DE19838852A1 - New urethane (meth)acrylate compounds containing siloxane groups are precursors of new polymers useful especially in hair treatment products. - Google Patents

Abstract

Urethane (meth)acrylates containing siloxane groups, are new. Urethane (meth)acrylates (I) contain siloxane groups, which are polymerizable by free radicals, and which are made up from: (a) compounds containing active H atoms, and alpha , beta -ethylenic double bonds which are polymerizable by free radicals; (b) diisocanates; (c) compounds containing two active H atoms; (d) compounds containing active H atoms and siloxane groups; and optionally (e) compounds containing two or more active H atoms and ionogenic and/or ionic groups; (f) monovalent alcohols, primary or secondary amines and/or monoisocyanates; and/or (g) compounds containing alpha , beta -ethylenic double bonds and substituted with isocyanate groups. Independent claims are also included for the following: (1) the production of (I) containing urea groups; (2) water-soluble and water-dispersible polymers comprising (I) co-polymerized with alpha , beta -ethylenically unsaturated monomer (M) which is polymerizable by free radicals; and (3) cosmetic and pharmaceutical agents containing the polymer of (2).

Description

The present invention relates to radically polymerizable, urethane (meth) acrylates containing siloxane groups, water-soluble or water-dispersible polymers, which contain these polymerized th, the use of these polymers, as well as cosmetic agents that contain these polymers.

In cosmetics, polymers with film-forming properties are used for strengthening, structural improvement and shaping of the hair ver turns. These hair treatment agents generally contain one Solution of the film former in an alcohol or a mixture Alcohol and water.

Hair setting agents are generally in the form of aqueous alcoholic solutions sprayed on the hair. According to the Ver Vaping the solvent will make the hair on each other Points of contact of the remaining polymer in the desired Held shape. On the one hand, the polymers should be so hydrophilic that that they can be washed out of the hair, on the other hand but should they be hydrophobic, so that the polymers be hair kept its shape even in high humidity and do not stick together. To be as efficient as possible To achieve a hair setting effect, it is also desirable Use polymers which have a relatively high molecular weight and have a relatively high glass transition temperature (at least 15 ° C).

When formulating hair setting agents, this should also be taken into account ensure that due to environmental regulations to control the Emission of volatile organic compounds (VOC = volatile or ganic compounds) in the atmosphere a reduction in alcohol and propellant content is required.

Another current requirement for hair treatment products is to give the hair a natural look and shine, e.g. B. even if it is naturally particularly strong and / or dark hair.

It is known polysiloxanes and polysiloxane derivatives that are not are covalently bound to a setting polymer, as a plasticizer component to be used in hair care products. Since silicone oils and Polysiloxane derivatives with setting polymers, which are generally polar Containing groups that are incompatible requires manufacture more stable formulations generally require the addition of further auxiliaries fabrics. Nonetheless, segregation often occurs during the La or after using the products on the hair. The An The scope of such formulations is therefore very limited restricts. In order to prevent the disadvantageous segregation, Ver Searches have been made to covalently attach polysiloxane groups to the To bind setting polymer.

EP-A-408 311 describes the use of copolymers which a) a ethylenically unsaturated, hydrophilic monomer, b) an ethyl nically unsaturated monomers with polysiloxane groups and c) a contains ethylenically unsaturated, hydrophobic monomer incorporated, in hair care products.

EP-A-412 704 describes a hair care product based on a Graft copolymer, which is monovalent siloxane polymer units has a backbone based on a vinyl polymer.

WO 93/03703 describes a hairspray composition comprising send: a) a surfactant, b) using an ionic resin a number average molecular weight of at least 300,000 and c) a liquid carrier. This can be the ionic Resin around the graft copolymers described in EP-A-412 704 Act.

EP-A-362 860 describes alcohol-modified silicone ester earth derivatives and cosmetic compositions containing them.

None of these publications describes setting polymers based on of α, β-ethylenically unsaturated polyurethanes, which in addition have at least one siloxane group.

It is known to use polyurethanes with film-forming properties to use cosmetics. So describe DE-A-42 25 045 and the WO 94/03515 the use of water-soluble or in water dispersible, anionic polyurethanes as hair setting agents. the DE-A-42 41 118 describes the use of cationic poly urethanes and polyureas as auxiliaries in cosmetic and pharmaceutical preparations. These polyurethanes do not include any Polysiloxane groups and can meet the requirements of hair setting agents polymers only partially meet. So is z. B. the suppleness of the hair could be improved.

EP-A-492 657 describes a cosmetic agent for use in skin and hair care products, which is a linear poly Contains siloxane-polyoxyalkylene block copolymer.

EP-A-0 389 386 describes block copolymers which are a polysilo xanediol, a block copolyester and a diisocyanate incorporated contain. They are suitable for the controlled release of more active Ingredients.

EP-A-277 816 describes polydimethylsiloxanes with two hydroxyl groups at one end of the chain and a trimethylsilyl group at the other, the general formula

wherein R is hydrogen, methyl or ethyl and n is one Value from 0 to 4,000, as well as polyure modified therewith thane. The manufacture of these siloxane-modified polyurethanes takes place by polycondensation of the polysiloxanes of the above formula with polyurethane prepolymers containing two or more isocyanate groups have pen. Free-radical fish polymerizable siloxane groups Polyurethanes and polymers that contain these in polymerized form, are not described. An application of the modified poly urethane in hair cosmetics is also not described.

EP-A-636 361 describes a cosmetic composition which in a carrier at least one pseudolatex based on egg Nes polycondensate comprises the at least one polysiloxane unit and at least one polyurethane and / or polyurea unit containing anionic or cationic groups. This Po Lycondensates have no radical polymerizable, α, β-ethy lenisch unsaturated double bond and are not to Silicone modification of other polymers used. The washout The availability of these film formers is not satisfactory. In addition, be Because of a high proportion of siloxane, they don't sit for a hair polymer required setting effect.

WO 97/25021 has an Of comparable to EP-A-0 636 361 indemnity.

EP-A-751 162 describes the use of polycondensates with polyurethane and / or urea units and condensed Polysiloxane units or grafted polysiloxane side chains for the production of cosmetic or dermatological compositions settlements. The components used accordingly essentially Chen that described in EP-A-636 361.

EP-A-0 705 594 describes a cosmetic agent which is a aqueous dispersion of a film-forming polymer and a water-soluble Liche or water-dispersible silicone composition contains. The film-forming polymer can be a polyurethane or act a polyurea.

DE-A-195 24 816 describes hydroxylated siloxane block copoly mers containing siloxane and hydrocarbon segments, wel linked via hydroxylated hydrocarbon structures are.

DE-A-195 41 326 and WO 97/17386 describe water-soluble surface or water-dispersible polyurethanes with terminal acid re-group. A polyurethane prepolymer is used for their production with terminal isocyanate groups with an aminosulfonic acid or Aminocarboxylic acid implemented. The polyurethane prepoly mere also siloxane compounds with two opposite isocyanate groups contain reactive groups condensed in, the publication but not an example of a corresponding polyurethane prepolymer contains.

