens first a polymerization of nonionic ethylenically unsaturated Monomers (3-chloro-2-hydroxypropyl acrylate or vinylimidazole) in a melt made 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 Silver halide emulsion layers. Use in the field of Cosmetics are not described. The procedure described has Disadvantages from an economic and procedural point of view. On the one hand, the process control is based on the two-stage Process-intensive. On the other hand, the process - for example due to an incomplete second Implementation step - to polymers with non-reproducible properties to lead. The second implementation step also requires some toxic compounds that continue to complicate manufacture and - especially when using the polymer in z. B. cosmetic scope - force cleaning.

WO 00/49998 describes polymerization processes of vinyl esters in polyether-containing compounds such as Polyethylene glycol. In addition, other monomers such as cationic monomers are used. The process includes the subsequent saponification of the polymer. Both The polymers described is the proportion of the optional additional monomers used limited to a maximum of 50% (see page 9 / line 32 et seq.). It is preferably 0 to 20%.

For conditioning and strengthening keratinous substances like hair, nails and skin have been synthetic for years Polymers used. Requirements for hair conditioners are z. B. a strong reduction in the required combing force in the wet as in dry hair, good detangling the first time Combing ("Detangling") and good compatibility with others Formulation components. Requirements for hair setting resins are z. B. a strong consolidation in high humidity, Elasticity, washability of the hair and compatibility with others Formulation components. It creates difficulties Combination of different properties. So show polymers with good Fixing properties often low elasticities, so that with mechanical stress on the hairstyle, the strengthening effect often significantly impaired by damage to the polymer film becomes. In addition, synthetic polymers are used in cosmetic Formulations containing pigments or cosmetically active components included, as a compatibility agent to achieve a homogeneous, stable formulation used.

Despite the extensive efforts, it still exists Improvement in polymers to create elastic hairstyles at the same time strong consolidation even in high humidity, good washability and good grip of the hair. The There is also a need for improvement in the production of polymers combable, detangled hair and for conditioning skin and Hair in its sensible properties such as handle, Volume, manageability, etc. Also clear aqueous Preparations of these polymers are desirable, which is therefore characterized by a good compatibility with other formulation components distinguished.

The task was therefore to find new polymers for in particular to provide hair cosmetic formulations, on the one hand the hairstyle strong strengthening at the same time high Elasticity and, on the other hand, the hair is easy to comb at the same time give it a voluminous appearance and clear with water Preparations result.

The object is achieved by the provision of the invention Dissolved polymers.

A first object of the invention relates to the use of cationic polymers, obtainable by polymerizing:
at least one quaternary nitrogen-containing radically polymerizable monomer (a1) and / or a direct precursor (a2) thereof
in the presence of polyether-containing compounds (b) and
optionally one or more further radically polymerizable monomers (c) with a water solubility above 60 g / l at 25 ° C. and
optionally one or more further radical-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 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,
and 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,
in cosmetic preparations.

The invention further relates to polymers obtainable by polymerizing:
at least one cationic, quaternary radically polymerizable monomer (a1)
in the presence of polyether-containing compounds (b) and
optionally one or more further radically polymerizable monomers (c) with a water solubility above 60 g / l at 25 ° C. and
optionally one or more further 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, and the water content in the reaction mixture during the polymerization is less than 20% by weight.

The use of said inventive means is also included Polymers in the applications listed below, especially in cosmetic preparations.

Another object of the invention relates to processes for the preparation of the polymers according to the invention, characterized in that
at least one cationic, quaternary radically polymerizable monomer (a1)
in the presence of polyether-containing compounds (b) and
optionally one or more further radically polymerizable monomers (c) with a water solubility above 60 g / l at 25 ° C. and
optionally one or more further 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, and the water content in the reaction mixture during the polymerization being less than 20% by weight.

The polymers according to the invention have excellent properties Dry and wet combability of the hair treated with them. Other advantages include the soft grip and the antistatic properties of the treated surfaces such as Textiles, hair, skin, paper, fiber and non-woven materials, however other surfaces too. Pigments or preparations with cosmetically active components are Stabilized polymers. Another advantage is that with the polymers according to the invention aqueous compositions such as Hair shampoos and washing gels can be clearly formulated. In addition, the polymers can be used in the form of aqueous or aqueous / alcoholic solutions, as an aqueous emulsion, Microemulsion, dispersion, opaque or transparent gels or Aerosols.

In the preparation of the polymers used according to the invention can be grafted onto the polymer during the polymerization polyether-containing compounds (b) come what the advantageous properties of the polymers. Depending on Degree of grafting are among those used in the present invention Polymers 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 optionally to understand (a2), (c) and (d). In doing so, they rise Polymers according to the invention with regard to their properties clearly differ from mixtures in which the polymerization in the presence larger amounts of water is realized (see comparative experiment 1) or in which the polyether component only after the Polymerization of the monomers is added (see comparative experiment 2). It mechanisms other than grafting are also conceivable, which cause these changed, advantageous properties can.

As polyether-containing compounds (b) both Polyalkylene oxides based on ethylene oxide, propylene oxide, butylene oxide and other alkylene oxides and polyglycerol can be used.

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) -.

The structural units can be both Homopolymers as well as statistical copolymers and block copolymers act.

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 of one another 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 are 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 hydroxyl groups of the polyethers produced on the basis of polyalkylene oxides and the secondary OH groups of polyglycerol can be freely available both in unprotected form and with alcohols, for example mono-, di-, tri- or polyalcohols, with a chain length of C ₁ - C ₂₄ or etherified or esterified and optionally crosslinked with carboxylic acids having a chain length of C ₁ -C ₂₄ 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-nonadecyl or n-eicosyl.

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

The molecular weight of the polyethers is smaller 1,000,000 (by number average), preferably in the range from 300 to 100,000, particularly preferably in the range from 500 to 50,000, entirely particularly preferably in the range from 600 to 20,000.

