EP2027162A1 - Process for preparing polymers in aqueous solvents - Google Patents

Abstract

The present invention relates to processes for preparing polymers which contain 50-95% by weight of at least one ester of (meth)acrylic acid, 5-50% by weight of at least one olefinically unsaturated, free-radically polymerizable anionogenic or anionic compound and from 0 to 30% by weight of at least one further free-radically polymerizable compound in copolymerized form, by free-radical polymerization in a solution comprising alcohol, wherein the polymerization initiator used is at least one water-soluble initiator.

Description

Process for the preparation of polymers in aqueous solvents

description

The present invention relates to processes for the preparation of polymers which

Contain 50-95% by weight of at least one ester of (meth) acrylic acid, 5-50% by weight of at least one olefinically unsaturated, free-radically polymerizable anionogenic or anionic compound and 0 to 30% by weight of at least one further free-radically polymerizable compound by radical polymerization in an alcohol-containing solution, at least one water-soluble initiator being used as the polymerization initiator.

Numerous methods for producing polymers for hair cosmetics are known from the prior art. These include, for example, solution, precipitation, suspension or emulsion polymerization.

EP-A 0 694 565 describes a process for the homogeneous polymerization of water-insoluble polymers which contain more than 50% by weight of monomers selected from the group consisting of C1-C18-alkyl acrylate or methacrylate esters, N-substituted acrylic or methacrylamides and mixtures of the same , contained in essentially non-aqueous organic solvents, characterized in that a water-soluble initiator is used as the polymerization initiator, which is dissolved in an amount of water sufficient to dissolve the initiator and the polymer obtained is characterized by lower residual monomer contents than it is when using equivalent amounts of water-insoluble Initiators can be obtained. The solvent used contains at most as much water as is necessary to keep the water-soluble initiator in dissolved form.

WO 94/24986 describes the preparation of hair setting polymers based on acrylic acid and acrylic acid esters by solution polymerization in ethanol. The polymerization in alcoholic solvent mixtures which contain in the range from more than 25 to 50% by weight of water is not described.

EP-A 0 379 082 describes the preparation of hair setting polymers based on acrylic acid and acrylic acid esters by solution polymerization in ethanol. The polymerization in alcoholic solvent mixtures containing water in the range from more than 25 to 50% by weight is not described.

The processes known from the prior art frequently have the disadvantage that the reaction times are long, in particular in the case of polymers containing acrylic acid, and that the polymers obtained sometimes have high residual monomer contents. For ecological reasons, it is desirable to keep the use of volatile organic compounds (VOC) as low as possible (low VOC). In view of the economic viability of processes, it is also desirable to use readily available and inexpensive starting materials.

The object of the present invention was to provide a process which is improved for the production of polymers suitable for cosmetic applications and which overcomes the aforementioned disadvantages of the known processes.

This object was achieved by a process for the preparation of polymers which i) 50-95% by weight of at least one ester of (meth) acrylic acid, ii) 5-50% by weight of at least one olefinically unsaturated, free-radically polymerizable anionogenic or anionic Compound and iii) contain 0 to 30% by weight of at least one further free-radically polymerizable compound in copolymerized form, by free-radical polymerization in an alcohol-containing solution, at least one water-soluble initiator being used as the polymerization initiator, characterized in that the polymerization solution is in the range from contains more than 25 to 50 wt .-% water.

The polymers produced by the process according to the invention are preferably slightly or not soluble in water. The polymers are soluble at 20 ° C. and 1013 mbar, preferably at most 10 g in 1 liter of water.

i) esters of (meth) acrylic acid Suitable esters of (meth) acrylic acid are, for example, methyl (meth) acrylate,

Ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-pentyl ( meth) acrylate, 3-pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, n-octyl (meth) acrylate, 1, 1, 3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate, Heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, arachinyl (meth) acrylate, behenyl (meth) acrylate, lignocerenyl (meth) acrylate, cerotinyl (meth) acrylate, melissinyl (meth) acrylate, palmitoleinyl (meth) acrylate, oleyl ( meth) acrylate, linoleyl (meth) acrylate, linolenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, phenoxyethyl (meth) acrylate, 4-t-butylcyclohexyl acrylate, cyclohexyl (meth) acrylate, ureido (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and mixtures thereof. The polymers obtainable by the process according to the invention contain 50 to 95, preferably 65-85 and in particular 70-80% by weight of component i) in copolymerized form. ii) anionogenic or anionic compounds

Compound ii) is an olefinically unsaturated, free-radically polymerizable anionogenic or anionic compound. An anionogenic compound is understood to mean a compound which can be converted into the corresponding anionic form by deprotonation with customary, preferably cosmetically acceptable organic or inorganic bases.

Compound ii) is preferably selected from the group of the olefinically unsaturated, free-radically polymerizable carboxylic acids and their salts. Compound ii) is particularly preferably selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, half-esters of olefinically unsaturated dicarboxylic acids with 4 to 10, preferably 4 to 6 carbon atoms and their salts. Compound ii) is very particularly preferably selected from the group consisting of acrylic acid, methacrylic acid, their salts and mixtures thereof.

The polymers obtainable by the process according to the invention contain 5-50, preferably 10-40 and particularly preferably 15-28% by weight of component ii) in polymerized form.

iii) further radically polymerizable compound

In general, all compounds which are different from i) and ii) can be used as compound iii). Preferred compounds iii) are selected from the following groups:

1111) Radically polymerizable compounds containing urethane groups

1112) (meth) acrylamides,

1113) cationogenic monomers,

1114) cationic monomers, iii5) compounds with at least 2 polymerizable double bonds, which are usually also referred to as crosslinkers, iü6) compounds iii7) to iii4) different from iii2) to iii4) containing compounds iii7) polyesters containing at least two free-radically polymerizable, olefinically unsaturated double bonds iü8) polyethers, containing at least two radically polymerizable, olefinically unsaturated double bonds

iii1) Radically polymerizable compounds containing urethane groups At least one olefinically unsaturated compound containing urethane groups can be used as component iii1). In the context of the present invention, olefinically unsaturated compounds containing urethane groups are understood to mean compounds which have at least one urethane group and at least one polymerizable, preferably contain radically polymerizable olefinic double bond. Component iii1) suitable olefinically unsaturated prepolymers containing urethane groups for the polymers obtainable by the process according to the invention are described, for example, in PKT Oldring (ed.), Chemistry and Technology of UV and EB Formulations for Coatings, Inks and Paints, Vol. 11, SITA Technology, London, 1991, pp. 73-123, to which reference is hereby made in full. (Poly) urethane (meth) acrylates are known to the person skilled in the art. They can be obtained by reacting a di- or polyisocyanate with a chain extender from the group of the diols / polyols and / or diamines / polyamines and / or dithio-Ie / polythiols and / or alkanolamines and then reacting the remaining free isocyanate groups with at least one hydroxyalkyl (meth) acrylate or hydroxyalkyl esters of other ethylenically unsaturated carboxylic acids. The amounts of chain extender, di- or polyisocyanate and hydroxyalkyl ester are preferably chosen so that 1.) the equivalent ratio of the NCO groups to the reactive groups of the chain extender (hydroxyl, amino or mercaptyl groups) is between 3: 1 and 1 : 2, preferably 2: 1, and

2.) the OH groups of the hydroxyalkyl esters of the ethylenically unsaturated carboxylic acids are present in stoichiometric amounts in relation to the free isocyanate groups of the prepolymer of isocyanate and chain extender.

It is also possible to prepare (poly) urethane (meth) acrylates by first reacting part of the isocyanate groups of a diisocyanate or polyisocyanate with at least one hydroxyalkyl ester and then reacting the remaining isocyanate groups with a chain extender. In this case too, the amounts of chain extender, isocyanate and hydroxyalkyl ester are chosen so that the equivalent ratio of the NCO groups to the reactive groups of the chain extender is between 3: 1 and 1: 2, preferably 2: 1, and the equivalent ratio of remaining NCO groups to the OH groups of the hydroxyalkyl ester is 1: 1. Of course, all intermediate forms of these two methods are also possible. For example, part of the isocyanate groups of a diisocyanate can first be reacted with a diol, then another part of the isocyanate groups can be reacted with the hydroxyl ester and then the remaining isocyanate groups can be reacted with a diamine. These various manufacturing processes for polyurethane (meth) acrylates are known (e.g. from EP-A 0 203 161) and therefore do not require a detailed description.

Urethane (meth) acrylates suitable as component iii1) are also described in DE

A 198 38 852 S.3, Z.45 to S.9, Z.20 described, whereupon at this point in full

Scope is referred to.

Urethane (meth) acrylates are understood to mean compounds which A) contain at least one compound which contains at least one active hydrogen atom and at least one free-radically polymerizable, α, β-ethylenically unsaturated double bond per molecule, B) at least one diisocyanate and

C) contain at least one compound, which contains two active hydrogen atoms per molecule, incorporated, and the salts thereof.

Component A)

Suitable compounds A) are e.g. the usual vinyl compounds known to the person skilled in the art which additionally have at least one group which is reactive toward isocyanate groups and which is preferably selected from hydroxyl groups and primary and secondary amino groups. These include e.g. the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with at least dihydric alcohols. As α, ß-ethylenically unsaturated mono- and / or dicarboxylic acids such. As acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, itaconic acid etc. and mixtures thereof can be used. Suitable alcohols are conventional diols, triols and polyols, e.g. 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol, diethylene glycol, 2,2,4-trimethylpentanediol-1, 5, 2,2-dimethylpropanediol-1, 3, 1, 4-dimethylolcyclohexane, 1, 6-dimethylolcyclohexane, glycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitol etc. The compounds A) are then, for. B. hydroxymethyl (meth) acrylate, hydroxyethyl ethacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-

Hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-2-ethylhexyl (meth) acrylate and di (meth) acrylic acid ester of the 1st , 1, 1-trimethylolpropane or glycerol. Suitable compounds A) are also the esters and amides of the aforementioned α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ - to C ₂ -amino alcohols which have a primary or secondary amino group. These include aminoalkyl acrylates and aminoalkyl methacrylates and their N-monoalkyl derivatives, which, for. B. wear an N- Cr to Ce monoalkyl radical, such as aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, N-methylaminomethyl (meth) acrylate, N-ethylaminomethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate , N- (n-propyl) aminomethyl (meth) acrylate, N-isopropylaminomethyl (meth) acrylate and preferably tert-butylaminoethyl acrylate and tert-butylaminoethyl methacrylate. These also include N- (hydroxy-Cr to C ₂ -alkyl) (meth) acrylamides, such as N-hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide etc. Suitable compounds A) are also the amides of the abovementioned α , β-ethylenically unsaturated mono- and dicarboxylic acids with di- and polyamines which have at least two primary or two secondary or one primary and one secondary amino group (s). These include e.g. B. the corresponding amides of acrylic acid and methacrylic acid, such as aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, aminopropyl (meth) acrylamide, amino-n-butyl (meth) acrylamide, methylaminoethyl (meth) acrylamide, ethylaminoethyl (meth ) acrylamide, methylaminopropyl (meth) acrylamide, ethylaminopropyl (meth) acrylamide or methylamino-n-butyl (meth) acrylamide. Suitable compounds A) are also the reaction products of epoxy compounds which have at least one epoxy group with the abovementioned α, β-ethylenically unsaturated mono- and / or dicarboxylic acids and their anhydrides. Suitable epoxy compounds are e.g. B. glycidyl ethers such as bisphenol A diglycidyl ether, resorcinol diglycidyl ether, 1, 3-propanediol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 5-pentanediol diglycidyl ether or 1, 6-hexanediol diglycidyl ether.

Component B)

Component B) is a customary aliphatic, cycloaliphatic and / or aromatic diisocyanate, such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, 2,4- and 2,6-tolylene diisocyanate and their isomer mixtures, o- and m-xylylene diisocyanate, 1 , 5-naphthylene diisocyanate, 1,4-cyclohexylene diisocyanate, dicyclohexylmethane diisocyanate and mixtures thereof. Component B) is preferably hexamethylene diisocyanate, isophore diisocyanate, o- and m-xylylene diisocyanate, dicyclohexylmethane diisocyanate and mixtures thereof. If desired, up to 3 mol% of the compounds mentioned can be replaced by triisocyanates.

Component C) Suitable compounds C) are, for. B. diols, diamines, amino alcohols, and mixtures thereof. The molecular weight of these compounds is preferably in a range from about 56 to 280. If desired, up to 3 mol% of the compounds mentioned can be replaced by triols or triamines. Suitable diols C) are e.g. B. ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethylol, di-, tri-, tetra-, penta- or hexaethylene glycol and mixtures thereof. Neopentyl glycol and / or cyclohexanedimethylol are preferably used.

Suitable amino alcohols C) are, for. B. 2-aminoethanol, 2- (N-methylamino) ethanol, 3-aminopropanol, 4-aminobutanol, 1-ethylaminobutan-2-ol, 2-amino-2-methyl-1-propanol, 4-methyl-4-aminopentane -2-ol etc.

Suitable diamines C) are e.g. B. ethylenediamine, propylenediamine, 1, 4-diaminobutane, 1, 5-diaminopentane and 1, 6-diaminohexane.