DE-A-195 41 658 describes water-soluble or water-dispersible yawable graft copolymers made from a polyurethane prepolymer with terminal isocyanate groups and one containing amino groups Protein, with the prepolymer also incorporating siloxane groups can hold.

Free-radical polymerizable, siloxane-containing polyurethanes and polymers which contain these polymerized in, are in the previously mentioned documents are not described.

EP-A-687 459 describes hair treatment compositions based on a aqueous polymer dispersion produced by radical graft copoly merization of a monoethylenically unsaturated siloxane macromono mers and at least one polymer is available, it being can be polyester or polyester amides. Radical fish unge Saturated, siloxane-containing polyurethanes are not described ben. Also an implementation of the monoethylenically unsaturated silo xan macromers with other, α, β-ethylenically unsaturated components ten is not described.

EP-A-687 462 and US-A-5,650,159 have either EP 687 459 comparable disclosure content, it being at the polymers that graft copolymers with the siloxane macromonomers be rised to act around polyurethanes and / or polyureas can.

WO 95/00108 describes liquid hair treatment compositions on Ba sis of graft copolymers from a vinyl polymer backbone and silicone-containing macromers grafted thereon. The vinylcopo Lymer backbone consists of a hydrophilic carboxylic acid containing monomer and optionally a lipophilic monomer. Si silicone-containing macromers which contain diisocyanates incorporated, are not described in this document.

US-A-5,162,472 describes silicone-containing polymers available by radical polymerization of a vinyl silicone-containing Mo nomers, which are (meth) acrylic acid esters of siloxane poly oils or vinyl silicone urethanes based on benzene-1- (1-iso cyanato-1-methylethyl) -3- (1- (methyl) ethynyl). Radi Kalfisch polymerizable polymers containing siloxane groups of diisocyanates are not described.

The present invention is based on the object of new, ra radically polymerizable, siloxane-containing ure than (meth) acrylate available. These are supposed to for the production of siloxane-modified polymers by radika Chemical polymerization are suitable. Preferably the re resulting siloxane-modified polymers as hair treatment be medium suitable. In particular, this hair treatment Medium on the one hand as a hair setting agent, on the other hand but also good washability (redispersibility) possesses Zen.

Surprisingly, it has now been found that the task performed free-radically polymerizable, siloxane-containing ure than (meth) acrylate is dissolved, the at least one compound with at least one active hydrogen atom and at least one radically polymerizable, α, β-ethylenically unsaturated Dop gel bond, at least one diisocyanate, at least one compound dung with 2 active hydrogen atoms per molecule and at least a compound having at least one siloxane group per molecule built-in included.

The present invention therefore relates to free-radically polymerizable, siloxane-containing urethane (meth) acrylates which

• a) at least one compound that has at least one active What hydrogen atom and at least one free-radically polymerized bare, α, β-ethylenically unsaturated double bond per molecule contains,
• b) at least one diisocyanate,
• c) at least one compound that has two active hydrogen atoms contains per molecule,
• d) at least one connection that has at least one active what hydrogen atom and at least one siloxane group per molecule contains,

incorporated, and the salts thereof.

In the context of the present invention, the expression C ₁ - to C ₃₀ -'Alkyl 'includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched C ₁ -C ₈ -alkyl, preferably C ₁ -C ₆ -alkyl and particularly preferably C ₁ -C ₄ -alkyl groups. These include, in particular, methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2 -Dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3- Dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethyl butyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2- Ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl etc.

Suitable longer-chain C ₈ to C ₃₀ alkyl or C ₈ to C ₃₀ alkylene groups are straight-chain and branched alkyl or alkylene groups. These are preferably predominantly linear alkyl radicals, as also occur in natural or synthetic fatty acids and fatty alcohols, as well as oxo alcohols, which, if necessary, can additionally be singly, doubly or polyunsaturated. These include B. n-hexyl (en), n-heptyl (en), n-octyl (en), n-nonyl (en), n-decyl (en), n-undecyl (en), n-dodecyl (en ), n-tridecyl (en), n-tetradecyl (en), n-pentadecyl (en), n-hexadecyl (en), n-heptadecyl (en), n-octadecyl (en), n-nonadecyl (en ) Etc.

The C ₅ - to C ₈ cycloalkyl group is, for. B. to cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The following are compounds that differ from acrylic acid and Me can derive thacrylic acid partially shortened by pasting the syllable "(meth)" in the verb derived from acrylic acid called.

Component a)

Suitable compounds a) are, for. B. the usual, the expert known vinyl compounds that additionally contain at least one ge Compared to isocyanate groups have reactive group that prefer wise is selected from hydroxyl groups and primary and se secondary amino groups. These include B. the esters α, β-ethyl nically unsaturated mono- and dicarboxylic acids with at least two valuable alcohols. As α, β-ethylenically unsaturated. Mono and / or dicarboxylic acids can e.g. B. acrylic acid, methacrylic acid, Fu marsic acid, maleic acid, crotonic acid, itaconic acid etc. and mixtures of which can be used. Suitable alcohols are common diols, Triols and polyols, e.g. B. 1,2-ethanediol, 1,3-propanediol, 1,4-Bu tanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, diethy lenglycol, 2,2,4-trimethylpentanediol-1,5, 2,2-dimethylpropane diol-1,3, 1,4-dimethylolcyclohexane, 1,6-dimethylolcyclohexane, Glycerine, trimethylolpropane, erythritol, pentaerythritol, sorbitol etc. When connecting a) is then z. B. Hydroxyme ethyl (meth) acrylate, hydroxyethyl ethacrylate, 2-hydroxy ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypro pyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybu tyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-2-ethyl hexyl (meth) acrylate and di (meth) acrylic acid esters of 1,1,1-trimethylolpropane or glycerine.

Suitable monomers a) are also the esters and amides of the aforementioned α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ - to C ₁₂ -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. carry an NC ₁ to C ₈ 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-C ₁ - to C ₂₂ -alkyl) (meth) acrylamides, such as N-Hydroxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc.

Suitable monomers a) are also the amides of the aforementioned α, β- ethylenically unsaturated mono- and dicarboxylic acids with di- and Polyamines that have at least two primary or two secondary or have a primary and a secondary amino group (s). In addition count e.g. B. the corresponding amides of acrylic acid and meth acrylic acid such as aminomethyl (meth) acrylamide, aminoethyl (meth) acrylic lamide, aminopropyl (meth) acrylamide, amino-n-butyl (meth) acrylamide, Methylaminoethyl (meth) acrylamide, ethylaminoethyl (meth) acrylamide, Methylaminopropyl (meth) acrylamide, ethylaminopropyl (meth) acryla mid, methylamino-n-butyl (meth) acrylamide etc.

Suitable monomers a) are also the reaction products of epoxide compounds that have at least one epoxy group with the previously mentioned α, β-ethylenically unsaturated mono- and / or di carboxylic acids and their anhydrides. Suitable epoxy compounds are z. B. glycidyl ethers, such as bisphenol A diglycidyl ether, Resor cindiglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,6-hexanediol dig lycidyl ether etc.