Homopolymers of ethylene oxide or copolymers of ethylene oxide and Propylene oxide are particularly preferred, the molar Ratio of ethylene oxide to propylene oxide preferably in a range from 1: 9 to 9: 1. It is advantageously used Homopolymers of ethylene oxide or copolymers, with a Ethylene oxide content from 9 to 99 mol%. For those who prefer to be used The proportion of ethylene oxide polymers is thus copolymerized ethylene oxide 10 to 100 mol%. As a comonomer for this Copolymers come propylene oxide, butylene oxide and / or Isobutylene oxide into consideration. Copolymers are suitable, for example from ethylene oxide and propylene oxide, copolymers from ethylene oxide and butylene oxide and copolymers of ethylene oxide, Propylene oxide and at least one butylene oxide. The ethylene oxide content the copolymer is preferably 10 to 99 mol%, the Propylene oxide proportion 1 to 90 mol% and the proportion of butylene oxide in the copolymers 1 to 30 mol%. In addition to straight chain also branched homopolymers or copolymers as polyether-containing ones Compounds (b) are used.

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

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

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 -C ₁₂ 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;
u 0 to 2000;
v 0 to 2000;
w 0 to 2000.

Polymers of general formula I with an average molecular weight of 600 to 20,000 (by 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 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.

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

Silicones are generally used in hair cosmetics Improved grip used. The use of polyether-containing silicone derivatives as polyether (b) in the Polymers according to the invention can therefore in addition to a Improve the grip of the hair.

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




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 where the radicals R ^{8 may 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 30,000,
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 , denotes any alkyl, cycloalkyl or aryl radical which has between 1 and 40 C atoms and which has further ionogenic groups like NH ₂ , COOH, SO ₃ H can wear.

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), homo- and Copolymers of polyalkylene oxide-containing ethylenically unsaturated Monomers such as polyalkylene oxide (meth) acrylates, Polyalkylene oxide vinyl ether, polyalkylene oxide (meth) acrylamides, Polyalkylene oxide allyamides or polyalkylene oxide vinyl amides be used. Copolymers can of course also be used such monomers with other ethylenically unsaturated monomers be used.

However, polyether-containing compounds b) can also Reaction products of polyethyleneimines with Akylenoxiden used become. 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 of 300 up to 20,000, preferably 500 to 10,000, very particularly preferably 500 up to 5000. The weight ratio between Alkylene oxide and polyethyleneimine used is in the range of 100: 1 to 0.1: 1, preferably in the range 50: 1 to 0.5: 1, very particularly preferably in the range from 20: 1 to 0.5: 1.

The polyether (b) is most preferably a Homopolymer of ethylene oxide or 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 be in 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:
  
  
  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,
  
  
  wobei die Reste R¹⁶ identisch oder verschieden ausgewählt werden können aus der Gruppe bestehend aus C₂-C₄₀ linear- oder verzweigtkettige Alkylreste, Formyl, C₁-C₁₀ linear- oder verzweigtkettige Acyl, N,N-Dimethylaminoethyl, 2-Hydroxyethyl, 2-Methoxyethyl, 2-Ethoxyethyl, Hyclroxypropyl, 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 = Waserstoff 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-(Trimesthylamino)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
  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-2-vinylimidazoliunmethylsulfat.
• 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:
  
  
  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,
  
  
  where the radicals R ¹⁶ can be selected identically or differently from the group consisting of C ₂ -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, hyclroxypropyl, methoxypropyl, ethoxypropyl or benzyl, preferred are 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.
  
  
  wherein 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 encompassed according to the invention can be unsubstituted, N-alkyl or N-alkylamino monosubstituted or N, N-dialkyl-substituted or N, N-dialkylamino-substituted, 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.
  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- (trimesthylamino) 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.
  Further preferred are (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,
  
  
  in which
  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
  X ^{- stands} for 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-2-vinylimidazolium methyl sulfate are particularly preferred.
• 4. Quaternary vinyl pyridines 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 above groups with one another (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, N-diallylammonium chloride, and mixtures of foregoing. Mixtures of (a1) are very particularly preferred 3-methyl-1-vinylimidazolium methyl sulfate and N, N-dimethyl-N, N-diallyl.

Direct precursors (a2) for component (a1) comprises generally all such radically polymerizable monomers, which by a reaction in a radically polymerizable monomer with a quaternary nitrogen can be implemented. For the as a result of the compounds obtained (a2 ') the same applies Definitions as given for (a1) above. For those as direct Preproduct for (a1) component (a2) in question the following radically polymerizable monomers are preferred:

1) Unsaturated primary, secondary or tertiary amines

The leading to the polymers of the invention Quaternization of the amines can, for example, by implementing the in the amino groups contained in the monomers (a2) Alkyl halides with preferably 1 to 24 carbon atoms in the alkyl group will be realized. Are particularly preferably used 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. Other suitable for quaternization Agents include dialkyl sulfates such as in particular Dimethyl sulfate or diethyl sulfate. A quaternization of basic Amino groups can also be combined with alkylene oxides such as ethylene oxides or propylene oxides can be realized in the presence of acids. Most are used as agents for quaternization used: methyl chloride, dimethyl sulfate or diethyl sulfate. Furthermore, a reaction with quaternized epichlorohydrin is the general formula (XII) possible (see below).

• 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-dimethylaminooctyl(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 = Wasserstroff 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 Meahyl, Ethyl, n-Propyl und Benzyl. Dabei gilt, wenn n = 0, dass nicht beide Reste R²⁸ gleichzeitig Wasserstoff sind.

By way of example but not restrictive, the following may be mentioned for 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-dialkylamino-substituted, 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-dimethylaminooctyl (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. Meahyl, 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, for example, by using unsaturated acids such as B. acrylic acid or methacrylic acid as starting compound (a2) would be obtained 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.