Preferred compounds C) are polymers with a number average molecular weight in the range from about 300 to 5000, preferably about 400 to 4000, in particular 500 to 3000. B. polyester diols, polyetherols, α, ω-diamino polyether and mixtures thereof. Polymers containing ether groups are preferably used.

The polyetherols C) are preferably polyalkylene glycols, e.g. B. polyethylene glycols, polypropylene glycols, polytetrahydrofurans etc., block copolymers of ethylene oxide and propylene oxide or block copolymers of ethylene oxide, propylene oxide and butylene oxide, which contain the alkylene oxide units randomly distributed or copolymerized in the form of blocks. Suitable α, ω-diaminopolyether C) are, for. B. by amination of polyalkylene oxides with ammonia.

Suitable polytetrahydrofurans C) can by cationic polymerization of tetrahydrofuran in the presence of acidic catalysts, such as. As sulfuric acid or fluorosulfuric acid can be produced. Such production processes are known to the person skilled in the art.

Useful polyester diols C) preferably have a number average molecular weight in the range from about 400 to 5000, preferably 500 to 3000, in particular 600 to 2000. Suitable polyester diols are all those which are customarily used for the production of polyurethanes, in particular those based on aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, phthalic acid, Na- or K-sulfoisophthalic acid etc., aliphatic dicarboxylic acids, such as adipic acid or succinic acid etc., and cycloaliphatic dicarboxylic acids such as 1, 2-, 1, 3- or 1, 4-cyclohexanedicarboxylic acid. Particularly suitable diols are aliphatic diols, such as ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethylene glycols, polypropylene glycols, 1,4-dimethylolcyclohexane, and also poly (meth) acrylate diols of the formula

wherein R 'is H or CH ₃ and R "is Ci-Ci8-alkyl (in particular C ₁ -C ₁₂ - or d-Cβ-alkyl), which have a molecular weight of up to about 3000. Such diols are conventional as manufactured and commercially available (Tegomer ^® grades MD, BD and OD of Fa. Goldschmidt). preferred are polyester based on aromatic and aliphatic dicarboxylic acids and aliphatic diols, in particular those in which the aromatic dicarboxylic acid constitutes 10 to 95 mol%, in particular 40 to 90 mol% and preferably 50 to 85 mol%, of the total dicarboxylic acid content (remainder aliphatic dicarboxylic acids). Particularly preferred polyester diols are the reaction products of phthalic acid / diethylene glycol, isophthalic acid / 1,4- Butanediol, isophthalic acid / adipic acid / 1, 6-hexanediol, 5-NaSO3-isophthalic acid / phthalic acid / adipic acid / 1, 6-hexanediol, adipic acid / ethylene glycol, isophthalic acid / adipic acid / neopentyl glycol, isophthalic acid / adipic acid / dimethylene glycol ylolcyclohexane and 5-NaSO ₃ - isophthalic acid / isophthalic acid / adipic acid / neopentyl glycol / diethylene glycol / dimethyl cyclohexane.

The compounds C) can be used individually or as mixtures. Further possible constituents of these urethane (meth) acrylates can be found in DE-A 198 38 852 p. 5, lines 40 to 9, line 20, to which reference is made in full. The following may also be mentioned as suitable component iii1):

NM a) reaction products of the reaction of hydroxy (meth) acrylates with diols and / or OH-terminated polyols and / or OH-terminated polyesters and / or diamines and diisocyanates. Such difunctional urethane acrylate oligomers and their preparation are described, for example, in WO 97/00664, p. 5, p. 17 to p. 6, p. 8 and the corresponding examples, to which reference is made in full here.)

iii1 b) carbamoyloxycarboxylates of the general formula I

R ¹ OO

-ORO ^^ NHR ³ (I) where

R ¹ H, halogen or C1-C8-alkyl,

R ^{2 is} optionally substituted CrCi ₂ alkylene, arylene, alkylarylene or arylalkylene, polyoxyalkylene, R ³ Ci-C ₈ alkyl.

Such carbamoyloxycarboxylates of the general formula I are disclosed in US 3,479,328 and US 3,674,838, which are hereby incorporated by reference in their entirety.

iii1 c) the divinyl urethanes of the general formula II disclosed in GB 1 443 715

in which

R H or methyl A (poly) alkyleneoxy and vinyl urethanes of the general formula

where R and A are defined as in formula II and X and n as defined in GB 1 443 715 p.2, lines 9-13. The vinyl urethanes likewise described in GB 1 443 715, to which reference is hereby made in full, are further possible components c) of the polymers according to the invention.

iii1 d) the N-substituted carbamoyloxyalkyleneoxyalkyl (meth) acrylates described in EP-A 0 036 813, to which reference is hereby made in full general formula IV

where R, R ', R "and X are as defined in EP-A 0 036 813, p.2, lines 13-28 and n is an integer from 0 to 20, preferably from 1 to 6 and particularly preferably from 1 to 4 means.

Nile) the urethane acrylate compounds known from DE-A-4 007 146, which is hereby incorporated by reference in their entirety, which can be obtained by reacting polyisocyanates with hydroxyalkyl acrylates, followed by reaction with primary or secondary amines.

iii1f) products of the reaction of isocyanates with polyols and hydroxyalkyl acrylates as described for example in DE 27 26 041 A, US 4,260,703 and US 4,481,093 and products of the reaction of isocyanates with hydroxyalkyl acrylates as in

JP 63297369 and JP 591571 12, to which reference is hereby made in full.

iii1g) the prepolymers described in EP-A 0 903 363, to which reference is hereby made in their entirety, which can be prepared by a process in which component A containing isocyanate groups and containing OH groups is obtained Component B is reacted, component A comprising at least one trifunctional isocyanate compound A1 and optionally one or more difunctional isocyanate compounds A2 and component OH containing OH groups at least one olefinically unsaturated compound B1 with at least one reactive OH group and optionally different OH groups - Group-containing compounds B2, wherein either component A comprises two different isocyanate compounds A1 or one isocyanate compound A1 and at least one isocyanate compound A2 or component B comprises at least two different compounds B2.

iii1 h) polyurethane polymers, which A) 40 to 80 wt .-%, based on the total weight of components A) to F), of at least one hydroxyl group-containing prepolymer with at least one radically or photochemically polymerizable α, β-ethylenically unsaturated double bond, the Prepolymer

A) is a reaction product or a mixture of a) at least one polyester acrylate and / or polyether acrylate and / or polyurethane acrylate and b) at least one epoxy acrylate,

B) 0.1 to 20% by weight, based on the total weight of components A) to F), of at least one compound having at least one compound which is reactive toward isocyanate groups tive hydroxyl and / or primary or secondary amino group and additionally at least one polar functional group,

C) 0.1 to 10% by weight, based on the total weight of components A) to F), of at least one compound selected from diamines, polyamines and mixtures thereof,

D) 0 to 20% by weight, based on the total weight of components A) to F), of at least one further compound different from A), B), C) and E) with at least two groups which are reactive toward isocyanate groups, it being are hydroxyl groups and mixtures of hydroxyl groups and / or primary or secondary amino groups,

E) 0 to 20% by weight, based on the total weight of components A) to F), of at least one compound having a group which is reactive toward isocyanate groups,

F) contains 10 to 50% by weight, based on the total weight of components A) to F), of at least one polyisocyanate, and the salts thereof, which are characterized in that the sum of the hydroxyl numbers of components A) and D) is in a range from 121 to 300 mg KOH / g. These polyurethane polymers are described in EP-A 0 942 022, to which reference is hereby made in full.

iii1 i) the reaction products of a) isocyanate trimers (mixtures) based on aliphatic or cycloaliphatic diisocyanates described in EP-A 1 002 818 (to which reference is hereby made in their entirety), which are up to 100 mol% consist of compounds of the iminooxadiazinedione structure type of the formula A,

in which R ¹ , R ² and R ³ independently of one another represent optionally branched C4-C20- (cyclo) alkylene, and

X stands for the same or different residues of isocyanate or of isocyanate secondary products, which are of the iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret or oxadiazinetrione structure type and N-constantly the abovementioned residues R ¹ , R ² and R ³ , with b) an alcohol component which contains at least one monovalent hydroxy-functional optionally branched CrCi ₂ alkyl ester of (meth) acrylic acid. iii1j) the allyl group-containing polyurethanes of the general formula V, as disclosed in WO 01/72862, to which reference is hereby made in full: R ¹ - [NHCO (OR) _y (OCH ₂ CH = CH ₂ ) _m ] n (V)

The meanings of R, R ¹ , y, m and n are described in WO 01/72862 on page 3, line 29 to page 4, line 10.

iii1 k) the (meth) acrylic acid esters described in WO 04/050888, to which reference is hereby made in full, which can be prepared by reacting an alcohol containing urethane groups with (meth) acrylic acid or an ester of (meth) acrylic acid with a saturated alcohol and optionally purifying the reaction mixture, the reaction being carried out in the presence of an enzyme (E).

iii1 l) the urethane (meth) acrylate oligomers described in WO 98/06783, to which reference is made in their entirety here, in particular to S.1, Z.22 to S.2, Z.6 .

iii1 m) the polyurethanes described in DE 44 34 554 A1, to which reference is made in their entirety here, in particular on pages 2, line 42 to page 4, line 27.

iii1 n) the urethane (meth) acrylate oligomers described in WO 04/067599, to which reference is hereby made in full, in particular on pages 10, lines 24 to 12, line 13. iii1 o) the urethane acrylates described in US Pat. No. 5,240,835, to which reference is made in full at this point, which can be prepared by the transesterification of alkyl acrylates with alcohols under the catalysis of a biocatalyst from Corynebacterium oxydans.

iii1 p) the carbamoyloxy (meth) acrylates described in WO 04/052843, to which reference is made in their entirety at this point, which can be prepared by a process as described on p.3, c.34 to p.10 , Z.28 of WO 04/052843.

iii1 q) the carbamoyloxy (meth) acrylates which are described in WO 94/25537 p.8, lines 29 to p.9, line 32, to which reference is made in full at this point. IiMy) the polyisocyanate secondary products described in DE-A 102 46 1 12, to which reference is hereby made in full, containing at least one allophanate group which has at least one acrylate, methacrylate or vinyl ether on the oxygen atom of the allophanate group bonded via two single bonds - carries double bond, characterized in that a polyisocyanate or polyisocyanate secondary product containing at least one oxadiazinetrione group with an acrylate, Alcohol containing methacrylate or vinyl ether double bond reacts at temperatures between -20 to 100 ° C.

iii1 r) WO 00/39183, to which reference is hereby made in full, describes compounds with isocyanate groups or blocked isocyanate groups, allophanate groups and free-radically polymerizable CC double bonds, the CC double bonds being linked by a carbonyl group or an O atom is activated in ether function (activated double bonds), derived from polyisocyanates and alcohols A, which carry an activated double bond in addition to the alcohol group.

These compounds are preferably reacted with alcohols ROH which carry only one OH group or with amines RNH ₂ or RR'NH in at least the amount which is sufficient to convert all isocyanate groups and blocked isocyanate groups into urethane or urea groups. Here, R and R 'independently of one another denote d-Ci ₂ alkyl, aryl, alkylaryl or arylalkyl, polyoxyalkylene, where the radicals may optionally be functionalized with hydroxyl groups.

Preferred alcohols for this reaction are CrCi ₂ -, in particular dC ₄ -alkanols such as, for example, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol.

Preferred amines for this reaction are CrCi ₂ -, in particular CrC ₄ - (di) alkylamines, (di) alkanolamines, alkylalkanolamines such as ethylamine, butylamine, diethylamine, ethanolamine, diethanolamine, 2-amino-2-methylpropanol. In this way, for example, compounds of the following general formulas are obtained:

From the reaction with alcohols:

From the reaction with amines:

in which

R Ci-Ci ₂ alkyl, aryl, alkylaryl or arylalkyl, polyoxyalkylene, optionally functionalized with hydroxyl groups

R 'H, Ci-Ci ₂ alkyl, aryl, alkylaryl or arylalkyl, polyoxyalkylene, optionally functionalized with hydroxyl groups n 0 to 10, preferably 0 to 5, particularly preferably 0 to 2 A Ci-Ci ₂ alkylene, Arylene, alkylarylene or arylalkylene, polyoxyalkylene and mixtures thereof.

Of course, the corresponding methacrylate derivatives of these compounds can also be used as component c). Suitable components c) are, for example

iii1 s) N-butyl-2-hydroxyethyl-carbamate (CAS 63225-53-6) of the formula

(such as commercially available as Ebecryl ^® CL 1039 (UCB)) and the corresponding methacrylic acid derivative,

iii1t) N-methyl-2-hydroxyethyl-carbamate (CAS 52607-81-5) of the formula

and the corresponding methacrylic acid derivative,

iii1 u) one or a mixture of the two components of the following formulas (the mixture is referred to herein as monomer C22 (see also the examples)): and the corresponding methacrylic acid derivatives,

iii1 v) one or a mixture of the two components of the following formulas

and the corresponding methacrylic acid derivatives,

iii1w) compound of the following formula

where n is 0 to 10, preferably 0 to 4, particularly preferably 0 to 2, and the corresponding methacrylic acid derivatives. iii1 x) diurethane dimethacrylate 7,7,9- (or 7,9,9-) trimethyl-4,13-dioxo-3,14-dioxa-5,12-diaza-hexadecane-1, 16-diol-dimethacrylate ( CAS, which is commercially available for example as PLEX 6661-0 ^® (Degussa) 72869-86-4).