Component b)

Component b) is customary aliphatic, cycloaliphatic and / or aromatic diisocyanates, such as tetrams ethylene diisocyanate, hexamethylene diisocyanate, methylenediphenyl di isocyanate, 2,4- and 2,6-tolylene diisocyanate and their isomer amount mix, o- and m-xylylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-cyclohexylene diisocyanate, dicyclohexylmethane diisocyanate and Mixtures thereof. Component b) is preferably around hexamethylene diisocyanate, isophorone diisocyanate, o- and m-xyly lene diisocyanate, dicyclohexylmethane diisocyanate and mixtures there from. If desired, up to 3 mol% of the compounds mentioned can be used can be replaced by triisocyanates.

Component c)

Suitable compounds of component c) are, for. B. Diols, Di amines, amino alcohols, and mixtures thereof. The molecular weight of these compounds is preferably in the range of about 56 to 280. If desired, up to 3 mol% of the above can be used Compounds can be replaced by triols or triamines.

Suitable diols c) are, for. B. ethylene glycol, propylene glycol, Bu ethylene glycol, neopentyl glycol, cyclohexanedimethylol, di-, tri-, Tetra-, penta- or hexaethylene glycol and mixtures thereof. Be preference is given to neopentyl glycol and / or cyclohexanedimethylol set.

Suitable amino alcohols c) are, for. B. 2-aminoethanol, 2- (N-methy lamino) ethanol, 3-aminopropanol, 4-aminobutanol, 1-ethylaminobu tan-2-ol, 2-amino-2-methyl-1-propanol, 4-methyl-4-aminopen tan-2-ol etc.

Suitable diamines c) are, for. B. Ethylenediamine, propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane.

Preferred compounds of component c) are polymers with a number average molecular weight in the range of about 300 to 5,000, preferably about 400 to 4,000, in particular 500 to 3,000. B. polyester diols, polyetherols, α, ω-Diami nopolyethers and mixtures thereof. Preferably ethergrup pen-containing polymers used.

The polyetherols c) are preferably polyal kylene glycols, e.g. B. polyethylene glycols, polypropylene glycols, Po lytetrahydrofurans etc., block copolymers of ethylene oxide and Propylene oxide or block copolymers of ethylene oxide, propyleno xide and butylene oxide, which are the alkylene oxide units at random distributed or polymerized in the form of blocks.

Suitable α, ω-diaminopolyethers c) are, for. B. by amination of Polyalkylene oxides can be produced with ammonia.

Suitable polytetrahydrofurans c) can by cationic poly merization of tetrahydrofuran in the presence of acidic catalysis goals, such as B. sulfuric acid or fluorosulfuric acid, herge will be presented. Such manufacturing processes are known to those skilled in the art known.

Usable polyester diols c) preferably have a number average Average molecular weight in the range of about 400 to 5,000 before assigned 500 to 3,000, in particular 600 to 2,000.

Suitable polyester diols are all those which are usually 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 sulfo isophthalic 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 poly (meth) acrylate diols of the formula

wherein R 'is H or CH ₃ and R "is C ₁ -C ₁₈ -alkyl (in particular C ₁ -C ₁₂ - or C ₁ -C ₈ -alkyl), which have a molecular weight of up to about 3000. Such diols can be produced in the usual way and are commercially available (Tegomer® types MD, BD and OD from Goldschmidt).

Polyester diols based on aromatic and ali are preferred phatic dicarboxylic acids and aliphatic diols, in particular those in which the aromatic dicarboxylic acid 10 to 95 mol%, in particular 40 to 90 mol% and preferably 50 to 85 mol%, des total dicarboxylic acid content (remainder aliphatic dicarboxylic acids) matters.

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-NaSO ₃ -isophthalic acid / phthalic acid / adipic acid / 1,6-hexanediol, adipic acid / ethylene glycol, Isophthalic acid / adipic acid / neopentyl glycol, isophthalic acid / adipic acid / neopentyl glycol / diethylene glycol / dimethylolcyclohexane and 5-NaSO ₃ -isophthalic acid / isophthalic acid / adipic acid / neopentyl glycol / diethylene glycol / dimethylolcyclohexane.

The compounds of component c) can be used individually or as Mi can be used.

Component d)

Component d) is preferably selected from:

• - Polysiloxanes of the general formula I.1
  wherein
  a and b independently represent 2 to 8,
  c stands for 3 to 100,
  R ¹ and R ² independently of one another are C ₁ - to C ₈ -alkyl, before given methyl, benzyl or phenyl,
  Z ¹ and Z ² independently of one another represent OH, NHR ³ or a radical of the formula II
  - (CH ₂ CH ₂ O) _v (CH ₂ CH (CH ₃ ) O) _w -H (II)
  stand, where
  in formula II, the sequence of the Alkylenoxidein units is arbitrary and
  v and w independently represent an integer from 0 to 200, where the sum of v and w <0,
  R ^{3 represents} hydrogen, C ₁ to C ₈ alkyl or C ₅ to C ₈ cycloalkyl;
• - Polysiloxanes of the general formula I.2
  wherein
  the order of the siloxane units is arbitrary,
  d and e independently of one another represent 0 to 100, the sum of d and e being at least 2,
  f stands for an integer from 2 to 8,
  Z ^{3 represents} OH, NHR ³ or a radical of the formula II,

and mixtures thereof.

According to a suitable embodiment, the polysiloxanes d) of the general formula I.1 no alkylene oxide radicals of the general Formula II on. These polysiloxanes d) then preferably have one number average molecular weight in the range of about 300 to 5,000, preferably 400 to 3,000.

Suitable polysiloxanes d) which have no alkylene oxide radicals are z. B. the Tegomer® brands from Goldschmidt.

According to a further suitable embodiment, the polysiloxanes d) are silicone-poly (alkylene oxide) copolymers of the formula I.1, where at least one or both radicals Z ¹ and / or Z ^{2 are} a radical of the general formula II.

In formula II, the sum of v and w is preferably so ge selects that the molecular weight of the polysiloxanes d) then in one Range from about 300 to 30,000.

Preferably the total number of alkylene oxide units in the poly is siloxanes d), that is, the sum of v and w in formula II then in a range from about 3 to 200, preferably 5 to 180.

According to a further suitable embodiment, the polysiloxanes d) are silicone-poly (alkylene oxide) copolymers of the formula I.2 which have at least one radical Z ^{3 of} the general formula II.

The sum of v and w is then preferably as in formula II derum chosen so that the molecular weight of the polysiloxanes d) then ranges from about 300 to 30,000. Preferred is the total number of alkylene oxide units in the polysiloxanes d), that is, the sum of v and w in formula II if in a range from about 3 to 200, preferably 5 to 180.

Suitable silicone-poly (alkylene oxide) copolymers d) under the International non-proprietary names Dimethicon are known are the Tego pren® brands from Goldschmidt, Belsil © 6031 from Wacker and Silvet® L from Witco.

Suitable polysiloxanes d) are also those in EP-A-277 816 be wrote Polydimethylsiloxane.

The urethane (meth) acrylate according to the invention preferably also contain at least one component incorporated, which is selected from

• a) Compounds that have two or more active hydrogen atoms and at least one ionic and / or ionic group per Mo lekül included,
• b) monohydric alcohols, amines with a primary or secondary the amino group, aliphatic, cycloaliphatic or aromatic monoisocyanates and mixtures thereof,
• c) α, β-ethylenically unsaturated compounds that additionally we contain at least one isocyanate group per molecule,

and mixtures thereof.