Hydroxy and / or amino groups can also be used accordingly containing monomers (a2) are reacted. Are preferred Hydroxyl groups of the polyvinyl alcohol units and vinylamine Units created by hydrolysis of vinyl formamide.

3) halides of radically polymerizable monomers, such as for example haloalkyl acrylates or Halogenalkylmethacrylate

Chlorine, bromine or iodine compounds are preferred. An example, but not restrictive, is to be mentioned 3-chloro-2-hydroxypropyl acrylate. Implementation to quaternary Amines are made by reaction with amines e.g. B. Trialkylamines such as trimethylamine or triethylamine.

Of course, mixtures of the respective Monomers from group (a2) are polymerized. The most preferred monomers (a2) include N-vinylimidazole, N, N-diallylamine and Aminoethyl.

The conversion of the compounds (a2) to quaternary amines (as a result of a2 ') can take place during or after the reaction. at a subsequent reaction can the intermediate polymer first isolated or - preferably - implemented immediately. 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 too quaternary amines are preferably the higher, the lower the Water solubility of the monomer (a2). Is that Water solubility of the monomer (a2) below 60 g / l so the reaction is like this performed that the ratio of the sum of the monomers (a2 ') and optionally (a1) and (c) to the sum of the monomers (a2) and (d) is at least 2 to 1, preferably 4 to 1, particularly preferably 10 to 1.

The polymerizable ones containing the quaternary nitrogen Monomer (a1) and / or its precursors (a2) can also in 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. The ratio is preferably at least 4 to 1, very particularly preferably at least 10 to 1, am most preferably at least 20 to 1.

Basically, all hydrophilic monomers come as monomers (c) with a water solubility above 60 g / l at 25 ° C, those with the monomers (a1) and optionally (a2) and (d) are copolymerizable. They are preferably ethylenically unsaturated Monomers. Various monomers suitable as monomers (c) are among others 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 Have carbon-carbon double bond, the mono-, di-, tri- or can be tetrasubstituted.

• a) N-Vinyllactame, bevorzugt mit einem 5- bis 7-Ring, wie z. B. N-Vinylpyrrolidon, N-Vinylpiperidon, N-Vinylcaprolactam,
• b) acyclische N-Vinylcarbonsäureamide, bevorzugt mit 2- bis 6 C- Atomen, wie z. B. N-Vinylformamid, N-Ethyl-N-vinylacetamid oder N-Methyl-N-vinylacetamid,
• c) Hydroxyalkylacrylate, bevorzugt mit 2 bis 6 C-Atomen, wie z. B. 2-Hydroxyethylacrylat, 2-Hydroxyethylmethacrylat, 2-Hydroxypropylmethacrylat, Butandiolmonoacrylat,
• d) ethylenisch ungesättigte Amide, wie beispielsweise Acrylamid oder Methacrylamid,
• e) N-Vinylimidazol,
• f) Ungesättigte Säuren, bevorzugt Carbon- oder Sulfonsäuren, wie beispielsweise Acrylsäure, Maleinsäure, Methacrylsäure, 2-Acrylamido-2-methylpropansulfonsäure,
• g) Ungesättigte Amine wie Dimethylaminoethylacrylat, Dimethylaminomethacrylat.

The monomers (c) are preferably

• a) N-vinyl lactams, preferably with a 5- to 7-ring, such as. B. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam,
• b) acyclic N-vinylcarboxamides, preferably having 2 to 6 carbon atoms, such as. B. N-vinylformamide, N-ethyl-N-vinylacetamide or N-methyl-N-vinylacetamide,
• c) Hydroxyalkylacrylate, preferably with 2 to 6 carbon atoms, such as. B. 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, butanediol monoacrylate,
• d) ethylenically unsaturated amides, such as, for example, acrylamide or methacrylamide,
• e) N-vinylimidazole,
• f) Unsaturated acids, preferably carboxylic or sulfonic acids, such as, for example, acrylic acid, maleic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid,
• g) Unsaturated amines such as dimethylaminoethyl acrylate, dimethylaminomethacrylate.

Any mixtures of different monomers (c) be used. Particularly preferred monomers (c) are N-vinyl lactams and N-vinyl imidazole. N- is very particularly preferred Vinylpyrrolidone.

Basically, all hydrophobic monomers come as monomers (d) with a water solubility below 60 g / l at 25 ° C, those with the monomers (a1) and optionally (a2) and (c) are copolymerizable. They are preferably ethylenically unsaturated Monomers. Various monomers suitable as monomers (d) are among others described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A21, chapter "Polyacrylates", pp. 157-178, 5. 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, Propylacryiat, 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 C₅-C₁₀-Cycloalkanolen, z. B. Maleinsäuredimethylester oder Maleinsäuredi-n-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, Vinyldodeoylether, 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, especially 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, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, methacrylate, methacrylate, methacrylate, methacrylate, t-methacrylate, are particularly preferred , 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 glycols, (alkyl) polypropylene glycols or ethoxylated fatty alcohols, for example C ₁₂ -C ₂₄ fatty alcohols 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 ₅ -C ₁₀ cycloalkanols, e.g. B. dimethyl maleate or di-n-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 aliphatic, saturated or unsaturated nature. Preferred carboxylic acids are, for. B. 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, lignoceric acid and melissinic acid, cerotinic 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. B. vinyl methyl ether, vinyl ethyl ether, vinyl dodeoyl ether, vinyl hexadecyl ether and vinyl stearyl ether.
• 7. Monoethylenically unsaturated monocarboxylic acids, provided 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.

Any mixtures of different monomers (d) be used. Particularly preferred monomers (d) are Vinyl acetate, methyl methacrylate, methyl acrylate and ethyl acrylate.