As component iii1) suitable polyurethane (meth) acrylates such as polyurethane mono- di-, tri-, tetra-, penta- or hexa- (meth) acrylates are commercially available under the trademarks Laromer ^® (BASF), Photomer ^® (Cognis), Sartomer ^® (Sartomer) or Ebecryl ^® (UCB).

They can be used in pure form (without diluents), as solutions in solvents such as ethanol or butyl acetate or as solutions in reactive diluents (such as tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), Trimethylolpropanformalmonoacrylat (Laromer ^® LR 8887), trimethylolpropane triacrylate (TMPTA), propoxylated glyceryl triacrylate (GPTA), 5 Ethoxylated trimethylolpropane triacrylate (EO3TMPTA), ethoxyethoxyethyl acrylate (E- OEOEA), PEG 400 diacrylate (PEG400DA), isobornyl acrylate (IBOA), propoxylated neopentylglycol diacrylate (PO2N PGDA), 2-phenoxyethylacrylate (POEA), butanediol diodiacrylate (DCPA), triethylene glycol divinyl ether, ethyl digycol acrylate (EDGA), lauryl acrylate (LA), 4-t-

10 butylcyclohexyl acrylate (TBCH) or as aqueous emulsions. Such polyurethane (meth) acrylates are:

Laromer ^® types LR 8949, LR 9005, LR 8983, UA 19 T, UA 9030V, UA 9028V, UA 9029V, UA 9033V, UA 9031V and LR 8987, Photomer ^® types 6891, 6892, 6893-20R, 6572, 6010 , 6019, 6184, 6210, 6217, 6230,

15 6363 and 6008

Sartomer ^® CN types such as the aliphatic urethane acrylates CN 934 CN 934X50, CN 944B85, CN 945A60, CN 945B85, CN 953B70, CN 961 E75, CN 961 H81, CN 962, CN 963A80, CN 963B80, CN 963E75, CN 963E80, CN 963J85, CN 964, CN 964A85, CN 964B85, CN 964H90, CN

20 964E75, CN 965, CN 965A80, CN 966A80, CN 966B85, CN 966H90, CN 966I80, CN 966J75, CN 966R60, CN 968, CN 982E75, CN 982P90, CN 983, CN 983B88, CN 984, CN 985B88 and the aromatic ones Urethane acrylates CN 970A60, CN 970E60, CN 970H75, CN 971A80, CN 972, CN 973A80, CN 973H85, CN 973J75, CN 975, CN 977C70, CN

25 978, CN 980, CN 980M50, CN 981, CN 981 A75, CN 981 B88, CN 982A75, CN 982B88 Ebecryl ^® grades, such as 220, 230, 244, 264, 265, 270. As the compound iii1) are particularly preferred Carbamoyloxycarboxylates of the general formula VIII

R ¹ OO

_ _n . ., - -ORO ^ NHR ³ (VIII)

OU being

R ¹ H, halogen, C _r C ₈ alkyl, preferably H or methyl, R ² optionally substituted Ci-Ci ₂ alkylene, arylene, alkylarylene or arylalkylene, optionally hydroxy-substituted polyoxyalkylene, 35 R ³ H, d -Cs-alkyl mean.

In general, those compounds iii1) are preferred which contain at most 4, preferably at most 3 and particularly preferably at most 2 radical polymerizable double bonds per molecule. The polymers obtainable by the process according to the invention contain 0-30, preferably 0.1-20, particularly preferably 0.5-10 and most preferably 0.5-5% by weight of the compound iii) copolymerized.

Component iii2)

Suitable components iii2) are the amides of (meth) acrylic acid which are different from iii3) and iii4). Such amides are, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, Nn-propyl- (meth) acrylamide, Ni-propyl- (meth) acrylamide, N- (n-butyl) methacrylamide, N- (sec-butyl) methacrylamide, N- (tert-butyl) methacrylamide, N- (n-pentyl) (meth) acrylamide, N- (n-hexyl) (meth) acrylamide, N- (n -Heptyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (tert-octyl) (meth) acrylamide N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N - ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide , N-myristyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (meth) acrylamide, N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-

Arachinyl (meth) acrylamide, N-behenyl (meth) acrylamide, N-lignocerenyl (meth) acrylamide, N-cerotinyl (meth) acrylamide, N-melissinyl (meth) acrylamide, N-palmitoleinyl (meth) acrylamide, N-oleyl ( meth) acrylamide, N-linoleyl (meth) acrylamide, N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-lauryl (meth) acrylamide. Suitable components iii2) are furthermore 2-hydroxyethylacrylamide, 2-hydroxyethyl methacrylamide, 2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide, 2-hydroxypropyl methacrylamide, 3-hydroxypropylacrylamide, 3-hydroxypropyl methacrylamide, 3-hydroxybutylacrylamide, 3-hydroxybutyl methacrylamide, 4-hydroxyamidyl acrylate, 4-hydroxyamidyl acrylamide 6-hydroxyhexyl acrylamide, 6-hydroxyhexyl methacrylamide, 3-hydroxy-2-ethylhexyl acrylamide and 3-hydroxy-2-ethylhexyl methacrylamide.

Components iii3) and iii4) Components iii3) and iii4) are monomers which contain at least one cationogenic and / or cationic group per molecule.

The cationogenic or cationic groups are preferably nitrogen-containing groups, such as primary, secondary and tertiary amino groups as well as quaternary ammonium groups. The nitrogen-containing groups are preferably tertiary amino groups.

Components iii3) and iii4) are preferably used in the uncharged form for the polymerization. However, use in a charged form is also suitable. Charged cationic groups can be generated, for example, from the amine nitrogen atoms by protonation, for example with monovalent or polyvalent carboxylic acids, such as lactic acid or tartaric acid, or mineral acids, such as phosphoric acid, sulfuric acid and hydrochloric acid. Components iii3) and iii4) are preferably selected from Esters of α, β-olefinically unsaturated mono- and dicarboxylic acids with amino alcohols, which may be mono- or dialkylated on the amine nitrogen, amides of α, β-olefinically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group, N, N-diallylamine,

N, N-diallyl-N-alkylamines and their derivatives, vinyl and allyl-substituted nitrogen heterocycles, vinyl and allyl-substituted heteroaromatic compounds and mixtures thereof.

Also suitable as components iii3) and iii4) are the esters of α, β-olefinically unsaturated mono- and dicarboxylic acids with amino alcohols. Preferred amino alcohols are C ₂ -C ₂ amino alcohols which are Ci-Ce mono- or dialkylated on the amine nitrogen. As an acid component of these esters are, for. B. acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Acrylic acid, methacrylic acid and mixtures thereof are preferably used.

Particularly preferred as components iii3) and iii-4) are N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N- (n-propyl) aminoethyl (meth) acrylate, N- (n-butyl) aminoethyl ( meth) acrylate, N- (tert-butyl) aminoethyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N ₁ N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N ₁ N - Dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N ₁ N-dimethylaminocyclohexyl (meth) acrylate. In particular, components iii3) and iii4) used are N- (tert-butyl) aminoethyl acrylate and N- (tert-butyl) aminoethyl methacrylate.

Suitable components iii3) and iii4) are furthermore the amides of the aforementioned α.β-olefinically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group. Diamines which have a tertiary and a primary or secondary amino group are preferred. Preferred components iii3) and iii4) are N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- ( dimethylamino) cyclohexyl] acrylamide and N- [4- (dimethylamino) cyclohexyl] methacrylamide are used.

N- [3- (dimethylamino) propyl] acrylamide and / or N- [3- (dimethylamino) propyl] methacrylamide are particularly preferably used.

Suitable components iii3) and iii4) are also N, N-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts. Alkyl is preferably d-C ₂₄ alkyl. N, N-Diallyl-N-methylamine is preferred. Suitable components iii3) and iii4) are also vinyl and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinylimidazole derivatives, e.g. B. N-vinyl-2-methylimidazole, vinyl and allyl substituted heteroaromatic compounds such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof. Suitable components iii3) and III4) are N-vinylimidazoles of the formula VII, wherein R ¹ to R ³ is hydrogen, C _r C ₄ alkyl or phenyl

Examples of compounds of the general formula VII can be found in the following Table 1:

Table 1

Me = methyl; Ph = phenyl

Components iii3) and iii4) are particularly preferably selected from N- (tert-butylamino) ethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- [3- (dimethylamino) propyl] (meth) acrylamide , Vinylimidazole and mixtures thereof. If the polymers prepared by the process of the invention contain compounds iii3) and / or iii4) in copolymerized form, they contain at least 0.1% by weight, preferably at least 1% by weight, particularly preferably at least 2% by weight and in particular at least 3% by weight. % and at most 30% by weight, preferably at most 20% by weight, particularly preferably at most 15% by weight and in particular at most 10% by weight of components iii3) and / or iii4), based on the total weight of the compounds used i) to iii).

The charged cationic groups can be generated from the amine nitrogen by quaternization with so-called alkylating agents. Examples of suitable alkylating agents are CrC ₄ alkyl halides or sulfates, such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Quaternization can generally take place both before and after the polymerization.

Component iii5) Component iii5) are compounds with at least 2 radically polymerizable non-conjugated double bonds per molecule.

Suitable components iii5) are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the underlying alcohols can be fully or partially etherified or esterified; however, components iii5) contain at least two free-radically polymerizable unsaturated groups.

Examples of the underlying alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol , But-2-en-1, 4-diol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1st , 12-dodecanediol, neopentyl glycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1st , 4-Cyclohexanediol, 1, 4-bis (hydroxymethyl) cyclohexane, hydroxypivalic acid neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane , Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thio-pentane-1,5-diol, as well as polyethylene glycols, polypropylene glycols and polytetrahydrofurans with molecular weights of 200 to 10,000 each.

In addition to the homopolymers of ethylene oxide or propylene oxide, block copolymers of ethylene oxide or propylene oxide or copolymers which contain built-in ethylene oxide and propylene oxide groups can also be used.

Examples of underlying alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, triethoxycyanoic acid, sorbitan, sugars such as sucrose, glucose, mannose. Preferred polyhydric alcohols in this connection are also di- and trisacarides. Of course, the polyhydric alcohols can also be used as the corresponding ethoxylates or propoxylates after reaction with ethylene oxide or propylene oxide. be set. The polyhydric alcohols can also first be converted into the corresponding glycidyl ethers by reaction with epichlorohydrin. Further suitable components III5), the Vinylester or the esters of monohydric unsaturated alcohols with olefinically unsaturated C ₃ - to C _ö carboxylic acids, examples game, acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamon alcohol , Citronellol, crotyl alcohol or cis-9-octadecen-1-ol. However, the monohydric, unsaturated alcohols can also be esterified with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.

Other suitable components iii5) are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid. Also suitable as components iii5) are straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated to aliphatic hydrocarbons, e.g. Divinylbenzene, divinyltoluene, 1, 7-octadiene, 1, 9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes with molecular weights from 200 to 20,000.

Also suitable as components iii5) are the amides of (meth) acrylic acid, itaconic acid and maleic acid and N-allylamines of at least divalent amines. Such amines are, for example, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,2-dodecanediamine, piperazine, diethylene triamine or isophoronediamine. The amides of allylamine and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above, are also suitable. Triallylamine and triallylmonoalkylammonium salts, for example triallylmethylammonium chloride or methylsulfate, are also suitable as component iii5). N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes, for example of urea, ethylene urea, propylene urea or tartaric acid diamide, for example N, N'-divinylethylene urea or N, N'-divinyl propylene urea, are also suitable. Also suitable are alkylenebisacrylamides such as methylenebisacrylamide and N ₁ N'- (2,2) butane and 1,1 '-bis- (3,3'-vinylbenzimidazolith-2-one) -1,4-butane.

Other suitable components III5) include alkylene glycol (meth) acrylates such as e-thylenglykoldiacrylat, ethylene glycol, tetraethylene, Tetraethy-Ienglykoldimethacrylat, diethylene glycol acrylate, Diethylenglykolmethacrylat, vinyl acrylate, allyl methacrylate, divinyidioxane, pentaerythritol allyl and mixtures of these components III5).

Other suitable components iii5) are divinyldioxane, tetraallylsilane or tetravinylsilane. Components iii5) used with particular preference are, for example, methylene bisacrylamide, triallylamine and triallylalkylammonium salts, divinylimidazole, pentaerythritol triallyl ether, N, N'-divinylethylene urea, reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic acid esters and acrylic acid esters with polyalkylene oxides or polyalkylene oxide oxides, or more polyalkylene oxide oxides or polyalkylene oxide oxides, or more polyalkylene oxide oxides, or more polyalkylene oxide oxides or polyalkylene oxide oxides, or more polyalkylene oxide oxides, or polyalkylene oxide oxides, or more polyalkylene oxide oxides or polyalkylene oxide oxides, or more / or propylene oxide and / or epichlorohydrin have been implemented.