Component e)

The urethane (meth) acrylates according to the invention can additionally we Contain at least one component e) in copolymerized form, the min at least one ionogenic and / or ionic group per molecule ent holds. These are preferably carboxylate groups and / or sulfonate groups or around nitrogen-containing groups.

Suitable diamines and / or diols e) with ionogenic or ionic groups are, for. B. dimethylolpropanoic acid and compounds of the formula

and or

wherein R ⁴ each represents a C ₂ -C ₁₈ alkylene group and Me represents Na or K.

Compounds of the formula can also be used as component e)

H ₂ N (CH ₂ ) _n -NH- (CH ₂ ) _m -COO ^- M ⁺

and or

H ₂ N (CH ₂ ) _n -NH- (CH ₂ ) _m -SO ₃ ^- M ⁺

where m and n independently of one another represent an integer of 1 to 8, in particular 1 to 6, and M for Li, Na or K stands.

If compounds with nitrogen-containing groups are used as component e), cationic urethane (meth) acrylates are obtained. Usable components e) are z. B. Compounds of the general formulas

wherein

• - R ⁵ and R ⁶ , which can be the same or different, are C ₂ -C ₈ -alkylene,
• - R ⁷ , R ¹⁰ and R ¹¹ , which can be identical or different, represent C ₁ -C ₆ -alkyl, phenyl or phenyl-C ₁ -C ₄ -alkyl,
  R ⁸ and R ⁹ , which can be identical or different, represent H or C ₁ -C ₆ -alkyl,
  o stands for 1, 2 or 3,
  XU stands for chloride, bromide, iodide, C ₁ -C ₆ -alkyl sulfate or SO ₄ ^2- / ₂ .

Component f)

The urethane (meth) acrylates according to the invention can contain a component f) incorporated, which is selected from monohydric alcohols, amines with a primary or secondary amino group, aliphatic, cycloaliphatic or aromatic monoisocyanates and mixtures thereof. Preferred compounds f) are generally compounds of the formula R ¹² -Z ⁴ , in which R ^{12 is} a C ₂ - to C ₃₀ -alkyl radical and Z ^{4 has} the meanings given in formula I.1 for Z ¹ and Z ^{2 or for} NCO stands.

Suitable monohydric alcohols f) have a straight-chain or branched alkyl radical having 2 to 30 carbon atoms, preferably 8 to 22 carbon atoms, which can optionally also be singly, doubly or polyunsaturated. Suitable C ₂ - to C ₃₀ -alkyl radicals are those mentioned above. The alcohols f) can be used individually or as mixtures.

Preferred monohydric alcohols f) are, for. B. ethanol, n-propanol, Nonanol, Undecanol, Tridecanol, Tetradecanol, Pentadecanol, Hexa decanol, heptadecanol, octadecanol, etc. and mixtures thereof. The alcohols can be isomerically pure or in the form of isomers Mixtures are used.

Preferred hydroxyl-containing compounds f) are furthermore the alkoxylates of the aforementioned C ₂ - to C ₃₀ -alkanols, of the general formula III

R ¹² - (CH ₂ OH ₂ O) _g (CH ₂ CH (CH ₃ ) O) _h -H (III)

where in formula III the sequence of the alkylene oxide units is arbitrary, g and h independently of one another stand for an integer from 0 to 200, the sum of g and h being <0, and R ^{12 has} the meaning given above.

Suitable higher primary or secondary amines f) are amines and amine mixtures which have one or two of the aforementioned C ₁ - to C ₃₀ -alkyl radicals. These can e.g. B. obtained by reacting natural or synthetic fatty acids or fatty acid mixtures with ammonia to nitriles and subsequent hydrogenation who the. These include B. alkylamines which have the alkyl radicals mentioned above for the monohydric alcohols f), that is, ethyl and the isomeric propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl amines, etc. and mixtures thereof.

Suitable monoisocyanates f) are, for. B. C ₁ - to C ₃₀ alkyl isocyanates, which are generated from the aforementioned amines and amine mixtures by Phos or from natural or synthetic fatty acids and fatty acid mixtures by Hofmann, Curtius or Lossen degradation he is available.

Suitable cycloaliphatic monoisocyanates f) are, for. B. Cyclohe xyl isocyanate, 2-, 3- and 4-methylcyclohexyl isocyanate, etc. and Mixtures thereof.

Suitable aromatic monoisocyanates f) are, for. B. Phenylisocya nat, 2-, 3- and 4-methylphenyl isocyanate, etc. and mixtures there from.

Component g)

The component g) is, for. B. to isocyanates of the general formula IV

wherein
the -C (CH ₃ ) ₂ -NCO group can be in the o-, m- or p-position to the vinyl group and R ^{11 is} hydrogen or C ₁ - to C ₈ -alkyl.

In formula IV, R ¹³ is preferably hydrogen, methyl or ethyl.

According to a first possible embodiment, it is the urethane (meth) acrylates according to the invention are nonionic Links. These then do not contain any of the aforementioned ver bindings e) built in.

According to a second possible embodiment, it is the urethane (meth) acrylates according to the invention to ionic compounds fertilize. These then have at least one ionic or ionogenic Group up, d. H. they contain at least one of the previously mentioned th connections of component e) installed. If this conn dungen e) as ionogenic or ionic group at least one Car have boxylatgruppe and / or sulfonate group, so result anionic urethane (meth) acrylates. Preferably the manufacturer ment of these anionic compounds as dimethylolpropanoic acid Compound e) used. If the connection is the Component e) to a compound with a nitrogen-containing Group acts, so result cationic urethane (meth) acrylates. A preferred compound e) for the production of cationic ure than (meth) acrylate is N-methyldipropylenetriamine.

The urethane (meth) acrylates according to the invention are prepared by reacting at least one diisocyanate b) and optionally one or more isocyanate-containing compounds f) and / or g) with the isocyanate-reactive groups of the other components a), c), d) and, if applicable, e) and / or f). If components containing hydroxyl groups are used to react with the components containing isocyanate groups, then preferably the entire amount of isocyanate is reacted with the components containing hydroxyl groups to form a polyurethane prepolymer containing isocyanate groups. This reaction generally takes place at an elevated temperature in the range from about 40 to 150.degree. C., preferably from about 50 to 100.degree. The reaction can be carried out without a solvent in the melt or in a suitable solvent or solvent mixture. These include ketones such as acetone and methyl ethyl ketone. In the reaction of the isocyanate group-containing compounds of components b), f) and / or g) with the hydroxyl group-containing compounds of components a), c), d) and e) and / or f), the ratio of NCO equivalents is the Compounds of components b), f) and / or g) to an equivalent active hydrogen atom of the other components are selected so that a polyurethane prepolymer results which still has free isocyanate groups. In general, the ratio of NCO equivalent to equivalent of active hydrogen atom of the hydroxyl-containing compounds is <1: 1 to 1.3: 1, preferably 1.05: 1 to 1.2: 1. The subsequent reaction of the isocyanate-containing polyurethane prepolymer to the Urethane (meth) acrylate according to the invention is preferably likewise carried out in one of the solvents mentioned above. If desired, however, the reaction can be carried out without a solvent. The temperature is generally in a range from about 0 to 60.degree. C., preferably about 10 to 50.degree. The amine group-containing components a), c), d), e) and / or f) are generally used in an amount such that the free isocyanate groups of the polyurethane prepolymer are at least partially, but preferably completely, converted. Any isocyanate groups still present are finally removed by adding alcohols, e.g. B. ethanol, amines, e.g. B. 2-amino-2-methyl-1-propanol, or mixtures thereof inactivated. Urethane (meth) acrylates which do not contain any hydroxyl group-containing components are produced by reacting the amine group-containing components with the isocyanate group-containing components at a temperature in the range from about 0 to 60.degree. Both the isocyanate components and the components containing amine groups can be submitted for the reaction. Suitable solvents for this reaction are, for. B. water, C ₁ -C ₄ alcohols such as methanol, n-propanol, isopropanol, n-butanol and preferably ethanol and the aforementioned Ke tone.