In addition to the above comonomers can be used as Comonomers (c) or (d) so-called macromonomers such as, for example silicone-containing macromonomers with one or more radicals polymerizable groups or alkyloxazoline macromonomers used as described for example in EP 408 311. Furthermore, fluorine-containing monomers such as are described, for example, in EP 558423, which have a crosslinking action or the molecular weight regulating compounds in combination or used alone. The assignment to the groups (c) or (d) occurs according to their solubility.

The person skilled in the art is aware that a monomer (a2) belongs to the group of Monomers (c) or (d) can fall as long as (a2) does not fall into one quaternary amine (a2 ') was implemented.

The basic monomers (c) or (d) can also be cationized by using mineral acids such as. B. sulfuric acid, Hydrochloric acid, hydrobromic acid, hydroiodic acid, Phosphoric acid or nitric acid, or with organic acids, such as B. formic acid, acetic acid, lactic acid, or Citric acid to 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-ethylhexylthioglycolate, thioglycolic acid or Dodecyl mercaptan) and tribromochloromethane or other compounds, which regulates the molecular weight of the polymers obtained act, are used.

It may also contain thiol groups Silicone compounds are used.

Silicone-free controllers are preferably used.

Monomers (a1), (a2), (c) or (d) can also be crosslinking Monomers are used, for example compounds with at least two ethylenically unsaturated double bonds, such as 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 or are also suitable branched, linear or cyclic aliphatic or aromatic Hydrocarbons that have at least two double bonds have, which not with aliphatic hydrocarbons may be conjugated. Amides of acrylic and Methacrylic acid and N-allylamines of at least divalent Amines such as 1,2-diaminoethane, 1,3-diaminopropane. Further are 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'-divinylethylene urea, reaction products polyhydric alcohols with acrylic acid or methacrylic acid, Methacrylic acid esters and acrylic acid esters of polyalkylene oxides or polyhydric alcohols with ethylene oxide and / or propylene oxide and / or epichlorohydrin have been implemented.

A very particularly preferred crosslinker is Divinylethylenharnstoff.

The crosslinking monomers are in an amount less than 5% by weight, based on the sum of the starting materials a) to d), used. Less than 3% by weight and very particularly preferably less than 1% by weight crosslinking Monomer used.

In the polymerization to produce the invention Polymers can optionally also other polymers, such as Example polyamides, polyurethanes, polyesters, homo- and copolymers of ethylenically unsaturated monomers. Examples for such polymers, some of which are also used in cosmetics are the polymers known under the trade names Amerhold ™ Ultrahold ™, Ultrahold Strong ™, Luviflex ™ VBM, Luvimer ™, Acronal ™, Acudyne ™, Stepanhold ™, Lovocryl ™, Versatyl ™, Amphomer ™ or Eastma AQ ™. Furthermore, cationic Guar derivatives such as guar hydroxypropyltrimonium chloride (INCI) are used become.

The comonomers (c) and / or (d) according to the invention can, if they contain ionizable groups, before or after Polymerization, in part or in full, with acids or bases be neutralized, for example the water solubility or -Dispersibility to a desired level.

As a neutralizing agent for monomers bearing acid groups For example, mineral bases such as sodium carbonate, Alkali hydroxides and ammonia, organic bases such as amino alcohols especially 2-amino-2-methyl-1-propanol, monoethanolamine, Diethanolamine, triethanolamine, triisopropanolamine, tri [(2-hydroxy) 1- Propyl] amine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol and diamines, such as lysine, be used.

To prepare the polymers, the monomers of Component a1) in the presence of the polyether using both Free radical initiators as well as by action high energy radiation, including exposure to high energy Electrons to be understood are polymerized.

As initiators for radical polymerization, the Peroxo and / or azo compounds customary for this are used are, for example alkali or ammonium peroxydisulfates, Diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert.- butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl 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). Are also suitable Initiator mixtures or redox initiator systems, such as. B. Ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate.

Organic peroxides are preferably used.

The amounts of initiator or initiator mixtures used 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% by weight.

The polymerization takes place in the temperature range from 40 to 200 ° C, preferably in the range of 50 to 140 ° C, particularly preferably in the range from 60 to 110 ° C. It is usually under carried out at atmospheric pressure, but can also be under reduced or increased pressure, preferably between 1 and 5 bar, expire. The reaction temperature is preferably chosen such that they at least match the melting temperature of the polyether Compound (b) under the respective reaction conditions, so that the reaction can be carried out in a melt of (b) can.

The polymerization can be, for example, solution polymerization, Bulk polymerization, emulsion polymerization, reverse Emulsion polymerization, suspension polymerization, reverse Suspension polymerization or precipitation polymerization be carried out without the applicable methods on it are limited. Bulk polymerization is preferred, the polymerization of a1 and optionally a2, c and / or d in Presence of b is carried out. Here is 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 preferably less than 5% by weight. Prefers is operated under essentially water-free conditions and carried out bulk polymerization. "In the in this context, essentially anhydrous means that in addition to the no additional water contained in the starting products Water is introduced into the reaction mixture. "During the Polymerization "in this context means that the radical polymerization of the radically polymerizable monomers has not yet been completed. This is a polymerization considered as incomplete as long as the content of Residual monomers compared to the starting amount of monomers is greater than 50%, preferably greater than 30%, particularly preferred greater than 10%, very particularly preferably greater than 5%, on most preferably greater than 2%. After the completion of the polymerization as defined above, it is possible for the reaction mixture Water also in higher amounts (i.e. more than 20% by weight on Add reaction mixture).