Very particularly preferred as component iii5) are pentaerythritol triallyl ether, methylene bisacrylamide, N, N'-divinylethylene urea, triallylamine and triallyl monoalkylammonium salts, and acrylic acid esters of glycol, butanediol, trimethylolpropane or glycerol or acrylic acid esters of glycerol reacted with ethylene oxide and / or epichlorohydrin , Trimethylolpropane or glycerin.

Mixtures of the aforementioned compounds can of course also be used. Component iii5) is preferably soluble in the reaction medium. If the solubility of component iii5) in the reaction medium is low, it can be dissolved in a monomer or in a monomer mixture or else added in solution in a solvent which mixes with the reaction medium. Components iii5) which are soluble in the monomer mixture are particularly preferred. If component iii5) is used to prepare the polymers, the amount used is at least 0.01, preferably at least 0.05, particularly preferably at least 0.1 and at most 5, preferably at most 2 and particularly preferably at most 1% by weight. %, based on the total amount of components i) to iii). If the polymers are to contain a component iii5) in copolymerized form, it is particularly advantageous to use mixtures of components iii1) and iii5). Such micro mixtures are commercially available and contain in addition to component iii), usually referred to as reactive substances such as tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), dipropylene glycol diacrylate (DPGDA), Trimethylolpropanformalmonoacrylat (Laromer ^® LR 8887), trimethylolpropane triacrylate ( TMPTA), propoxylated glyceryl triacrylate (GPTA), ethoxylated trimethylolpropane triacrylate (EO3TMPTA), ethoxyethoxyethylacrylate (EOEOEA), PEG 400 diacrylate (PEG400DA), isobornylacrylate (IBOA), propoxylated neopyl 2-ylpylglycol (BDDA), butane diol acrylate (BDMA), dihydrodicyclopentadienyl acrylate (DCPA), triethylene glycol divinyl ether, ethyl digycol acrylate (EDGA), lauryl acrylate (LA), 4-t-butylcyclohexyl acrylate (TBCH).

Components i6)

The compounds iü6) which differ from iii2) to iii4) are preferably selected from compounds of the general formula VI

O

-NR ^ R "(VI) where R ^{1 is} a group of the formula CH ₂ = CR ⁴ - with R ⁴ = H or dC ₄ alkyl and R ² and R ³ independently of one another are H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl or R ² and R ³ together with the nitrogen atom to which they are attached represent a five- to eight-membered nitrogen heterocycle or R ^{2 represents} a group of the formula CH ₂ = CR ⁴ - and R ¹ and R ³ independently of one another are H, alkyl , Cycloalkyl, heterocycloalkyl, aryl or hetaryl or R ¹ and R ³ together with the amide group to which they are attached represent a lactam with 5 to 8 ring atoms. Preferred as component i6) are N-vinyl lactams. Unsubstituted N-vinyl lactams and N-vinyl lactam derivatives which, for example, have one or more CrC ₆ alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc., are suitable as component i6) ., can have. These include, for example, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone , N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam etc. and mixtures thereof.

Preferred components iü6) are those for which in formula VI R ² for CH ₂ = CH and R ¹ and R ³ together with the amide group to which they are attached represent a lactam with 5 ring atoms. N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, acrylamide or mixtures thereof are particularly preferably used, with N-vinylpyrrolidone being most preferred.

Components iii7)

The term polyester is known to the person skilled in the art. Polyesters are polymers with ester bonds - [- CO-O -] - in the main chain. Components iii7) according to this invention are, for example, polyester (meth) acrylates which contain at least two free-radically polymerizable, olefinically unsaturated double bonds per molecule. Polyester (meth) acrylates are known in principle to the person skilled in the art. They can be produced by various methods. For example, (meth) acrylic acid can be used directly as an acid component in the construction of the polyester. In addition, it is possible to use hydroxyalkyl esters of (meth) acrylic acid as the alcohol component directly in the construction of the polyesters. However, the polyester (meth) acrylates are preferably prepared by (meth) acrylating polyesters. For example, polyesters containing hydroxyl groups can first be built up, which are then reacted with acrylic or methacrylic acid. At least 2 of the hydroxyl groups per molecule of the hydroxyl-containing polyester are preferably reacted with (meth) acrylic acid, so that at least two free-radically polymerizable, olefinically unsaturated double bonds are contained per molecule of the reaction product. It is also possible first to build up carboxyl-containing polyesters, which are then reacted with a hydroxyalkyl ester of acrylic or methacrylic acid. Here, too, at least two of the carboxyl groups per molecule of the carboxyl-containing polyester are reacted with the hydroxyalkyl ester of (meth) acrylic acid sets, so that at least two free-radically polymerizable, olefinically unsaturated double bonds are contained per molecule of the reaction product. It is preferred to use mixtures of polyester (meth) acrylates which contain on average more than 2 free-radically polymerizable, olefinically unsaturated double bonds per molecule of polyester (meth) acrylate.

Polyester acrylates suitable as component iii7) are described, for example, in EP-A 0 279 303, to which reference is made in full here (EP

A 0 279 303, p.5, lines 28-44).

DE 2 853 921 also describes suitable polyester acrylates, namely those made from aliphatic and / or aromatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, malic acid, maleic acid , Itaconic acid or its derivatives and polyhydric alcohols, such as ethylene glycol, polyethylene glycols, propylene glycol, polypropylene glycols, butanediol, hexanediol, neopentylglycol, hydroxypivalic acid neopentylglycol ester, trimethylolpropane, glycerol, pentaerythritol and / or trishydroxyethylsaturated acid, acrylic acid, α-ethoxylated acid, α-ethoxylated acid, α-ethoxylated acid, and Methacrylic acid, crotonic acid, cinnamic acid and / or dicarboxylic acid half-esters of monoalkanols, such as maleic, fumaric and itaconic acid half-esters with dC ₄ monoalcohols, acrylic acid and methacrylic acid being preferred.

EP-A 0 686 621, to which reference is made in full here, also describes suitable components iii7). These are reaction products of (meth) acrylic acid with a hydroxy compound. Suitable hydroxyl compounds are compounds having one or more hydroxyl groups. Monoalcohols, C ₂ -C ₆ -alkylenediols, trimethylolpropane, glycerol or pentaerythritol or, for example, compounds alkoxylated with ethylene oxide or propylene oxide and containing hydroxyl groups are mentioned.

Hydroxy-containing polyesters are also suitable as hydroxy compounds. Such hydroxyl-containing polyesters can be prepared, for example, in the customary manner by esterifying dicarboxylic acids or polycarboxylic acids with diols or polyols. The starting materials for such hydroxyl-containing polyesters are known to the person skilled in the art. Preferred dicarboxylic acids are succinic acid, glutaric acid, adipic acid, sebacic acid, o-phthalic acid, their isomers and hydrogenation products, and esterifiable derivatives, such as anhydrides, for example maleic anhydride, or dialkyl esters of the acids mentioned. Trimellitic acid, for example, is suitable as the polycarboxylic acid. The polyesterols to be used also include polycaprolactone diols and triols, the preparation of which is likewise known to the person skilled in the art. Preferred hydroxy compounds are at least 2, in particular 2 to 6, free hydroxyl-containing saturated polyesters, which may optionally also contain ether groups or polyethers (as component iü8)) with at least 2, in particular 2 to 6, free hydroxyl groups. Components iii7), such as polyester (meth) acrylates, have at least 2 free-radically polymerizable double bonds per molecule. It is further preferred to use mixtures of components iii), for example polyester (meth) acrylates, which contain on average more than 2 free-radically polymerizable, olefinically unsaturated double bonds per molecule of polyester (meth) acrylate. Such mixtures result, for example, by mixing compounds with 2 and compounds with 3 or more polymerizable double bonds per molecule. Of course, the mixtures can also contain compounds which contain only one or no double bond per molecule. Such compounds are then contained in such quantities that the average number of polymerizable double bonds per molecule is still more than 2.

Components iii8)

The term polyether is known to the person skilled in the art. Polyethers are polymers whose organ. Repetition units are held together by ether functionalities (COC). Examples of polyethers are polyalkylene glycols (polyethylene glycols, polypropylene glycols, polyepichlorohydrins) as polymers of 1,2-epoxides, epoxy resins, polytetrahydrofurans (polytetramethylene glycols), polyoxetanes, polyphenylene ethers (polyaryl ethers) or polyethers (ether) ketones (ketones) e. Components iii8) according to this invention are, for example, polyether (meth) acrylates which contain at least 2 free-radically polymerizable double bonds per molecule. These are also known in principle to the person skilled in the art. They can be produced by various methods. For example, polyethers containing hydroxyl groups, which are esterified with acrylic acid and / or methacrylic acid to give the polyether (meth) acrylates, by reacting di- and / or polyhydric alcohols with different amounts of ethylene oxide and / or propylene oxide using well-known methods ( see, for example, Houben-Weyl, Volume XIV, 2, Macromolecular Substances II, (1963)). Polymerization products of tetrahydrofuran or butylene oxide can also be used. DE 2 853 921, to which reference is made in full here, also describes suitable components iii8), such as, for example, aliphatic or aromatic-aliphatic polyethers, which are obtained by reacting di- and / or polyhydric alcohols with different amounts of ethylene and / or Propylene oxide are obtained and the free hydroxyl groups thereof are etherified in whole or in part with ethylenically unsaturated alcohols, for example allyl alcohol, methallyl alcohol, crotyl alcohol, cinnamon alcohol and / or esterified with α, β-ethylenically unsaturated monocarboxylic acids. Polyether acrylates suitable as component i8) are described, for example, in EP-A 0 279 303, to which reference is made in full here. These polyether acrylates can be obtained by reacting A) 1 equivalent of a 2 to 6-valent oxyalkylated C _{2 to} CIO alcohol with B) 0.05 to 1 equivalent of a 2 to 4-valent C _{2 to} CIO carboxylic acid or their anhydrides and C) 0.1 to 1.5 equivalents ten acrylic acid and / or methacrylic acid and reaction of the excess carboxyl groups with the equivalent amount of an epoxy compound. EP-A 0 686 621, to which reference is made in full here, also describes suitable components iii8). These are reaction products of (meth) acrylic acid with a hydroxy compound. Suitable hydroxyl compounds are compounds having one or more hydroxyl groups. Examples include compounds alkoxylated with ethylene oxide or propylene oxide and containing hydroxyl groups. Preferred hydroxy compounds are saturated polyethers with at least 2, in particular 2 to 6, free hydroxyl groups. Examples of suitable polyethers containing hydroxyl groups are those which can be obtained by known processes by reacting dihydric and / or polyhydric alcohols with different amounts of ethylene oxide and / or propylene oxide. In the case of the ethylene glycol / propylene glycol mixed condensation products, the reaction can expediently be controlled in such a way that primarily hydroxyl groups predominantly form at the end. Similarly, polymerization products of tetrahydrofuran or butylene oxide containing hydroxyl groups can also be used.

Examples of component iii8) are polyalkylene glycol (meth) acrylates. In a preferred embodiment of the invention, such compounds are used as component i8) whose molecular weight M _{w is} at least 200 g / mol, particularly preferably at least 400 g / mol, very particularly preferably at least 500 g / mol and most preferably more than 700 is g / mol. In a further preferred embodiment of the invention, compounds iii7) and / or iii8) or mixtures of compounds iii7) and / or iü8) are used as component iii), the average number of olefinic, free-radically polymerizable double bonds per molecule being more than 2 is. Such mixtures result, for example, by mixing compounds with 2 and compounds with 3 or more polymerizable double bonds per molecule. Of course, the mixtures can also contain compounds which contain only one or no double bond per molecule. Such compounds are then contained in such quantities that the average number of polymerizable double bonds per molecule is still more than 2.

At this point it should be emphasized that there are suitable compounds as component iii) which can be assigned to groups iii7) and iii8), since they contain both ester and ether groups. Component iii) according to the invention are thus also at least two compounds which contain free-radical polymerization and contain olefinically unsaturated double bonds and which simultaneously contain both ether and ester structures. Commercially available products that are suitable as component iii) are, for example:

Photomer ^® 5010, Photomer ^® 5429, Photomer ^® 5430, Photomer ^® 5432, Photomer ^® 5662, Photomer ^® 5806, Photomer ^® 5930 from Cognis; the Resin ^® brands from UCB such as Resin ^® 80, 81, 83, 450, 657, 770, 809, 810, 830, 835, 870, 1657, 1810, 1870, 2047 ^** , 2870; the CN ^® brands from Sartomer such as CN293, CN294, CN296, CN292, CN2297A, CN2279, CN2280, CN2470, CN295, CN2300, CN2200, CN2203, CN2282, CN2284, CN2270, CN2271, CN2272, CN2273, CN2276, CN2250, CN2251, CN2252, CN2253, CN2255, CN2256, CN2257, CN2258, CN2259, CN2260, CN2261; AROPLAZ ^® 4097-WG4-55 from Reichhold;

Syntholux ^® -PE brands from Synthopol as polyester acrylates and the Syntholux ^® - PA brands from Synthopol as polyether acrylates; Laromer ^® brands Laromer ^® PE 55F, Laromer ^® PE 56F, Laromer ^® PE 46T, Laromer ^® 9004, Laromer ^® PE 44F, Laromer ^® 8800, Laromer ^® LR 8981, Laromer ^® LR 8992, Laromer ^® PE 22WN, Laromer ^® PE 55WN, Laromer ^® PO 33F, Laromer ^® LR 8863, Laromer ^® PO 43F, Laromer ^® LR 8967, Laromer ^® LR 8982, Laromer ^® LR 9007 (BASF).