Urethane (meth) acrylates containing acid groups can be partially used wise or complete neutralization with a base, amino group pen containing by neutralization with an acid or by Quaternization, into a water-soluble or water-dispersible Form to be transferred. As a rule, the salts obtained have the urethane (meth) acrylates a better water solubility or Dispersibility in water than that not neutralized Shape. Suitable bases for the neutralization of acidic groups Urethane (meth) acrylates and acids or quaternizing agents for the protonation or quaternization of ure containing amine groups Than (meth) acrylates are used below in the neutralization or quaternization of the polymers based on the invention Called urethane (meth) acrylates.

If desired, the urethane (meth) acry according to the invention late also in non-neutralized or non-quaternized Form for reaction with free-radically polymerizable compounds genes, as described below, can be used.

Another object of the invention is the use of to before described, radically polymerizable, siloxane groups containing urethane (meth) acrylates as a component for the production of Polymers. It is thus possible to use polymers containing siloxane groups by radical copolymerization of the urethane (meth) acrylates with to establish at least one other connection, which one if at least one radically polymerizable, α, β-ethyl has nisch unsaturated double bond. In this further Component can be at least one radical polymer manageable monomer, oligomer and / or polymer and mixtures thereof Act.

Another object of the invention is a water-soluble or water-dispersible polymer, the at least one invented proper urethane (meth) acrylate and at least one radical polymerizable, α, β-ethylenically unsaturated monomer M) einpo contains lymerized.

The water-soluble or water-dispersible ones according to the invention The urethane (meth) acrylates generally contain polymers an amount of about 0.05 to 80 wt .-%, preferably 0.1 to 50% by weight, in particular 0.5 to 35% by weight, based on the total amount of urethane (meth) acrylate and monomer M), polymerized.

The monomer M) is preferably selected from

• 1. Essentially hydrophobic, nonionic compounds, preferably esters of α, β-ethylenically unsaturated mono- and / or dicarboxylic acids with C ₁ -C ₃₀ alkanols, amides α, β-ethylenically unsaturated mono- and / or dicarboxylic acids with mono- and Di- C ₁ -C ₃₀ -alkylamines, esters of vinyl alcohol or allyl alcohol with C ₁ -C ₃₀ monocarboxylic acids, vinyl ethers, vinyl aromatics, vinyl halides, vinylidene halides, C ₂ -C ₈ monoolefins, non-aromatic hydrocarbons with at least 2 conjugated double bonds and mixtures of that,
• 2. Compounds with a radically polymerizable, α, β- ethylenically unsaturated double bond and at least one ionogenic and / or ionic group per molecule,
• 3. Essentially hydrophilic, nonionic compounds, preferably N-vinylamides, N-vinyllactams, primary amides α, β-ethylenically unsaturated monocarboxylic acids, vinyl- and allyl-substituted heteroaromatic compounds, esters α, β-ethylenically unsaturated mono- and dicarboxylic acids with C. ₁ -C ₃₀ alkanediols, esters and amides α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C ₃₀ amino alcohols which have a primary or secondary amino group, polyether acrylates, and mixtures thereof,

and mixtures thereof.

Suitable monomers M1) are essentially hydrophobic, non-ionic cal monomers. These include B. vinyl formate, vinyl acetate, Vi nyl propionate, vinyl n-butyrate, vinyl stearate, vinyl laurate, styrene, α-methylstyrene, o-chlorostyrene, vinyl toluenes, vinyl chloride, vinyl lidene chloride, ethylene, propylene, butadiene, isoprene, chloroprene, Methyl, ethyl, butyl, dodecyl vinyl ether etc.

Preferred monomers M1) are, for. B. the esters α, β-ethylenically unge saturated mono- and dicarboxylic acids with C ₁ -C ₃₀ alkanols, preferably C ₁ -C ₂₂ alkanols. The amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with mono- and dialkylamines which have 1 to 30 carbon atoms, preferably 1 to 22 carbon atoms, per alkyl radical are also preferred. They are preferably compounds of the general formula V

wherein
R ^{14 represents} hydrogen or C ₁ - to C ₈ -alkyl,
R ^{15 represents} a straight-chain or branched C ₁ - to C ₃₀ -alkyl radical, and
Y stands for O or NR ¹⁶ , where R ^{15 stands} for hydrogen, C ₁ - to C ₈ -alkyl or C ₅ - to C ₈ -cycloalkyl.

In the formula VR ¹⁴ is preferably hydrogen, methyl or ethyl.

Y is preferably O or NH.

Suitable radicals R ¹⁵ are the aforementioned C ₁ -C ₃₀ -alkyl radicals. In particular, R ¹⁵ stands for methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, ethylhexyl , 1,1,3,3-tetramethylbutyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, margarinyl, stearyl, palmitoleinyl, oleyl or linolyl.

In particular, the monomer M1) is selected from Me ethyl (meth) acrylate, methyl ethacrylate, ethyl (meth) acrylate, ethyl thacrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, n-Oc tyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhe xyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-Undecyl (meth) acrylate, tridecyl (meth) acrylate, Myri styl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylic lat, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, Arrachi nyl (meth) acrylate, behenyl (meth) acrylate, lignocerenyl (meth) acrylic lat, cerotinyl (meth) acrylate, melissinyl (meth) acrylate, palmitole nyl (meth) acrylate, oleyl (meth) acrylate, linolyl (meth) acrylate, lino lenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tert-butyl (meth) acrylamide, n-octyl (meth) acrylamide, 1,1,3,3-Te tramethylbutyl (meth) acrylamide, ethylhexyl (meth) acrylamide, n-No nyl (meth) acrylamide, n-decyl (meth) acrylamide, n-undecyl (meth) acrylic lamide, tridecyl (meth) acrylamide, myristyl (meth) acrylamide, pentad cyl (meth) acrylamide, palmityl (meth) acrylamide, heptade cyl (meth) acrylamide, nonadecyl (meth) acrylamide, Arrachi nyl (meth) acrylamide, behenyl (meth) acrylamide, lignocers nyl (meth) acrylamide, cerotinyl (meth) acrylamide, Melissi nyl (meth) acrylamide, palmitoleinyl (meth) acrylamide, Oleyl (meth) acrylamide, linolyl (meth) acrylamide, linoles nyl (meth) acrylamide, stearyl (meth) acrylamide, lauryl (meth) acrylamide and mixtures thereof.