With the particularly preferred bulk polymerization, one can proceed in such a way that at least one monomer from group (a1) and / or (a2) and / or possibly further comonomers of groups (c) and / or (d) dissolves in the polyether-containing compound (b) and after adding a polymerization initiator, the mixture polymerized. The polymerization can also be semi-continuous be carried out by first part, z. B. 10% of the polymerizing mixture of the polyether-containing compound (b), at least one monomer from group (a1) and / or (a2), possibly further comonomers of groups (c) and / or (d) and Initiator presents the mixture to the polymerization temperature heated and after the polymerization started the rest of the polymerizing mixture according to the progress of the polymerization admits. The polymers can - most preferably - also can be obtained by having the polyether-containing compounds of group (b) in a reactor to which Heated 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 either all at once, batchwise or preferably continuously and polymerized.

Emulsifiers can be added for the polymerization. As For example, ionic or emulsifiers are used non-ionic surfactants, the HLB value of which is in the range from 3 to 18. to Definition of the HLB value is based on the publication of Griffin WC (1954) J Soc Cosmetic Chem Band. 5, p. 249. The The amount of surfactants, based on the polymer, is 0 to 10% by weight. No surfactants are preferred for the polymerization added.

The polymerizations for the preparation of the invention In the presence of at least one non-aqueous polymer, organic solvent or in mixtures of at least an organic solvent and water. It is preferred to use per 100 parts by weight of the sum of the starting materials (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 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 as well as glycols such as ethylene glycol, propylene glycol and butylene glycol as well as the methyl or ethyl ethers of the dihydric alcohols, Diethylene glycol, triethylene glycol, glycerin and dioxane.

• 1. 2 bis 60 Gew.-% mindestens eines Monomers (a1) mit quaternären Aminogruppen und
• 2. 0 bis 30 Gew.-% eines oder mehreren weiteren copolymerisierbaren Monomeren (c) und
• 3. 0 bis 30 Gew.-% eines oder mehreren weiteren copolymerisierbaren Monomeren (d) in Gegenwart von
• 4. 40 bis 98 Gew.-% mindestens einer polyetherhaltigen Verbindung (b),

wobei sich für eine definierte Polymerisation die Gew.-% der einzelnen Komponenten a1-d auf jeweils 100 Gew.-% addieren. Polymers according to the requirements described above are preferred, which are obtainable by radical polymerization of

• 1. 2 to 60 wt .-% of at least one monomer (a1) with quaternary amino groups and
• 2. 0 to 30% by weight of one or more further copolymerizable monomers (c) and
• 3. 0 to 30% by weight of one or more further copolymerizable monomers (d) in the presence of
• 4. 40 to 98% by weight of at least one polyether-containing compound (b),

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

• 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 wt .-% 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. Are very particularly preferred

• 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 be in the range from 10 to 300, preferably 11 to 100, particularly preferably 15 to 60. The each desired K value can be done in a manner known per se adjust by the composition of the input materials. 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 are between 0.1% and 5% by weight. Other solvents too instead of N-methylpyrrolidone can be used. Ethanol is particularly preferred. Relate to the limits given above prefers the determination of 1% polymer solutions in Ethanol.

After the reaction, the polymer solutions can be removed can be steam distilled from, for example, residual monomers. After steam distillation, depending on the amount of quaternized amino groups and the type of polyether (b) aqueous solutions or dispersions. Obtaining aqueous solutions is preferred. Advantageously, the invention Polymers for reasons of better manageability Completion of the polymerization water added. The is Polymer content preferably 20 to 60% by weight.

The polymers can be dried in various ways such as B. spray drying, fluidized spray drying, roller drying or freeze drying in powder form. As Spray drying is preferred. Out The polymer dry powder thus obtained can be dissolved or redispersing in water an aqueous solution or Prepare dispersion. The powder transfer has the Advantage of a better shelf life, a simpler one Possibility of transportation as well as a lower inclination for germ contamination.

• 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 fotographischer 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 Gelatineersatzstoff
• 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. A use may be mentioned as an example

• 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 such. B. in fabric softeners or in detergents and care products
• e) as stabilizers for, for example, dispersions z. B. 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 excellent for use in cosmetic Formulations, in particular hair cosmetic formulations.

The concept of cosmetic formulations is broad too understand and means all such preparations that are suitable for application on skin and / or hair and / or nails and another as an exclusively medical-therapeutic purpose follow.

Hair cosmetic formulations include in particular styling agents and / or conditioning agents in hair cosmetic preparations such as Hair treatments, hair foams (English Mousses), (hair) gel or Hair sprays, hair lotions, hair rinses, hair shampoos, Hair emulsions, top fluids, leveling agents for perms, Hair dye and bleach, "hot oil treatment" preparations, Conditioners, setting lotions or hair sprays. Yes after Application area 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 Conditioners for the skin, e.g. B. in skin or body care products, Foam and shower baths. The use in the Oral hygiene and other hygiene formulations, in Anti-acne agents, in sunscreens, in tanning agents, in pigmented 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 wt .-% water and / or alcohol
• c) 0-79.5% by weight of other constituents.

Alcohol includes all alcohols commonly used in cosmetics understand e.g. B. ethanol, isopropanol, n-propanol.

Other ingredients include those that are common in cosmetics To understand additives, for example blowing agents, defoamers, surfactant compounds, d. H. Surfactants, emulsifiers, Foaming agents and solubilizers. The used Surfactant compounds can be anionic, cationic, amphoteric or be neutral. Other common ingredients can also be z. B. preservatives, perfume oils, opacifiers, active ingredients, UV filters, care substances such as panthenol, collagen, vitamins, Protein hydrolyzates, alpha and beta hydroxycarboxylic acids, Protein hydrolyzates, stabilizers, pH regulators, dyes, Viscosity regulators, gelling agents, dyes, salts, Humectants, moisturizers, complexing agents and other common additives.