As component iii) it is also possible to use vinyl acetate, vinyl propionate, vinyl butyrate, ethylene, propylene, isobutylene, butadiene, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.

Components iii) can also be silicone-containing compounds, in particular also (poly) urethane acrylates containing silicone groups.

The polymers obtainable by the process according to the invention contain 0-30, preferably 0.1-20, particularly preferably 0.5-10 and most preferably 0.5-5% by weight of component iii) copolymerized.

Solution polymerization

According to the invention, the polymers are prepared by solution polymerization in a solution containing alcohol, the polymerization solution containing in the range from more than 25 to 50% by weight of water. Suitable alcohols are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, 3-methyl-1-butanol (isoamyl alcohol), n-hexanol, cyclohexanol or glycols such as ethylene glycol, propylene glycol and butylene glycol and alkyl ethers of polyhydric alcohols such as diethylene glycol, triethylene glycol, polyethylene glycols with number average molecular weights up to about 3000, glycerol and dioxane. The alcohol is particularly preferably or comprises ethanol and / or isopropanol, in particular ethanol.

In addition to alcohol and water, the solvent may also contain other solvents. In principle, all solvents suitable for radical polymerization are suitable, such as, for example, acetone, acetonitrile, aniline, anisole, benzonitrile, tert-butyl methyl ether (TBME), gamma-butyrolactone, quinoline, chloroform, cyclohexane, diethyl ether, dimethylacetamide, dimethylformamide, dimethyl sulfo- xide, dioxane, glacial acetic acid, acetic anhydride, ethyl acetate, ethylene dichloride, ethylene glycol dimethyl ether, formamide, hexane, methylene chloride, methyl ethyl ketone, N-methyl formamide, petroleum ether / light petrol, piperidine, propylene carbonate (4-methyl-1, 3-dioxol-2-one) , Sulfolane, tetrachlorethylene, carbon tetrachloride, tetrahydrofuran, toluene, 1, 1, 1-trichloroethane, trichlorethylene, triethylene glycol dimethyl ether (triglyme).

Polymerization solution is understood to mean that substance mixture which is present after all components have been added and the polymerization has ended and before the first workup step, such as drying, neutralization or steam distillation.

The polymerization solution comprises more than 25 to at most 50% by weight of water and preferably more than 20 to at most 60% by weight of alcohol, the total amount of water and alcohol preferably being at most 95, particularly preferably at most 90 and in particular at most 80% by weight. % of the polymerization solution.

The amount of water is preferably in the range from over 25 to 45, particularly preferably in the range from 28 to 40% by weight, based on the polymerization solution. The amount of alcohol is preferably in the range from 25 to 45, particularly preferably in the range from 30 to 40,% by weight, based on the polymerization solution. The amount of substances further contained in the polymerization solution, which are essentially components i), ii), iii) and the initiator, is preferably at least 5, particularly preferably at least 10 and in particular at least 20,% by weight of the polymerization solution. This amount is very particularly preferably in the range from 27 to 37% by weight and most preferably in the range from 29 to 35% by weight, based on the polymerization solution. This amount can also be referred to as the solids content of the polymerization solution. A process according to the invention is preferred in which the temperature at which the polymerization is carried out is in the range from 30 ° C. to 120 ° C., particularly preferably in the range from 40 ° C. to 100 ° C.

The polymerization is usually carried out under atmospheric pressure, but it can also take place under reduced or elevated pressure. A suitable pressure range is between 1 and 10 bar.

In a preferred embodiment of the process, the polymerization is carried out at a pressure in the range from 2 to 10 bar.

At least one water-soluble polymerization initiator selected from the group consisting of peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxide esters, azo compounds and mixtures thereof is preferably used as the initiator for the radical polymerization.

A water-soluble polymerization initiator is understood to mean an initiator which is soluble in at least 1 g, preferably at least 10 g, in 1 liter of water at 20 ° C. and 1013 mbar.

In a preferred embodiment of the invention, the water-soluble polymerization initiator is selected from the group consisting of water-soluble azo compounds, hydrogen peroxide, lithium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate and mixtures thereof.

The water-soluble polymerization initiator is furthermore preferably selected from the group consisting of

2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride

2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride

2,2'-azobis [2- (2-imidazolin-2-yl) propane disulfate dihydrate 2,2'-azobis (2-methylpropionamide) dihydrochloride

2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate

2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride

2,2'-Azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride

2,2'-azobis [2- (2-imidazolin-2-yl) propane] 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide

2,2'-azobis {2-methyl-N- [2- (1-hydroxybutyl)] propionamide}

2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] and mixtures thereof.

Water-soluble redox initiator systems can also be used as polymerization initiators. Such redox initiator systems contain at least one peroxide-containing compound in combination with a redox coinitiator, for example reducing sulfur compounds, for example bisulfites, sulfites, thiosulfates, dithionites and tetrathionates of alkali metals and ammonium compounds. Combinations of peroxodisulfates with alkali metal or ammonium bisulfites can be used, for example ammonium peroxodisulfate and ammonium disulfite. The amount of the peroxide-containing compound to the redox coinitiator is in the range from 30: 1 to 0.05: 1.

In combination with the initiators or the redox initiator systems, additional transition metal catalysts can be used, e.g. Salts of iron, cobalt, nickel, copper, vanadium and manganese. Suitable salts are e.g. Iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, or copper (I) chloride. Based on the monomers, the reducing transition metal salt is used in a concentration of 0.1 ppm to 1000 ppm. Combinations of hydrogen peroxide with iron (II) salts can be used, such as 0.5 to 30% hydrogen peroxide and 0.1 to 500 ppm Mohr's salt.

In combination with the initiators mentioned above, redox

Coinitiators and / or transition metal catalysts are used, e.g. Benzoin, dimethylaniline, ascorbic acid and complexes of heavy metals such as copper, cobalt, iron, manganese, nickel and chromium. The amounts of redox coinitiators or transition metal catalysts usually used are about 0.1 to 1000 ppm, based on the amounts of monomers used. Further suitable initiators are described in chapters 20 and 21 of Macromolecules, Vol. 2, 2nd Ed., H.G. Elias, Plenum Press, 1984, New York, to which reference is made in full here. Suitable photoinitiators are also described in S. P. Pappas, J. Rad. Cur., JuIy 1987, p. 6, to which reference is made in full here.

The amount of the at least one water-soluble initiator used for the polymerization of the monomers is preferably from 0.0001 to 10, particularly preferably 0.001 to 5 and in particular 0.02 to 3% by weight, based on the total amount of the monomers used.

To adjust the molecular weight, the polymerization can be carried out in the presence of at least one regulator. As a regulator, the usual compounds known to those skilled in the art, such as, for. B. sulfur compounds, e.g. B. mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid or dodecyl mercaptan and tribromochloromethane or other compounds which act regulatingly on the molecular weight of the polymers obtained. A preferred regulator is cysteine.

The solution polymerization can be carried out both as a batch process and in the form of a feed process, including monomer feed, step and gradient procedure. In general, preference is given to the feed process, in which part of the polymerization batch is optionally introduced, heated to the polymerization temperature and then the rest of the polymerization batch, usual usually via one or more spatially separate feeds, continuously, stepwise or by superimposing a concentration gradient while maintaining the polymerization of the polymerization zone.

To achieve the purest possible polymers with a low residual monomer content, the polymerization (main polymerization) can be followed by a post-polymerization step. The post-polymerization can be carried out in the presence of the same or a different initiator system as the main polymerization. The postpolymerization preferably takes place at least at the same temperature, preferably at a higher temperature than the main polymerization. If desired, the reaction mixture can be subjected to stripping with steam or steam distillation after the polymerization or between the first and the second polymerization step, which is carried out particularly advantageously to remove components with an undesirable odor. It is advantageous to neutralize the polymerization solution with one of the neutralizing agents mentioned below to at least 20, in particular at least 25% (based on the total amount of the neutralizable groups) before stripping with steam or before steam distillation. In a further embodiment of the invention, the concentrated polymer / solvent mixture obtained after steam distillation is diluted with alcohol, in particular ethanol.

The monomers used for the polymerization are preferably converted to at least 95, particularly preferably at least 99 and in particular at least 99.9% (degree of polymerization).

The polymers present in solution after the polymerization can be converted into powder by customary drying processes known to the person skilled in the art. Preferred processes are spray drying, spray fluidized-bed drying, roller drying and belt drying. Freeze drying and freeze concentration can also be used.

If desired, solvents can also be prepared by conventional methods, e.g. B. Partial or complete removal under reduced pressure.

The polymers produced by the process according to the invention can be anionic or anionogenic polymers. For use in cosmetic preparations, it is advantageous if the acid groups of these polymers are partially or completely neutralized with a base, since the salts of the polymers obtained generally have better solubility or dispersibility in water than the non-neutralized polymers.

Alkali metal bases such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrocarbon can be used as the base for the neutralization of these polymers. gene carbonate and alkaline earth metal bases such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate and ammonia or amines can be used.

Suitable amines are e.g. B. Ci-C6-alkylamines, preferably n-propylamine and n-butylamine, dialkylamines, preferably diethylpropylamine and dipropylmethylamine, trialkylamines, preferably triethylamine and triisopropylamine, Ci-C ₆ -alkyldiethanolamines, preferably methyl- or ethyldiethanolamine and di-ci- C6-alkylethanolamines. Particularly for use in cosmetic preparations, especially in hair treatment agents, 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-ethylpropane-1, 3-diol, diethylaminopro- have been used to neutralize polymers containing acid groups. pylamine, triisopropanolamine and triethanolamine have been proven. If triethanolamine is used as the neutralizing agent, the viscosity of the mixture present after steam distillation and before adding alcohol again is lower than, for example, when using AMP. The neutralization of the polymers containing acid groups can also be carried out with the aid of mixtures of several bases, for. B. Mixtures of sodium hydroxide solution or potassium hydroxide solution and triisopropanolamine.

Further suitable neutralizing agents are disclosed in WO 03/099253, p.2 lines 1 to 3, line 6, to which reference is made in full. The polymers are preferably neutralized after the end of the polymerization, ie when the monomer conversion is at least 99% by weight. The degree of neutralization can be 5 to 100%, preferably 30 to 95%, depending on the application. However, the neutralizing agent can also be added in more than an equivalent amount.

Cosmetic preparations

Stricter environmental regulations and growing ecological awareness increasingly demand ever lower proportions of volatile organic components (VOC) in cosmetic aerosol preparations, such as aerosol hair sprays.

The VOC content in hair sprays is essentially determined by the non-aqueous solvents and the blowing agents. Therefore, water is increasingly being used as a solvent instead of non-aqueous solvents. However, this replacement of the organic solvents poses some problems. For example, formulations of the film-forming polymers known from the prior art which meet the corresponding VOC requirements cannot be sprayed, or can only be sprayed after further dilution, and are therefore only suitable to a limited extent for use in hair sprays. Polymer films that result from such preparations sometimes do not have the necessary mechanical quality and therefore insufficient strengthening action and poor hold for the hair.

The copolymers produced by the process according to the invention are outstandingly suitable for producing cosmetic, in particular skin and / or hair cosmetic, preparations. They serve e.g. as polymeric film formers. They can be used and formulated universally in a wide variety of cosmetic, preferably hair cosmetic, preparations and are compatible with the customary components.

The copolymers are advantageously suitable for producing elastic hairstyles with strong setting at the same time, even in the presence of high atmospheric humidity. The copolymers are distinguished by good propellant gas compatibility, good solubility in aqueous / alcoholic solvent mixtures, in particular by their suitability for use as optically clear low-VOC formulations and by good washability and combability without flaking effect. In addition, they improve hair treated with them in their sensible properties such as grip, volume or manageability. Hair spray formulations based on the copolymers produced by the process according to the invention are notable for good sprayability and good theological properties and extremely low stickiness of the resulting films. The cosmetic, preferably hair cosmetic preparations containing the copolymers do not tend to foam after application. In addition to the good compatibility with the usual cosmetic ingredients, the applied copolymer films dry quickly. Another object of the present invention is accordingly the use of the copolymers obtainable by the process according to the invention in cosmetic preparations and such cosmetic preparations per se.

Cosmetically acceptable carrier B The cosmetic preparations are preferably aqueous preparations which contain at least 10, preferably at least 20 and particularly preferably at least contain at least 30 wt .-% water. The cosmetic preparations according to the invention preferably contain at most 80 (VOC-80), preferably at most 55% by weight (VOC-55) volatile organic constituents.

The invention accordingly relates to cosmetic preparations in which the proportion of volatile organic components is at most 55% by weight, based on the cosmetic preparation.