The compounds M2) have at least one ionogenic or ionic cal group per molecule, which is preferably selected from Carboxylate groups and / or sulfonate groups and their through part wise or complete neutralization with a base obtainable chen salts, as well as tertiary amine groups, partially or fully can be constantly protonated and quaternized. Suitable bases for neutralization or acids for protonation and alky The afore-mentioned agents for quaternization are used.

Suitable monomers M2) are, for. B. the aforementioned, α, β-ethyls nically unsaturated mono- and / or dicarboxylic acids and their halves esters and anhydrides, such as acrylic acid, methacrylic acid, fumaric acid, Maleic acid, itaconic acid, crotonic acid, maleic anhydride, mono butyl maleate, etc. Preferred are acrylic acid, methacrylic acid and their alkali metal salts such as their sodium and potassium salts set.

Suitable monomers M2) are also acrylamidoalkanesulfonic acids and their salts such as 2-acrylamido-2-methylpropanesulfonic acid and their alkali metal salts, e.g. B. their sodium and potassium salts.

Further suitable compounds M2) are the esters of the aforementioned α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ - to C ₁₂ -amino alcohols which are C ₁ - to C ₈ -dialkylated on the amine nitrogen. These include B. N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth ) acrylate, N, N-dimethylaminocyclohexyl (meth) acrylate etc. N, N-dimethylaminopropyl acrylate and N, N-dimethylaminopropyl (meth) acrylate are preferably used.

Suitable monomers M2) are also the amides of those mentioned above th α, β-ethylenically unsaturated mono- and dicarboxylic acids with Diamines that have a tertiary and a primary or secondary amino have group. These include B. N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dime thylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacryl amide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) - butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide, N- [4- (dimethylamino) cy clohexyl] methacrylamide etc.

Suitable monomers M3) are essentially hydrophilic, non-ionic niche monomers. These include B. N-vinyl amides, such as N-vinyl form amide, N-vinylacetamide, N-vinylpropionamide etc. Preference is given to N- Vinylformamide used.

Suitable monomers M3) are also N-vinyl lactams and their derivatives, the z. B. one or more C ₁ -C ₆ -alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. may have. These include B. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2 -piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam etc.

Suitable monomers M3) are also primary amides of the ge above called α, β-ethylenically unsaturated monocarboxylic acids such as acrylic amide, methacrylamide, ethacrylamide etc.

Suitable monomers M3) are also vinyl and allyl substances tuted heteroaromatic compounds such as 2- and 4-vinylpyri din, allyl pyridine, and preferably N-vinyl heteroaromatics, such as N- Vinylimidazole, N-vinyl-2-methylimidazole etc.

Suitable monomers M3) are also the esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, etc., with C ₁ -C ₃₀ alkanediols. These include B. 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxybutyl methacrylate, hydroxybutyl methacrylate, 6-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate Hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylate, etc. Hydroxyethyl acrylate and hydroxyethyl methacrylate are preferably used. Suitable monomers e) are also the esters of the aforementioned acids with triols and polyols, such as. B. glycerine, erythritol, pentaerythritol, sorbitol etc.

Suitable compounds M3) are also polyether acrylates of the general formula VI

wherein
the sequence of the alkylene oxide units is arbitrary,
k and l independently of one another represent an integer from 0 to 50, the sum of k and l being at least 5,
R ^{17 represents} hydrogen or C ₁ - to C ₈ -alkyl, and
R ^{18 represents} hydrogen or C ₁ - to C ₆ -alkyl,
W represents O or NR ¹⁹ , where R ^{19 represents} hydrogen, C ₁ - to C ₈ -alkyl or C ₅ - to C ₈ -cycloalkyl.

The polyether acrylates M3) are preferably Ver bonds of the general formula VI, in which the sum of k and l is an integer from 5 to 70, preferably 6 to 50, is.

In formula VI, R ¹⁷ preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular hydrogen, methyl or ethyl .

^{R 18} in the formula VI is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl or n-hexyl.

W in the formula VI is preferably O or NH.

Suitable polyether acrylates M3) are, for. B. the polycondensation products of the aforementioned α, β-ethylenically unsaturated mono- and / or dicarboxylic acids and their acid chlorides, amides and hydrides with polyetherols. Suitable polyetherols can easily be prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule such as water or a short-chain alcohol R ¹⁶ -OH. The alkylene oxides can be used individually, alternately in succession or as a mixture. The polyether acrylates M3) can be used alone or in mixtures for the production of the poly mers used according to the invention.

According to a first preferred embodiment, they contain water-soluble or water-dispersible poly according to the invention mere at least one urethane (meth) acrylate according to the invention, such as previously described, at least one substantially hydrophobic, non-ionic compound M1) and at least one ionogen or ionic compound M2) incorporated. If necessary, these can Polymers in addition at least one other compound of the compo nente M3) included in polymerized form.

Preferably the polymer contains

• - 0.1 to 50 wt .-%, preferably 0.5 to 35 wt .-%, at least a urethane (meth) acrylate as in any one of claims 1 to 3 defined,
• - 40 to 75 wt .-%, preferably 45 to 73 wt .-%, at least one component M1),
• - 10 to 35 wt .-%, preferably 18 to 30 wt .-%, at least one component M2),
• - 0 to 30 wt .-%, at least one component M3),

polymerized.

According to a further preferred preferred embodiment ent hold the water-soluble or water-dispersible according to the invention gable polymers at least one ure according to the invention than (meth) acrylate, as described above and at least one im Substantially hydrophilic, nonionic compound M3) incorporated. Optionally, these polymers can additionally contain at least one Another compound that is selected from the compounds of the Components M1) and / or M2) contain polymerized.

Preferably the polymer contains

• - 0.1 to 50 wt .-%, preferably 0.5 to 35 wt .-%, at least a urethane (meth) acrylate as in any one of claims 1 to 3 defined,
• - 0 to 50 wt .-% of at least one component M1),
• - 0 to 20 wt .-%, at least one component M2),
• - 25 to 80 wt .-%, at least one component M3),

polymerized.

The polymers according to the invention preferably have as a component M2) at least one compound with at least one anionogenic and / or anionic group per molecule. The acid number of this Polymer is then preferably in a range from 30 to 190 mg KOH / g.

The polymers according to the invention preferably have as a component M2) at least one compound with at least one cationogenic and / or cationic group per molecule. Preferably the Amine number or the quaternary ammonium number of the invention Polymers then in a range from about 30 to 190 mg KOH / g.