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

For example, conventional hair cosmetic polymers are suitable anionic polymers. Such anionic polymers are homo- and Copolymers of acrylic acid and methacrylic acid or their Salts, copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water soluble or water-dispersible polyester, polyurethane (Luviset® P.U.R.) and Polyureas. Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (e.g. Luvimer® 100P), Copolymers of N-tert-butyl acrylamide, ethyl acrylate, acrylic acid (Ultrahold® 8, Strong), copolymers of vinyl acetate, crotonic acid and possibly other vinyl esters (e.g. Luviset® brands), Maleic anhydride copolymers, optionally reacted with alcohols, anionic polysiloxanes, e.g. B. carboxy-functional, copolymers Vinyl pyrrolidone, t-butyl acrylate, methacrylic acid (e.g. Luviskol® VBM).

Furthermore, the group includes those to be combined with the Examples of suitable polymers according to the invention 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 from Poly (methyl vinyl ether / maleic acid) in ethanol), amphomeric HC (National Starch; acrylate / Octylacrylamide copolymer), Amphomer® 28-4910 (National Starch; Octylacrylamide / acrylates / butylaminoethyl methacrylate copolymer) Advantage® HC 37 (ISP; terpolymer made of Vinyl caprolactam / vinyl pyrrolidone / dimethylaminoethyl methacrylate), Acudyne® 258 (Rohm &Haas; Acrylate / hydroxyester acrylate copolymer), Luviset® PUR (BASF, Polyurethane-1), Luviflex® Silk (BASF), Eastman® AQ48 (Eastman).

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

Other suitable hair cosmetic polymers are cationic polymers with the name Polyquaternium according to INCI, z. B. copolymers Vinyl pyrrolidone / N-vinyl imidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care), copolymers N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with Diethyl sulfate (Luviquat® PQ 11), copolymers of N-vinylcaprolactam N-vinyl pyrrolidone / N-vinyl imidazolium salts (Luviquat® Hold); cationic Cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7).

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

Neutral hair polymers are also other hair cosmetic polymers suitable as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, Polyvinylcaprolactam and copolymers with N-vinylpyrrolidone, Polyethyleneimines and their salts, polyvinylamines and their salts, Cellulose derivatives, polyaspartic acid salts and derivatives.

The preparations can be used to set certain properties also conditioning substances based on Contain silicone compounds. Suitable silicone compounds are for example polyalkylsiloxanes, polyarylsiloxanes, Polyarylalkylsiloxanes, polyether siloxanes, silicone resins or dimethicone Copolyols (CTFA) and amino functional silicone compounds such as Amodimethicone (CTFA).

The polymers according to the invention are particularly suitable as Fixing agents in hair styling preparations, in particular Hair sprays (aerosol sprays and pump sprays without propellant) and Hair foams (aerosol foams and pump foams without propellant gas).

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

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% by weight of a blowing agent
• d) 0-20% by weight of further constituents.

Blowing agents are common for hair sprays or aerosol foams blowing agent used. Mixtures of are preferred Propane / butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152a), 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 Treibmittels
• 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 further constituents.

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

Examples of nonionic emulsifiers (INCI nomenclature) are Laurethe, e.g. B. Laureth-4; Cetethe, e.g. B. Cetheth-1, Polyethylenglycolcetylether; Cetearethe, e.g. B. Cetheareth-25, Polyglycol fatty acid glycerides, hydroxylated lecithin, lactyl ester of Fatty acids, alkyl polyglycosides.

Examples of cationic emulsifiers are cetyldimethyl-2- hydroxyethylammonium dihydrogen phosphate, cetyltrimonium chloride, Cetyltrimmonium bromide, cocotrimonium methyl sulfate, quaternium-1 to x (INCI).

Anionic emulsifiers can be selected, for example from the group of alkyl sulfates, alkyl ether sulfates, Alkyl sulfonates, alkyl aryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, Alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, Alpha-olefin sulfonates, especially the alkali and alkaline earth metal salts, z. As sodium, potassium, magnesium, calcium, and ammonium and Triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can be between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 Have 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 gel formers customary in cosmetics can be used as gel formers be used. These include slightly cross-linked polyacrylic acid, for example carbomer (INCI), cellulose derivatives, e.g. B. Hydroxypropyl cellulose, hydroxyethyl cellulose, cationically modified Celluloses, polysaccharides, e.g. B. Xanthum Gummi, 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-44.

• a) 0,05-10 Gew.-% des erfindungsgemäßen Polymerisates
• b) 25-94,95 Gew.-% Wasser
• c) 5-50 Gew.-% Tenside
• d) 0-5 Gew.-% eines weiteren Konditioniermittels
• e) 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 wt .-% surfactants
• d) 0-5% by weight of a further conditioning agent
• e) 0-10% by weight of further cosmetic ingredients.

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

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

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.

Suitable amphoteric surfactants are, for example, alkyl betaines, Alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, Alkyl carboxyglycinates, alkyl amphoacetates or propionates, Alkyl amphodiacetates or dipropionates.

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

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

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

In the shampoo formulations can be used to achieve certain Effects of conventional conditioning agents in combination with the polymers according to the invention are used. Which includes for example called cationic polymers Polyquaternium according to INCI, especially copolymers Vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care), copolymers from N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ 11), copolymers 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, as well conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, Polyarylalkylsiloxanes, polyether siloxanes or silicone resins. Further suitable silicone compounds are Dimethicone Copolyole (CTFA) and amino functional silicone compounds such as Amodimethicone (CTFA). Cationic guar derivatives such as Guar hydroxypropyltrimonium chloride (INCI) can be used.

embodiments

The following examples demonstrate the improved properties of the polymers according to the invention in comparison with polymers which either water in larger 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 of a cationic polymer after the inventive method

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

The reaction was carried out in a 2 l glass apparatus (HWS) Anchor stirrer and temperature control (inside) carried out. The template was developed with the liquid product Pluronic PE 4300 and a Part of the feed 1 filled and then heated to 85 ° C. At 80 ° C 8 g of feed 2 were added and then 4 minutes maintained. Then feeds 1 and 2 were started simultaneously. The feed 1 was over 6 h, the feed 2 in parallel over 6 h added. The mixture was then polymerized at 85 ° C for 2 h. The mixture was then cooled to room temperature and feed 3 diluted. See property assessment below.