In addition to water and the copolymers obtainable by the process according to the invention, the cosmetic preparations also have at least one cosmetically acceptable carrier B, which is selected from i) water-miscible organic solvents, preferably C ₂ -C ₄ -

Alkanols, especially ethanol, ii) oils, fats, waxes, iii) esters of C ₆ -C ₃ o-monocarboxylic acids different from ii) with mono-, di- or trihydric alcohols, iv) saturated acyclic and cyclic hydrocarbons, v) fatty acids , vi) fatty alcohols, vii) propellants (propellant gases) and viii) mixtures thereof. Suitable carriers B and further active ingredients and additives to be used advantageously are described in detail below.

Suitable cosmetically and pharmaceutically compatible oil or fat components are described in Karl-Heinz Schrader, Fundamentals and Recipes of Cosmetics, 2nd edition, Verlag Hüthig, Heidelberg, pp. 319-355, to which reference is made here.

The cosmetic preparations can, for example, have an oil or fat component as cosmetically acceptable carrier B, which is selected from: hydrocarbons of low polarity, such as mineral oils; linear saturated hydrocarbons, preferably with more than 8 carbon atoms, such as tetradecane, hexadecane, octadecane, etc .; cyclic hydrocarbons such as decahydronaphthalene; branched hydrocarbons; animal and vegetable oils; To grow; Wax star; Vaseline; Esters, preferably esters of fatty acids, such as. B. the esters of dC ₂₄ -monoalcohols with d- C ₂₂ -monocarboxylic acids, such as isopropyl isostearate, n-propyl myristate, iso-propyl myristate, n-propyl palmitate, iso-propyl palmitate, hexacosanyl palmitate, octacosanyl palmitate, tria-contanyl palmitate tacmitate, rat, octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, tetratriaconta- nyl stearate; Salicylates such as Ci-Ci _O salicylates, e.g. B. octyl salicylate; Benzoate esters such as Cio-Ci ₅ alkyl benzoates, benzyl benzoate; other cosmetic esters, such as fatty acid triglycerides, propylene glycol monolaurate, polyethylene glycol monolaurate, C ₁₀ -C ₁₅ alkyl lactates, etc. and mixtures thereof.

Suitable silicone oils B) are e.g. B. linear polydimethylsiloxanes, poly (methylphenylsiloxanes), cyclic siloxanes and mixtures thereof. The number average molecular weight of the polydimethylsiloxanes and poly (methylphenylsiloxanes) is preferably in a range from about 1000 to 150,000 g / mol. Preferred cyclic siloxanes have 4- to 8-membered rings. Suitable cyclic siloxanes are e.g. B. commercially available under the name Cyclomethicone. Preferred oil or fat components B) are selected from paraffin and paraffin oils; Vaseline; natural fats and oils, such as castor oil, soybean oil, peanut oil, olive oil, sunflower oil, sesame oil, avocado oil, cocoa butter, almond oil, peach kernel oil, castor oil, cod liver oil, pork lard, walnut, spermacet oil, sperm oil, wheat germ oil, macadamia nut oil, evening primrose oil, evening primrose oil Fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cetyl alcohol; Fatty acids such as myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid and various saturated, unsaturated and substituted fatty acids; Waxes such as beeswax, carnauba wax, candililla wax, walrus and mixtures of the oil or fat components mentioned above. Suitable hydrophilic carriers B) are selected from water, 1-, 2- or polyhydric alcohols with preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol, etc.

The cosmetic preparations can be skin cosmetic, hair cosmetic or dermatological, hygienic or pharmaceutical preparations. Because of their film-forming and flexible properties, the copolymers which can be prepared by the process according to the invention are particularly suitable as additives for hair and skin cosmetics.

The cosmetic preparations which contain the copolymers according to the invention are preferably in the form of a spray, gel, foam, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.

The cosmetic compositions according to the invention preferably contain at least one copolymer according to the invention, at least one carrier B as defined above and at least one constituent different therefrom, which is preferably selected from cosmetically active ingredients, emulsifiers, surfactants, preservatives, perfume oils, thickeners, hair polymers, hair and skin conditioners , Graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaching agents, gel formers, care agents, colorants, tinting agents, browning agents, dyes, pigments, consistency agents, humectants, refatting agents, collagen, protein hydrolyzates, lipids, antioxidants, antioxidants, antioxidants, antioxidants, antioxidants.

The preparations according to the invention preferably have a pH of 2.0 to 9.3. The pH range between 4 and 8 is particularly preferred. Organic solvents or a mixture of solvents with a boiling point below 400 ° C. in an amount of 0.1 to 15% by weight, preferably 1 to 10, can be used as additional cosolvents % By weight. Unbranched or branched hydrocarbons such as pentane, hexane, isopentane and are particularly suitable as additional co-solvents cyclic hydrocarbons such as cyclopentane and cyclohexane. Further, particularly preferred water-soluble solvents are glycerol, ethylene glycol and propylene glycol in an amount of up to 30% by weight.

In a preferred embodiment of the invention, the cosmetic preparations have a maximum volatile organic component content

80% by weight, preferably at most 55% by weight and in particular at most 35% by weight. A preferred object is therefore cosmetic, preferably hair cosmetic, preparations which correspond to the Iow VOC standard, that is to say VOC 80 or VOC 55 standard. The use of the copolymers is particularly preferred in hairspray preparations which contain the following constituents: partially or completely neutralized copolymer according to the invention;

Water; cosmetically customary organic solvent such as ethanol, isopropanol and dimethoxymethane, in addition also acetone, n-propanol, n-

Butanol, 2-methoxypropan-1-ol, n-pentane, n-hexane, cyclohexane, n-heptane, n-

Octane or dichloromethane or mixtures thereof; cosmetically customary propellants such as n-propane, isopropane, n-

Butane, i-butane, 2,2-dimethylbutane, n-pentane, isopentane, dimethyl ether, difluoroethane, fluorotrichloromethane, dichlorodifluoromethane or dichlorotetrafluoroethane,

HFC-152 A (1, 1-difluoroethane), HFC-134a (1, 1, 2,2-tetrafluoroethane), N ₂ , N ₂ O and

CO or their mixtures.

The abovementioned agents are suitable for neutralizing the copolymers obtainable by the process according to the invention and for adjusting the pH of the cosmetic, preferably hair cosmetic, preparations. Alkanolamines are advantageously used. Examples are 2-amino-2-methyl-1-propanol (AMP), diethanolamine, diisopropanolamine, ethanolamine, methylethanolamine, N-lauryl-diethanolamine, triethanolamine, triisoproanolamine as well as those in WO 03/099253, p.2 Z.1 to S.3, Z.6 mentioned. Accordingly, both primary amino groups and alkanolamines bearing secondary amino groups can be used.

In addition, alkali metal hydroxides (e.g. NaOH, preferably KOH) and other bases for neutralization can be used (e.g. histidine, arginine, lysine, ethylene diamine, diethylene triamine, melamine, benzoguanamine). All of the stated bases can be used alone or as a mixture with other bases for neutralizing acidic cosmetic products.

In a preferred embodiment of the invention, amines containing hydroxyl groups are selected from the group consisting of N ₁ N-dimethylethanolamine, N-methyldiethanolamine, triethanolamine, 2-amino-2-methylpropanol and mixtures thereof and those in WO 03/099253 for neutralization , S.2 Z.1 to S.3, Z.6 selected. The present invention accordingly relates to aqueous cosmetic, preferably skin and / or hair cosmetic preparations which, in addition to the at least one copolymer obtainable by the process according to the invention and the carrier B, comprise at least one active ingredient or additive selected from the group consisting of viscosity-modifying substances , hair-care substances, hair-setting substances, silicone compounds, light stabilizers, fats, oils, waxes, preservatives, pigments, soluble dyes, particulate substances and tensides.

Such hair cosmetic formulations contain in a preferred embodiment

i) 0.05 to 20% by weight of at least one copolymer as described above, ii) 20 to 99.95% by weight of water and / or alcohol, iii) 0 to 50% by weight of at least one propellant, iv) 0 to 5% by weight of at least one emulsifier, v) 0 to 3% by weight of at least one thickener, and vi) up to 25% by weight of further constituents.

Alcohol is to be understood as meaning all of the abovementioned alcohols customary in cosmetics, preferably ethanol, isopropanol, n-propanol, ethanol being particularly preferred.

Propellant (propellant gases)

Of the compounds mentioned, the blowing agents (blowing gases) used above all are the hydrocarbons, in particular propane, n-butane, n-pentane and mixtures thereof, and also dimethyl ether and difluoroethane. If appropriate, one or more of the chlorinated hydrocarbons mentioned are also used in blowing agent mixtures, but only in small amounts, approximately up to 20% by weight, based on the blowing agent mixture. The cosmetic preparations are also particularly suitable for pump spray preparations without the addition of propellants or for aerosol sprays with conventional compressed gases such as nitrogen, compressed air or carbon dioxide as the blowing agent. A water-containing standard aerosol spray formulation comprises, for example, the following components: ^■ 100% neutralized copolymer

^■ alcohol

^■ water

^■ dimethyl ether and / or propane / n-butane and / or propane / isobutane,

The total amount of volatile organic components is preferably at most 80, particularly preferably at most 55% by weight of the preparation.

The cosmetic preparations preferably contain at least one copolymer as described above, at least one cosmetic as defined above acceptable carrier B and at least one other, different active or additive, which is selected from cosmetically active ingredients, emulsifiers, surfactants, preservatives, perfume oils, thickeners, hair polymers, hair conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers , Bleaching agents, gelling agents, care agents, coloring agents, tinting agents, browning agents, dyes, pigments, consistency agents, moisturizers, refatting agents, collagen, protein hydrolyzates, lipids, antioxidants, defoamers, antistatic agents, emollients, lanolin and component components, protein hydrolysers

Plasticizers.

Other polymers

To adjust the properties of cosmetic preparations in a targeted manner, it can be advantageous to use the copolymers obtainable by the process according to the invention in a mixture with other (hair) cosmetically customary polymers. In a further preferred embodiment, the cosmetic preparation contains 0.01 to 15% by weight, preferably 0.5 to 10% by weight, of at least one further synthetic or natural nonionic, preferably a film-forming polymer. Natural polymers are also understood to mean chemically modified polymers of natural origin. Film-forming polymers are understood to mean those polymers which, when used in 0.01 to 5% aqueous, alcoholic or aqueous-alcoholic solution, are able to deposit a polymer film on the hair. Anionic, cationic, amphoteric, zwitterionic and neutral polymers, for example, are suitable as such other conventional polymers. Such polymers are known to the person skilled in the art and require no further explanation.

Measurement methods

Determination of the K value

The K values are measured according to Fikentscher, Cellulosechemie, vol. 13, pp. 58 to 64 (1932) at 25 ° C. in N-methylpyrrolidone (NMP) solution and represent a measure of the molecular weight. The NMP solution the polymer contains 1g polymer in 100 ml solution. In the event that the polymers are in the form of aqueous dispersions, depending on the polymer content of the dispersion, corresponding amounts of the dispersion are made up to 100 ml with NMP, so that concentrations of 1 g of polymer in 100 ml of solution are formed.

The K value is measured in a Micro Ubbelohde capillary type M Ic from Schott.

Determination of the Droplet Size Distribution (DSD) by Malvern ^® Scattered Light The droplet size distribution was determined using particle system for detecting liquid aerosols "Malvern ^® Master Sizer X" (Malvern Instruments Inc., Southborough MA, USA).

Measuring principle: The measuring system is based on the method of laser light diffraction on the particle, which is suitable not only for spray analysis (aerosols, pump sprays) but also for the size determination of solids, suspensions and emulsions in the size range from 0.1 μm to 2000 μm. A particle collective (= droplet) is illuminated by a laser. Part of the incident laser light is scattered at each droplet. This light is received at a multi-element detector and the associated light energy distribution is determined. The associated particle distribution is calculated from this data using the evaluation software.

Execution:

The aerosols were sprayed at a distance of 29.5 cm from the laser beam. The spray cone entered at right angles to the laser beam. Spraying device: spray head Kosmos .020D vortex .018 "21-6443-20, valve: DPV 33876 (from Precision Valve)

Before each measurement, the aerosol cans were fixed to a permanently installed holding device, so that it was achieved that all aerosols to be tested were measured at exactly the same distance.

Before the actual particle measurement, a so-called "background measurement" was carried out. This eliminated the effects of dust and other contaminants in the measurement area. The aerosol was then sprayed into the test room. The entire particle volume was recorded and evaluated over a test period of 2s.

Evaluation: Evaluation is carried out using a tabular representation over 32 class widths from 0.5 μm to 2000 μm and a graphic representation of the particle size distribution. Since the spray tests result in approximately uniform distributions, the mean diameter "D" (v, 0.5) is given. This numerical value indicates that 50% of the total measured particle volume is below this value.

In the case of aerosol systems which can be sprayed well in the cosmetic field, this value is in the range from 30 μm to 80 μm, depending on the polymer content, valve and spray head geometry, solvent ratio and propellant quantities.