The polymers according to the invention are produced by ra radical polymerization according to customary methods known to those skilled in the art Procedure. This includes radical polymerization in bulk, Emulsion, suspension and in solution, preferably the emulsion and solution polymerization. The amounts of to be polymerized Compounds based on solvents or dispersants generally chosen so that about 30 to 80 wt .-% Lö solutions, emulsions or dispersions are obtained. The polymers rization temperature is usually 30 to 120 ° C, preferably 40 to 100 ° C. The polymerization medium for the solution polymeri sation can only from an organic solvent as also from mixtures of water and at least one water-mixed organic solvents exist. Preferred organic Solvents are e.g. B. alcohols such as methanol, ethanol, n-Pro panol, isopropanol, n-butanol, ketones such as acetone and methyls ethyl ketones, tetrahydrofuran, etc. The solution polymerization can both as a batch process and in the form of a feed process, including monomer feed, step and gradient operation, be performed. In general, the feed process is preferred drive, where you can optionally part of the Polymerisa tion approach presented, heated to the polymerization temperature and then the remainder of the polymerization batch, more commonly wisely via one or more spatially separate inlets, continuously, stepwise or with superimposition of a con centering gradient while maintaining the polymerization fed to the polymerization zone.

As initiators for the radical polymerization are customary che peroxo or azo compounds used. These include B. Tue benzoyl peroxide, tert-butyl perpivalate, tert-butyl per-2-ethylhe xanoate, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylpe roxy) hexane, aliphatic or cycloaliphatic azo compounds, z. B. 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyroni tril), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis (1-cy clohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile, 4,4'-azo bis (4-cyanovaleric acid) and its alkali metal and ammonium salts, e.g. B. the sodium salt, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (2-amidino propane) and the acid addition salts of the last two mentioned Connections, e.g. B. the dihydrochlorides.

Hydroperoxides and hydrogen peroxide are also used as initiators in combination with reducing agents and persalts. Ge suitable hydroperoxides are, for example, t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide and pinane hydroperoxide each because in combination with, for example, a salt of the hydroxy methanesulfinic acid, a ferrous salt or ascorbic acid. Ge Suitable persalts are in particular alkali metal peroxydisulfates.

The amount of initiator used, based on the monomers, is in Generally based in a range of about 0.1 to 2% by weight based on the total weight of the monomers to be polymerized.

The K values of the resulting copolymers are preferably in a range from about 15 to 90, preferably 20 to 70, esp special 25 to 60 (1% by weight solution in ethanol). To achieve of the desired K value, especially in the case of emulsion or suspension polymerization, the use of a regulator be good. Aldehydes, for example, are suitable as regulators Formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and iso butyraldehyde, formic acid, ammonium formate, hydroxylammonium sul fat and hydroxylammonium phosphate. Furthermore, controllers can be used which contain sulfur in organically bound form th, such as di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide etc., or regulators that contain sulfur in the form of SH groups, such as n-butyl mercaptan, n-hexyl mercaptan or n-dodecyl mercaptan. Water-soluble, sulfur-containing polymers are also suitable ons regulators, such as hydrogen sulfites and disulfites. White Furthermore, allyl compounds, such as allyl alcohol, are suitable as regulators or allyl bromide, benzyl compounds such as benzyl chloride or Al alkyl halides such as chloroform or carbon tetrachloride.

If desired, the polymer solution is added to the Polymerization reaction one or more polymerization initiations gates and heats the polymer solution, e.g. B. on the Polymerisa tion temperature or to temperatures above the Polymerisati on temperature to complete the polymerization. Appropriate net are the azo initiators specified above, but also all of them their usual, for a radical polymerization in aqueous Solution suitable initiators, for example peroxides, Hydropero xides, peroxodisulfates, percarbonates, peroxoesters and hydrogen peroxide. This turns the polymerization reaction into a Hö higher sales, such as B. of 99.9% led. The one at the Polyme ization resulting solutions can optionally by a State-of-the-art drying process into solid Powder to be transferred. Preferred methods are, for example the spray drying, the spray fluidized bed drying, the rollers drying and belt drying. The Ge freeze drying and freeze concentration. If so desired the solvent can also be used by conventional methods, e.g. B. Destil lation at reduced pressure, partially or completely ent be removed.

According to a suitable embodiment, it is he inventive polymers to nonionic polymers.

According to a further suitable embodiment, the water-soluble or water-dispersible polymers according to the invention are anionic or anionogenic polymers. The acid groups of the polymers can be partially or fully neutralized with a base. As a rule, the obtained salts of the polymers have better water solubility or dispersibility in water than the non-neutralized polymers. Alkali metal bases such as sodium hydroxide, potassium hydroxide, soda, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate and alkaline earth metal bases such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate as well as ammonia and amines can be used as the base for the neutralization of the polymers. Suitable amines are e.g. B. C ₁ -C ₆ -alkylamines, preferably n-propyla min and n-butylamine, dialkylamines, preferably diethylpropylamine and dipropylmethylamine, trialkylamines, preferably triethylamine and triisopropylamine, C ₁ -C ₆ -alkyldiethyanolamines, preferably methyl or ethyldiethanolamine and di- C ₁ -C ₆ alkyl ethanolamines. Especially for use in hair treatment agents, 2-amino-2-methyl-1-propanol, 2-amino-2-ethylpropane-1,3-diol, diethylaminopropylamine and triisopropanolamine have proven useful for neutralizing the acid group-containing polymers. The neutralization of the acid group-containing polymers can also be made with the help of Mi mixtures of several bases, for. B. Mixtures of caustic soda and triisopropanolamine. The neutralization can be partially z. B. to 5 to 95%, preferably 30 to 95%, or completely, ie to 100%.

According to a further suitable embodiment, the water-soluble or water-dispersible polymers according to the invention are cationic or cationogenic polymers. The amine groups or polymers containing protonated or quaternized amine groups, because of their cationic groups, are generally readily soluble in water or water / alcohol mixtures or at least dispersible without the aid of emulsifiers. Charged cationic groups can be removed from the tertiary amine nitrogen present either by protonation, e.g. B. with carboxylic acids such as lactic acid, or mineral acids such as Phosp hors acid, sulfuric acid and hydrochloric acid, or tion by Quaternisie, z. B. with alkylating agents, such as C ₁ - to C ₄ -Alkylhalogeni or sulfates generate. Examples of such Alkylierungsmit tel are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.

According to a further suitable embodiment, the inven polymers according to the invention, both acid groups and amino groups exhibit. The amount of the difference between acid groups and amino groups (| ΔSZ-AZ |) is preferably in a range of about 15 to 150, preferably 30 to 100. Acid number and amine number are each defined as mg KOH / g test substance.

It becomes a water-miscible one in the manufacture of the polyurethanes organic solvent used, this can then by conventional methods known to the person skilled in the art, e.g. B. by De Stillation at reduced pressure, are removed. Before the Ab water can separate the solvent from the polyurethane be admitted. After replacing the solvent with water, er one holds a solution or dispersion of the polymer from which, if desired, the polymer can be obtained in the usual way, z. B. by spray drying.

The polymers according to the invention have siloxane groups. Before preferably the amount based on the total weight of the built-in comm component-related siloxane content about 0.05 to 30 wt .-% before added 0.05 to 25% by weight, in particular 0.1 to 20% by weight. Your K- Values (measured according to E. Fikentscher, Cellulose-Chemie 13 (1932), Pp. 58-64, on a small solution in ethanol) are in general nen in a range from about 15 to 90, preferably 20 to 60. Their glass transition temperature is generally at least 0 ° C, preferably at least 20 ° C, particularly preferably at least at least 25 ° C and especially at least 30 ° C. Show the invention corresponding polymers have two or more glass transition temperatures, so at least one of them is in the specified range. Before the other (s) is / are then below the previously indicated temperature range.