Comparative Example 1 Producing a cationic Polymers by polymerization in aqueous solution

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

The polymerization was carried out analogously to that described for Example 1 carried out. The reaction was carried out in a 2 l glass apparatus (HWS) with anchor stirrer and temperature control (inside). The Template was created with the liquid product Pluronic PE 4300, water 40 and a portion of feed 1 filled and then to 85 ° C. heated. 8 g of feed 2 were added at 80 ° C. and then Waited 4 minutes. Then feeds 1 and 2 became simultaneous started. Feed 1 was over 6 h, feed 2 in parallel added over 6 h. Then was at 85 ° C for 2 h afterpolymerized. The mixture was then 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 DADMAC 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 intermediate, 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 l 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 is mixed intensively at room temperature. See property assessment below.

Example 2 Comparison of the properties of the invention Polymers with the polymers of Comparative Examples 1 and 2

The polymers were used in a surfactant solution 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)
ad 100% water

i) Determination of combability

The following instructions describe the procedure for determining the wet and dry combability of hair after treatment with conditioning agents. All measurements are carried out in a climatic room at 65% relative humidity and 21 ° C. Equipment used Wet combability: Frank Zug / Druck-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 ends

• - Naßkämmbarkeit nach Shampooanwendung an europäischen, gebleichten Haaren
• - Trockenkämmbarkeit nach Shampooanwendung an asiatischen Haaren

The following tests are carried out:

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

Pretreatment / hair cleaning

Before using for the first time, the Asian hair tresses are in one 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 Washed hair with sodium lauryl ether sulfate.

The European hair is then bleached with a 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 in the bleaching paste completely immersed so that extensive wetting of the entire hair surface is guaranteed. Then the Weft stripped between the fingers around the excess Remove bleaching paste. The exposure time, the remaining bleach on the hair will be the level of needed Adjusted for damage, usually is 15 to 30 minutes, can but fluctuate due to hair quality. After that the bleached hair tresses thoroughly under running tap water (2 minutes) rinsed and washed with sodium lauryl ether sulfate. Then the hair should be because of the so-called creeping bleach briefly in an aqueous, acidic solution (e.g. Citric acid) and rinsed with tap water.

applications

In the hair is 1 minute in the surfactant formulation to be tested dipped, shampooed for 1 minute and then under for 1 minute running water (lukewarm) rinsed out.

I) Wet combability Determination of blank value for wet combability

The washed hair will be dried overnight in the climate room. Before the measurement, they will shampooed twice with Texapon NSO for a total of 1 minute and 1 Minute rinsed so that it is defined wet, d. H. are swollen. Before the start of the measurement, the braid is combed until none Interlocking of the hairs are more present and thus repeated combing a constant application of force is required. Then the braid is fixed to the bracket and with the fine toothed side of the comb into the fine toothed side of the Comb combed. The insertion of the hair in the test comb has each measurement to be carried out evenly and stress-free. The Measurement is started and using software (EGRANUDO program, Fa. Frank) evaluated. The single measurement is made 5 to 10 times repeated. The calculated mean is noted.

Determination of wet combability

After determining the blank value, the hair is treated depending on the desired application. The combing force is measured analogously to the blank value determination. Evaluation of combing force decrease wet [%] = 100 - (measured value 100 / blank value)

II) Dry combability Determination of blank value for dry combability

The washed hair are dried in a climate room overnight. Before starting the measurement the braid is combed until no hair is caught are more available and therefore one with repeated measuring combs constant effort is required. Then the Tresse fixed to the bracket and into the fine-toothed side of the Comb combed. The hair has been inserted into the test comb to be carried out evenly and stress-free with every measurement. The Measurement is started and using software (mtt-win, DIASTRON) evaluated. The individual measurement is repeated 5-10 times. The calculated mean is calculated together with the Standard deviation noted.

Determination of dry combing value

After determining the blank value, the hair is treated depending on the desired application and dried overnight. The combing force is measured analogously to the blank value determination. Evaluation of combing force decrease wet [%] = 100 - (measured value 100 / blank value)

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

Claims (33)

1. Use of cationic polymers, obtainable by polymerizing
at least one quaternary nitrogen-containing radically polymerizable monomer (a1) and / or a direct precursor (a2) thereof
in the presence of polyether-containing compounds (b) and
optionally one or more further radically polymerizable monomers (c) with a water solubility above 60 g / l at 25 ° C. and
optionally 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 when using a preliminary product (a2), this is at least partially converted into a compound with quaternary nitrogen (a2 ') after or during the polymerization, 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
in cosmetic preparations. 2. Use according to claim 1, wherein the monomer (a1) and / or the compound (a2 ') is selected from the group consisting of from quaternary vinylamines, N, N, N-trialkylaminoalkyl acrylates and methacrylates, N, N, N-trialkyiaminoalkylacrylamides and methacrylamides, 3-alkyl-1-vinylimidazoles, 3-aryl-1-vinylimidazoles, quaternary vinyl pyridines and quaternary Diallylamines, as well as the salts. 3. 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)


in which
R ¹⁴ and R ^{15 are} independently selected from the group consisting of hydrogen, C ₁ -C ₈ linear or branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl, and