Determination of the strength (bending stiffness)

The strengthening of polymeric film formers was measured not only by subjective assessment (so-called "hand test") but also physically by measuring the bending stiffness of thin strands of hair (in each case approx. 3 g and 24 cm in length) % By weight solution of the respective polymer (dissolved in ethanol / water 55:45 w / w), whereby three times immersion and removal and subsequent squeezing between filter paper ensured uniform wetting of the hair strand and distribution of the polymer solution. The excess polymer solution was then stripped between the thumb and forefinger and the strands of hair were shaped by hand in such a way that they had an approximately round cross section.At 20 ° C and 65% relative humidity, the samples were stored overnight in the climatic room 65% relative humidity was carried out by means of a tension / pressure tester Ends placed on two cylindrical rollers of the sample holder. Right in the middle, the strand was then bent from above with a rounded stamp until the polymer film broke (approx. 40 mm). The force (F _max ) required for this was determined with a load cell (50 N). A measured value represents the arithmetic mean of the individual measurements on 5 to 10 strands of the same treatment. The values determined in this way were compared to those of a commercially available comparative polymer (as described) and stated in%.

Determination of washability

An analogous to the determination of the setting polymer treated hair tress was in an approximately 37 ° C warm Texapon ^® NSO - solution (6ml of Texapon ^® NSO (28%) in 11 hot water) for about 15 seconds by δmaliges immersing and squeezing washed. The lock of hair was then rinsed clear and treated again in the same way. After that, the lock of hair was well squeezed out on filter paper and left to dry overnight. The dry strand of hair was screwed in and examined for residues.

Determination of the curl retention basic formulation: (aerosol hairspray)

5% by weight of active ingredient polymer to be tested (100% neutral with AMP)

15% by weight ethanol

40% by weight water

40% by weight dimethyl ether. For the determination of curl retention, hair strands weighing approx. 2 g and

15.5 cm in length and made from medium brown, Caucasian human hair. Treatment of hair strands:

The hair tresses were washed twice with an aqueous Texapon ^® NSO solution. The locks of hair were then rinsed out with warm water until no more foam was visible and rinsed with demineralized water, combed and placed on filter paper to dry.

To produce a water wave, the strands of hair are placed in a solution of ethanol and water (1: 1) for 15 minutes to swell. The strand of hair is carefully combed before the curl preparation. The strand of hair is attached to the plexiglass rod with a rubber band. It is then combed and wound in a spiral. The curl is firmly fixed with a cotton cloth and rubber band and dried overnight at 70 ° C. The cooled curl retention strands are carefully opened and stripped from the plexiglass rod without deforming the water wave. From a distance of 15 cm, the gem. o.a. Composition aerosol hair spray 1, 8g evenly sprayed onto the curl. The curl is turned evenly. In a horizontal position, the curls are dried for 1 h at room temperature. After drying, the curls are attached in a holder. With the help of a scale, the initial length of the curls is read off at the beginning and the length extension is tracked during storage in a humid climate. After 5 hours storage at 25 ° C and 90% RH The length of the curl reached is read again in the climatic chamber and the curl retention acc. calculated the following equation:

L - U curl retention in% = ^* 100

L - L ₀

L = length of the hair (15.5 cm) L ₀ = length of the lock of hair after drying L _t = length of the lock of hair after climatic treatment The mean value from the 5 individual measurements is given as curl retention.

Determination of stickiness A clear, 20% by weight ethanolic or ethanolic / aqueous solution of the polymer to be characterized is first prepared. In order to obtain a clear solution, it may be necessary to neutralize the polymer. A film of the polymer is then applied to the glass plate from the ethanolic or ethanolic / aqueous solution using a doctor blade (120 μm gap width). This rectangular glass plate has a length of approx. 20 cm and a width of approx. 6.5 m. The polymer film applied thereon has a length of approximately 16 to 18 cm and a width of approximately 5.5 cm. The film is then dried in air for about 10 hours and then stored in a climate control cabinet at 20 ° C and 80% relative humidity for a further 12 hours.

Under these conditions, a plastic-carbon tape (eg Pelikan ^® 2060, 50 mm wide) with a force of approx. 250 N is located on a round rubber stamp (diameter 400 mm, Shore A hardness 60 ± 5) pressed onto the polymer film for 10 seconds. The amount of black pigment remaining adhering to the polymer film after the stamp was removed corresponds to the stickiness of the film. There is a visual assessment of the black color of the film. The rating scale ranges from 0 to 5, with 0 not sticky and 5 very sticky.

Determination of the appearance of the aerosol formulation

The preparation of 5% by weight of the respective polymer neutralized with AMP, 40% by weight of DME, 15% by weight of ethanol and 40% by weight of water were placed in a transparent glass aerosol container. The clarity of the resulting liquid / propellant mixture was then assessed visually.

Examples

Abbreviations: MMA methyl methacrylate MAS methacrylic acid AS acrylic acid

Production of urethane acrylate 1 (component iii)

672.0 g of a polyester composed of adipic acid and neopentyl glycol with an OH number of approx. 200, 140.0 g of hydroxyethyl acrylate, 0.6 g of hydroquinone monomethyl ether, 1, 20 g of 2,6, di-tert were placed in a round bottom flask . Butyl-4-methylphenol, 0.12 g of tetrabutyl ortho-titanate and heated to 50 ° C. Then 400.0 g of isophorone diisocyanate were added dropwise within 30 minutes. The mixture was left to react for a further 7 hours at 90-95 ° C., the NCO content dropping to 0.56%. It was cooled to 60 ° C., then 520.0 g of ethanol were added and the mixture was left to react at 65-70 ° C. for about 2 hours until the isocyanate content (NCO value) had dropped to 0. The resin obtained was filtered through a 50 μm filter and filled.

Production of urethane acrylate 2 (component iii)

672.0 g of a polyester composed of adipic acid and neopentyl glycol with an OH number of approx. 200, 140.0 g of hydroxyethyl acrylate, 0.6 g of hydroquinone monomethyl ether, 1, 21 g of 2,6, di-tert were placed in a round bottom flask. Butyl-4-methylphenol, 0.12 g of cesium acetate and heated to 50 ° C. Then 400.0 g of isophorone diisocyanate were added dropwise within 30 minutes. The mixture was left to react for a further 7 hours at 90-95 ° C., the NCO content dropping to 0.56%. It was cooled to 60 ° C., then 520.0 g of ethanol were added and the mixture was left to react for about 2 hours at 65-70 ° C. until the isocyanate content (NCO value) had dropped to 0. The resin obtained was filtered through a 50 μm filter and filled.

Production of urethane acrylate 3 (component iii)

672.0 g of a polyester composed of adipic acid and neopentyl glycol with an OH number of approx. 200, 140.0 g of hydroxyethyl acrylate, 0.6 g of hydroquinone monomethyl ether, 1, 21 g of 2,6, di-tert were placed in a round bottom flask. Butyl-4-methylphenol presented and heated to 50 ° C. Then 400.0 g of isophorone diisocyanate were added dropwise within 30 minutes. The mixture was left to react at 90-95 ° C. for a further 20 hours, the NCO content dropping to 0.1%. The mixture was cooled to 60 ° C., then 10.0 g of methanol were added and the mixture was left to react at 90-95 ° C. for about 4 hours until the isocyanate content (NCO value) reached 0 had dropped. The resin obtained was mixed with 510.0 g of tripropylene glycol diacrylate at room temperature and filtered through a 50 μm filter and filled.

Urethane acrylate 5 (component

Urethane acrylate 6 (component iii)

Urethane acrylate 7 (component

Polymer A:

Inlet 1

234.00g methyl methacrylate (MMA)

30.00g methacrylic acid (MAS)

30.00g acrylic acid (AS)

6.00g urethane acrylate 3 (UA 3)

Inlet 2 6.00 g Wako ^® V-50 (2,2'-azobis (2-methylpropionamide) dihydrochloride) 270.00 g ethanol 204.00 g demineralized water (VE = fully desalinated)

As a template, 15.00 g of feed 1 and 24.00 g of feed 2 were mixed with 120.0 g of cosmetic ethanol and 90.00 g of demineralized water in a 1 liter glass reactor. This template was heated to reflux under a nitrogen atmosphere. After reaching the reflux temperature, feeds 1 and 2 were started together. Feed 1 was in 3 hours and feed 2 in 4 hours under reflux. The reaction mixture was further polymerized under reflux for 2 hours. Feed 3 (1.05 g sodium peroxodisulfate, 12.00 g ethanol cosm., 8.00 g demineralized water) was then metered in over 30 minutes and the mixture was re-polymerized under reflux for 2 hours. Feed 4 (1.05 g of sodium peroxodisulfate, 12.00 g of ethanol cosm., 8.00 g of deionized water) was then metered in in 30 minutes and the polymerization was continued for a further 2 hours under reflux.

Polymer B:

Inlet 1

1 17.00g methyl methacrylate

15.00g methacrylic acid

15.00 g acrylic acid 3.00 g Laromer ^® UA 19 T.

Inlet 2

3.00g sodium peroxodisulfate

135.00g ethanol cosm. 102.00 g demineralized water

As a template, 2.34 g of feed 1 and 24.00 g of feed 2 were mixed in a 1 liter glass reactor with 60.0 g of cosmetic ethanol and 45.00 g of demineralized water. This template was heated to reflux under a nitrogen atmosphere. After reaching the reflux temperature, feeds 1 and 2 were started together. Feed 1 was metered in under reflux in 3 hours and feed 2 in 4 hours under reflux. The reaction mixture was further polymerized under reflux for 2 hours. Feed 3 (0.70 g of sodium peroxodisulfate, 6.00 g of ethanol cosm., 4.00 g of demineralized water) was then metered in in 30 minutes and the mixture was subsequently polymerized under reflux for 2 hours. Feed 4 (0.70 g sodium peroxodisulfate, 6.00 g ethanol cosm., 4.00 g demineralized water) was then metered in over 30 minutes and the polymerization was continued for a further 2 hours under reflux.

Polymer C

The following feeds were produced with stirring at 20 ° C.:

Inlet 1 120 g MMA 15 g MAS 15 g AS Inlet 2

3 g sodium peroxodisulfate 135 g ethanol 102 g water

A mixture of 100 g of ethanol, 15% by weight of the total amount of feed 1 and 15% by weight of the total amount of feed 2 was prepared at 20.degree. The mixture was heated to 78 ° C under normal pressure. While maintaining the polymerization temperature, feed 1 and feed 2 were started after 78 ° C. had been reached. Feed 1 was metered in within 3 hours and feed 2 within 4 hours with a constant feed stream. After the end of feed 2, the reaction mixture was kept at 78 ° C. for a further 2 hours and then cooled to room temperature (approx. 20 ° C.).

Polymer D

The polymer was produced analogously to polymer A. Feed 3 (0.60 g of sodium peroxodisulfate, 12.00 g of ethanol cosm., 8.00 g of demineralized water) was metered in in 30 minutes and the polymerization was continued under reflux for 2 hours. Feed 4 (0.60 g of sodium peroxodisulfate, 12.00 g of ethanol cosm., 8.00 g of demineralized water) was then metered in in 30 minutes and polymerization was continued for a further 2 hours under reflux.

Polymer E

Inlet 1

228.15g methyl methacrylate

29.25g methacrylic acid

29.25g acrylic acid

5.85 g urethane acrylate 1

Inlet 2

4.70g sodium peroxodisulfate

199.0g demineralized water

As a template, 14.60 g of feed 1 and 10.20 g of feed 2 were mixed with 403.00 g of isopropanol and 87.80 g of demineralized water in a 1 liter glass reactor. This template was heated to 80 ° C under a nitrogen atmosphere. After reaching the temperature, feeds 1 and 2 were started together. Feed 1 was metered in in 3 hours and feed 2 in 4 hours. The reaction mixture was further polymerized under reflux for 2 hours. Feed 3 (0.88 g of sodium peroxodisulfate, 6.00 g of deionized water) was then metered in and polymerization was continued for 2 hours. Feed 4 (0.88 g of sodium peroxodisulfate, 6.00 g of demineralized water) was then metered in and polymerization was continued for a further 2 hours. Polymer F

Feed 1 234.0 g methyl methacrylate

30.0g methacrylic acid

30.0g acrylic acid

6.0 g urethane acrylate 1

Inlet 2

3.60g Wako ^® V-50 (2.2'-

270.0g isopropanol

204.0 g demineralized water

As a template, 15.0 g of feed 1 and 23.90 g of feed 2 were mixed with 120.0 g of isopropanol and 90.0 g of demineralized water in a 1 liter glass reactor. This template was heated to 80 ° C under a nitrogen atmosphere. After reaching the temperature, feeds 1 and 2 were started together. Feed 1 was metered in in 3 hours and feed 2 in 4 hours. The reaction mixture was further polymerized under reflux for 2 hours. Then feed 3 (0.60 g sodium peroxodisulfate, 8.00 g demineralized water, 12.0 g isopropanol) was added within 30 min. metered in and polymerized for 2 hours. Feed 4 (0.60 g sodium peroxodisulfate, 8.00 g demineralized water, 12.0 g isopropanol) was then added within 30 min. metered in and polymerized for 4 hours. The solution obtained had an FG of 32.6% (remainder of monomers: table). This solution was partially neutralized with 27.90 g of 2-amino-2-methyl-1-propanol. 350.0 g of this solution were subjected to steam distillation (15 min). 228.0 g of a white concentrated mixture were obtained, which was then diluted with 70.0 g of ethanol.