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)


wherein R ¹⁴ , R ¹⁵ and W have the same meaning as in the general formula IIIa and IIIb in claim 3, 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 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
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 6, 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. 4. Use according to one of claims 1 to 3, wherein the Monomers (a1) and / or the compound (a2 ') is selected from 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. 5. Use according to any one of claims 1 to 4, wherein the Polymers starting from mixtures 3-methyl-1-vinylimidazolium methyl sulfate and N, N-dimethyl-N, N-diallylammonium chloride are available as component (a1). 6. Use according to any one of claims 1 to 5, wherein the Monomer (a2) is selected from free-radically polymerizable unsaturated primary, secondary and tertiary amines, unsaturated acids and unsaturated halides. 7. Use according to one of claims 1 to 6, wherein the monomer (a2) is an amine selected from the group of compounds consisting of a) aminoalkyl acrylates and methacrylates and aminoalkyl acrylates and methacrylamides of the general formula (VIII)


wherein for R ¹⁴ to R ¹⁸ the definitions given for formula (IV) in claim 4 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, b) N-vinylimidazoles of the general formula IX, where the definitions given for formula (V) in claim 6 apply independently of one another for R ¹⁹ to R ²¹ ,


c) diallylamines of the general formula (X)


with R ²⁷ = hydrogen or C ₁ - to C ₂₄ -alkyl, 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. 8. Use according to one of claims 1 to 7, wherein the Monomer (a2) is selected from 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. 9. Use according to any one of claims 6 to 8, wherein the Quaterization 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. 10. Use according to claim 6, wherein the monomer (a2) is a unsaturated halide is selected from the Haloalkyl acrylates or haloalkyl methacrylates. 11. Use according to claim 10, wherein the quaternization with a trialkylamine. 12. Use according to one of claims 1 to 11, wherein the Monomer (c) is selected from the group consisting of N-vinyl lactams, N-vinyl carboxamides, hydroxyalkyl acrylates, ethylenically unsaturated amides, vinylimidazoles, unsaturated acids and unsaturated amines. 13. Use according to one of claims 1 to 12, wherein the Monomer (c) is selected from the group consisting of N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinylformamide, N-ethyl-N-vinylacetamide or N-methyl-N-vinylacetamide, 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. 14. 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 ethylenically unsaturated dicarboxylic acids, hydrocarbons with at least one radically polymerizable carbon-carbon double bond, vinyl, vinylidene or allyl halides, vinyl, allyl and methallyl esters of C ₁ -C ₄₀ linear, C ₃ -C ₄₀ branched 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 carbon atoms. 15. Use according to one of claims 1 to 14, wherein the Monomer (d) is selected from the group consisting of 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, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, Ethyl ethacrylate, n-butyl ethacrylate, iso-butyl ethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decyl ethacrylate, 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 acid. 16. 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, -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 are} 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 when 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. 17. 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 (by number average) and the variables have the following meaning independently of one another:
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. 18. Use according to any one of claims 1 to 17, wherein the polyether-containing compound, a polymer, copolymer or Block copolymer of at least one compound selected from Is ethylene oxide and propylene oxide. 19. Use according to one of claims 1 to 15, wherein the polyether-containing compound (b) a polyether-containing Silicone derivative is. 20. Use according to one of claims 1 to 15, wherein the polyether-containing compound (b) by reacting Polyethyleneimines with alkylene oxides is obtained. 21. Use according to one of claims 1 to 15, wherein the polyether-containing compound (b) by polymerization of ethylenically unsaturated alkylene oxide-containing monomers and optionally further copolymerizable monomers available are. 22. Use of polymers according to one of claims 1 to 21, wherein the quantitative ratios 1.2-60% by weight 2. 40-98% by weight 3.0-30% by weight 4.0-30% by weight amount and the wt .-% of the individual components a1, b and optionally c and d add up to 100 wt .-%. 23. Use of polymers according to one of claims 1 to 22, wherein the quantitative ratios 1.3-30% by weight 2. 70-97% by weight 3. 0-15% by weight 4. 0-15% by weight amount and the wt .-% of the individual components a1, b and optionally c and d add up to 100 wt .-%. 24. Use of polymers according to one of claims 1 to 23, wherein the quantitative ratios 1. 4-12% by weight 2. 88-96% by weight 3.0% by weight 4. 0% by weight amount and the wt .-% of the individual components a1 and b add up to 100 wt .-%. 25. Cationic polymer, obtainable by polymerizing at least one cationic, quaternary, free-radically polymerizable monomer (a1)
in the presence of polyether-containing compounds (b) and
optionally one or more further radically polymerizable monomers (c) with a water solubility above 60 g / l at 25 ° C. and
optionally one or more further 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, and the water content in the reaction mixture during the polymerization is less than 20% by weight. 26. Cationic polymer according to claim 25, wherein a) the monomers (a1) as in one of claims 2 to 5 b) the polyether-containing compound (b) as in one of claims 16 to 21, c) the monomers (c) as in one of claims 12 or 13, and / or d) the monomers (d) are as defined in one of claims 14 or 15. 27. Cationic polymer according to one of claims 25 or 26, the composition of the polymer as in one of the Claims 22 to 24 is defined. 28. A process for the preparation of cationic polymers, according to one of claims 25 to 27, characterized in that
at least one cationic, quaternary radically polymerizable monomer (a1)
in the presence of polyether-containing compounds (b) and
optionally one or more further radically polymerizable monomers (c) with a water solubility above 60 g / l at 25 ° C. and
optionally one or more further 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, and the water content in the reaction mixture during the polymerization being less than 20% by weight. 29. Hair cosmetic formulation, which is composed as follows: a) 0.05-20% by weight of a cationic polymer according to one of claims 1 to 26 b) 20-99.95 wt .-% water and / or alcohol c) 0-79.05% by weight of further constituents. 30. Hair cosmetic formulation, which is composed as follows: 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% by weight of a blowing agent d) 0-20% by weight of other constituents. 31. Hair cosmetic formulation, which is composed as follows: 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. 32. Hair cosmetic formulation, which is composed as follows: a) 01-10% 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 further constituents. 33. Hair cosmetic formulation, which is composed as follows: 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 wt .-% surfactants d) 0-5% by weight of a further conditioning agent e) 0-10% by weight of further cosmetic ingredients.