Polymer G

Inlet 1

234.0g methyl methacrylate

30.0g methacrylic acid

30.0g acrylic acid

6.0 g urethane acrylate 1

Inlet 2

3.60g Wako ^® V-50 (2.2'-

204.0 g demineralized water

As a template, 15.0 g of feed 1 and 10.40 g of feed 2 were mixed with 414.0 g of isopropanol and 90.0 g of demineralized water in a 2 l glass reactor. This template was heated to 80 ° C under a nitrogen atmosphere. After reaching the temperature, the additives run 1 and 2 started together. Feed 1 was metered in in 3 hours and feed 2 in 4 hours. The reaction mixture was further polymerized under reflux for 2 hours. Then feed 3 (0.90 g sodium peroxodisulfate, 8.00 g demineralized water) was added within 30 min. metered in and polymerized for 2 hours. Feed 4 (0.90 g sodium peroxodisulfate, 8.00 g demineralized water) was then added within 30 min. metered in and polymerized again for 2 hours.

The solution obtained had an FG of 30.9% by weight. 345.0 g of this solution were partially neutralized with 12.0 g of 2-amino-2-methyl-1-propanol and subjected to steam distillation (15 min). The concentrated mixture was then diluted with 106.0 g of ethanol, whereby a solution with a solids content of 27.0% by weight was obtained.

Polymer H

Inlet 1 210.0g methyl methacrylate

36.0g methacrylic acid

36.0g acrylic acid

37.5g ethyl dimethyl (2 - ((2-methyl -1-oxoallyl) oxy) ethyl) ammonium ethyl sulfate (48% aqueous solution) - acrylate 4

Inlet 2 3.60g Wako ^® V-50

270.0g isopropanol

184.5g demineralized water

As a template, 16.0 g of feed 1 and 23.0 g of feed 2 were mixed with 120.0 g of isopropanol and 90.0 g of demineralized water in a 2 l glass reactor. This template was heated to 80 ° C under a nitrogen atmosphere. After the temperature had been reached, feeds 1 and 2 were started together. Feed 1 was metered in in 3 hours and feed 2 in 4 hours. The reaction mixture was further polymerized under reflux for 2 hours. Then feed 3 (0.60 g sodium peroxodisulfate, 8.00 g demineralized water, 12.0 g isopropanol) was added within 30 min. metered in and polymerized for 2 hours. Feed 4 (0.60 g sodium peroxodisulfate, 8.00 g demineralized water, 12.0 g isopropanol) was then added within 30 min. metered in and polymerized again for 4 hours.

The solution obtained has an FG of 32.6% (remainder of monomers: table). 803.0 g of this solution would be partially neutralized with 35.50 g of 2-amino-2-methyl-1-propanol and steam distillation would be added (15 min). A white viscous mixture was obtained which was cosm with ethanol. was diluted, a solution having a solids content of 36.4% by weight being obtained. Polymer I

Inlet 1

700.0g methyl methacrylate

90.0g methacrylic acid

90.0g acrylic acid

18.0g urethane acrylate 1

360.0g isopropanol

Inlet 2

10.70g Wako ^® V 50 (2.2 '->

82.0 g demineralized water

32.0 g isopropanol

As a template, 63.00 g of feed 1 were mixed with 803.0 g of isopropanol and 746.0 g of demineralized water in a 5 l stainless steel reactor. This template was pressed 3 times with a nitrogen atmosphere (5.0 bar) and then heated to 80 ° C. at 0.5 bar. Then 6.30 g of feed 2 were added. After 10 minutes, feeds 1 and 2 were started together. Feed 1 was metered in over 3 hours and feed 2 over 4 hours at 80 ° C. under autogenous pressure. The reaction mixture was further polymerized at 80 ° C. under autogenous pressure for 2 hours. The temperature was then raised to 90 ° C. under autogenous pressure and feed 3 (2.70 g sodium peroxodisulfate, 36.00 g demineralized water) was metered in in 30 minutes and the polymerization was continued at 90 ° C. for 2 hours under autogenous pressure. Feed 4 (2.70 g of sodium peroxodisulfate, 36.00 g of demineralized water) was then metered in in 30 minutes and polymerization was continued at 90 ° C. for 2 hours under autogenous pressure.

The solution obtained (solids content of 32.0% by weight) was partially neutralized with 131.10 g of 2-amino-2-methyl-1-propanol and subjected to steam distillation. The mixture was then cosm with ethanol. diluted to give a solution with a solids content of 35.7% by weight

Polymer J

The polymer was synthesized analogously to polymer I. 968.0 g of the solution were partially neutralized with 71.10 g of triethanolamine and subjected to steam distillation (15 min). The viscous solution was then cosm with ethanol. diluted to give a solution with a solids content of 32.5% by weight.

Polymer K

Inlet 1 228.0g methyl methacrylate

30.0g methacrylic acid 30.0g acrylic acid

12.0g Ebecryf CL 1039

Inlet 2 6.00g Wako ^® V-50

200.0g demineralized water

270.0g ethanol cosm.

As a template, 15.0 g of feed 1 and 24.0 g of feed 2 with 120.0 g of ethanol were in a 2-liter glass reactor. and 90.0g demineralized water mixed. This template was heated to 80 ° C under a nitrogen atmosphere. After reaching the temperature, feeds 1 and 2 were started together. Feed 1 was metered in in 3 hours and feed 2 in 4 hours. The reaction mixture was further polymerized under reflux for 2 hours. Then feed 3 (0.90 g sodium peroxodisulfate, 8.00 g demineralized water, 12.0 g ethanol cosm.) Was added within 30 min. metered in and post-polymerized under reflux for 2 hours. Then feed 4 (0.90 g sodium peroxodisulfate, 8.00 g demineralized water, 12.0 g ethanol cosm.) Was added within 30 min. metered in and polymerized again under reflux for 2 hours.

Polymers L, M, N

The polymers L, M, N were synthesized analogously to polymer K.

The numbers given in the cells for the respective components are the weight percentages of the respective component in the total amount of the components i) + ii) + iii) used for the polymerization.

Residual amount of monomer, determined after the polymerization and before steam distillation

Determination of the residual monomers

Monomeric acrylic acid and methacrylic acid were determined by HPLC. For this purpose, 0.2 to 1 g of the polymer solution was dissolved in 5 ml of methanol and precipitated with 45 ml of 0.1% by weight H ₃ PO ₄ by slow dropwise addition with stirring, then filtered through 0.2 μm Braunrand filter and placed in the HPLC Equipment injected. Column: SymmetryShield ^® RP18 e from Waters

Eluent: water MiIIi-Q: H ₃ PO ₄ conc. : Methanol in the ratio 900ml: 1 ml: 100ml

UV detector: 205 nm

Monomer MMA was determined by internal standard gas chromatography.

For this purpose, approx. 250 mg sample with 2 ml int. Standard solution (1 mg 1,4-dioxane in 2 ml

Dimethylacetamide) and 1 ml of water. After loosening the samples, the

Steam room analyzed.

Separation column: DB 1 (100% dimethylpolysiloxane)

Detector: FID

^* [mg / kg]: Milligrams of unpolymerized component i) to ii) per kilogram of polymer

Application properties of the polymers produced according to the invention

^a) Particle size from VOC55 aerosol: 5% of the polymer which has already been completely neutralized with AMP, 40% DME, 15%

Ethanol, 40% water; Spraying device: spraying head: Kosmos .020D vortex .018 "21-6443-20,

Valve: DPV 33876 (Fa. Precision Valve) ^b) Fixation: 3.0% by weight solution of the polymer, which has already been completely neutralized with AMP, in ethanol / water (55:45 w / w)

The effects of different types of neutralizing agents and amounts of polymer were examined below. The following quantities are in% by weight, unless expressly stated otherwise.

^c) Particle size from VOC55 aerosol: 5% of polymer I, 40% DME, 15% ethanol, 40% water, with an additional amount of AMP necessary for complete neutralization of polymer I being added. 21-6443-20,

Valve: DPV 33876 (Precision Valve) ^d) consolidation:

3.0% by weight solution of polymer I in ethanol / water (55:45 w / w), an amount of AMP necessary for complete neutralization of polymer I being additionally added.

^e) Particle size from VOC55 aerosol:

5% of polymer J, 40% DME, 15% ethanol, 40% water, with an additional amount of triethanolamine necessary for complete neutralization of polymer J being added

Spraying device: spraying head: Kosmos .020D vortex .018 "21-6443-20,

Valve: DPV 33876 (from Precision Valve) ^f) Consolidation: 3.0% by weight solution of polymer J in ethanol / water (55:45 w / w), with an additional one being used to completely neutralize polymer J necessary amount of triethanolamine was added.

^g) Particle size from VOC55 aerosol:

5% of polymer J, 40% DME, 15% ethanol, 40% water, with an additional amount of AMP necessary for the complete neutralization of polymer J being added. Spraying device: spraying head: Kosmos .020D vortex .018 "21-6443-20, valve : DPV 33876 (Precision Valve) ^h) Fixing:

3.0% by weight solution of polymer J in ethanol / water (55:45 w / w), with an additional amount of AMP necessary for complete neutralization of polymer J being added.

Claims

Claims

1. Process for the preparation of polymers which i. 50-95% by weight of at least one ester of (meth) acrylic acid, ii. 5-50% by weight of at least one olefinically unsaturated, free-radically polymerizable anionogenic or anionic compound and iii. 0 to 30% by weight of at least one further radically polymerizable

Containing the compound in copolymerized form, by free-radical polymerization in a solution containing alcohol, at least one water-soluble initiator being used as the polymerization initiator, characterized in that the polymerization solution contains in the range from more than 25 to 50% by weight of water.

2. The method according to claim 1, characterized in that the polymerization solution comprises at most 50 wt .-% of at least one alcohol and the total amount of water and alcohol is at most 95 wt .-% of the polymerization solution.

3. The method according to any one of claims 1 or 2, characterized in that the polymerization solution in the range of 28 to 40 wt .-% water and in the range of 30 to 40 wt .-% alcohol.

4. The method according to any one of claims 2 or 3, characterized in that the at least one alcohol is or comprises ethanol and / or isopropanol.

5. The method according to any one of claims 1 to 4, characterized in that the water-soluble polymerization initiator is selected from the group consisting of peroxides, hydroperoxides, peroxodisulfates, percarbonates,

Peroxide esters, azo compounds and their mixtures.

6. The method according to any one of claims 1 to 5, characterized in that the water-soluble polymerization initiator is selected from the group consisting of hydrogen peroxide, lithium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate and mixtures thereof.

7. The method according to any one of claims 1 to 6, characterized in that the polymerization initiator is selected from the group consisting of

2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane disulfate dihydrate, 2,2'-azobis (2nd -methylpropionamide) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride,

2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] ,

2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide, 2,2'-azobis {2-methyl-N- [2- (1-hydroxybuthyl) ] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] and mixtures thereof.

8. The method according to any one of claims 1 to 7, characterized in that the temperature at which the polymerization is carried out is in the range from 30 to 120 ° C.

9. The method according to any one of claims 1 to 8, characterized in that the polymerization is carried out under a pressure in the range of 2 to 10 bar.

10. The method according to any one of claims 1 to 9, characterized in that

Component i) is selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, methylethacrylate, ethylethacrylate, n-propylethacrylate, i- Propylethacrylate, n-butylethacrylate, tert.-butylethacrylate, i-butylethacrylate, n-butyl (meth) acrylate, tert.-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, isopentyl acrylate, neopentyl acrylate, n-octyl (meth) acrylate, 1, 1, 3,3-

Tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, Pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, arrachinyl (meth) acrylate, behenyl (meth) acrylate, lignocerenyl (meth) acrylate, cerotinyl (meth) acrylate, melissinyl (meth) acrylate, palmitoleinyl (meth) acrylate, oleyl (meth) acrylate, linoline (meth) acrylate, linolenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, Phenoxyethyl acrylate, t-butylcyclohexyl acrylate, cyclohexyl (meth) acrylate, ureido (meth) acrylate, tetrahydrofurfuryl (meth) acrylate and mixtures thereof.

1 1. The method according to any one of claims 1 to 10, characterized in that component i) is selected from the group consisting of methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, i -Butyl methacrylate, sec- Butyl methacrylate and mixtures thereof.

12. The method according to any one of claims 1 to 1 1, characterized in that component ii) is selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, Glutaconic acid, aconitic acid, fumaric acid, half-esters of monoethylenically unsaturated dicarboxylic acids with 4 to 10, preferably 4 to 6, carbon atoms.

13. The method according to any one of claims 1 to 12, characterized in that component iii) is selected from esters of (meth) acrylic acid containing urethane groups.

14. Polymers obtainable by a process according to one of claims 1 to 13.

15. Use of the polymers according to claim 14 in cosmetic preparations.

16. Cosmetic preparations containing at least one polymer according to claim 14.