The polymers according to the invention are used as auxiliaries in the cosme tics and pharmacy, in particular as or in coating with tel (n) for surfaces containing keratin (hair, skin and nails) and as coating agents and / or binders for solid dosage forms useful. They are also used as or in coating agent (s) for the textile, paper, printing, leather and adhesive industries useful. They are particularly useful in hair cosmetics. The aforementioned polymers can also be used in creams and as Ta tablet coating agents and tablet binders can be used. They are also suitable as binders and adhesives for cosmetics cal products, e.g. B. in the production of pen-shaped cosmetics shear products, such as deodorant sticks, make-up sticks, etc.

The present invention also relates to a cosmetic one or pharmaceutical agent containing the polymers according to the invention contains. In general, the agent contains the polymers in one Amount in the range from 0.2 to 30% by weight, based on the total amount weight of the agent.

The cosmetic agents according to the invention are particularly suitable others as coating agents for surfaces containing keratin (Hair, skin and nails). The ones used in them, if necessary neutralized or quaternized compounds are water-soluble Lich or water dispersible. Are those in the invention Agents used compounds water-dispersible, they can in the form of aqueous microdispersions with particle diameters from usually 1 to 250 nm, preferably 1 to 150 nm, to the An turn around. The solids content of the preparations was genes usually in a range from about 0.5 to 20% by weight, preferably 1 to 12% by weight. These microdispersions be usually do not require emulsifiers or surfactants for their Sta bilization.

The agents according to the invention can preferably be in the form of a hair treatment agent, such as a mousse, hair mousse, hair gel, shampoo and, in particular, in the form of a hairspray. For use as hair setting agents, compositions are preferred which contain poly urethanes which have at least one glass transition temperature T _g 20 ° C, preferably ≧ 30 ° C. The K value of these polymers is preferably in a range from 23 to 90, in particular 25 to 60. The siloxane content of these polymers is generally from 0.05 to 20% by weight, based on the total weight of the built-in components.

It is preferably a hair treatment agent. This lie gen usually in the form of an aqueous dispersion or in the form an alcoholic or aqueous-alcoholic solution. At Suitable alcohols are ethanol, propanol, isopropanol Etc.

The hair treatment agents according to the invention also contain im General customary cosmetic auxiliaries, for example Plasticizers like. Glycerin and glycol; Emollients; Perfumes; UV absorber; Dyes; antistatic agents; Means of verb enhancement of combability; Preservatives; and defoamer.

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

The polyurethanes described above can also be used in the compositions in combination with other hair polymers. Such polymers are in particular:

• - non-ionic, water-soluble or water-dispersible Polymers or oligomers such as polyvinyl caprolactam e.g. B. Lu viskol Plus (BASF), or polyvinylpyrrolidone and their copo lpolymer, especially with vinyl esters such as vinyl acetate, e.g. B. Luviskol VA 37 (BASF); Polyamides, e.g. B. based on Itacon acid and aliphatic diamines;
• - amphoteric or zwitterionic polymers, such as those under Amphomer® (National Starch) available Octyl acrylamide / methyl methacrylate / tert-butylaminoethyl methacryl lat / 2-hydroxypropyl methacrylate copolymers and zwitterioni cal polymers, such as those found in German Patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 are disclosed. Acrylamidopropyl trimethyl ammonium chloride / acrylic acid or methacrylic acid copolymers Sates and their alkali and ammonium salts are preferred zwitterionic polymers. Also suitable zwitterionic ones Polymers are methacroylethyl betaine / methacrylate copolymers, those under the name Amersette® (AMERCHOL) in the trade are available, and copolymers of hydroxyethyl methacrylate, Methyl methacrylate, N, N-dimethylaminoethyl methacrylate and Acrylic acid (Jordapon®);
• - anionic polymers such as vinyl acetate / crotonic acid copolymers, as they are, for example, under the names Resyn® (NATIO NAL STARCH), Luviset® (BASF) and Gafset® (GAF) in stores vinyl pyrrolidone / vinyl acrylate copolymers are available for example under the trademark Luviflex® (BASF). A the preferred polymer is that under the name Luviflex® VBM-35 (BASF) available vinylpyrrolidone / acrylate terpolymer, Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers, for example under the name Ultrahold® strong (BASF), as well as Luvimer® (BASF, Terpolymer from t-butyl acrylate, ethyl acrylate and methacrylic acid), or
• - cationic (quaternized) polymers, e.g. B. Cationic Po lyacrylate copolymers based on N-vinyl lactams and their Derivatives (N-vinylpyrrolidone, N-vinylcaprolactam etc.) as well as common cationic hair conditioner polymers, e.g. B. Luviquat® (Copolymer of vinylpyrrolidone and vinylimidazolium methochlo rid), Luviquat® Hold (copolymer of quaternized N-Vi nylimidazole, N-vinylpyrrolidone and N-vinylcaprolactam), Mer quat® (polymer based on dimethyldiallylammonium chloride), Gafquat® (quaternary polymers produced by the reaction of Polyvi nylpyrrolidone with quaternary ammonium compounds was formed hen), polymer JR (hydroxyethyl cellulose with cationic Groups), polyquaternium types (CTFA designations) etc .;
• - non-ionic, siloxane-containing, water-soluble or dispersible yawable polymers, e.g. B. polyether siloxanes such as Tegopren® (Goldschmidt) or Belsil® (Wacker).

The polymers according to the invention can be used as a mixture with a their amide group-containing hair polymer used. These include z. B. the polyurethanes described in DE-A-42 25 045, the previously described vinyl pyrrolidone / acrylate terpolymers and Acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers (e.g. Ultrahold® strong from BASF AG), the amidgrup described above pen-containing amphoteric polymers (e.g. Amphomer®) and in particular other copolymers that contain a proportion of amide-containing Mo have nomers, such as N-vinyl lactams, of at least 30% by weight (e.g. Luviskol®plus and Luviskol®VA37 from BASF AG).

The polymers according to the invention can also be used as a mixture with a other hair polymers containing siloxane groups are used, preferably siloxane-containing polyurethanes.

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

A preferred hair treatment agent contains:

• a) 0.5 to 20 wt .-% of at least one, soluble in water or dispersible polymer according to the invention,
• b) 30 to 99.5% by weight, preferably 40 to 99% by weight, of a solvent selected from water and water-miscible solvents, preferably C ₂ to C ₅ alcohols, in particular ethanol, and mixtures thereof,
• c) 0 to 70% by weight of a propellant, preferably dimethyl ther,
• d) 0 to 10 wt .-% of at least one of a) different, in Water soluble or dispersible hair polymer,
• e) 0 to 0.3% by weight of at least one water-insoluble silicone,
• f) 0 to 1% by weight of at least one nonionic, siloxane content gene, water-soluble or dispersible polymer,

as well as common additives.

The agent according to the invention can as component d) at least one other hair polymer that is soluble or dispersible in water contain. The proportion of this component is then in general nen about 0.1 to 10 wt .-%, based on the total weight of the Means. Water-soluble or water-dispersible can thereby be preferred yawable polyurethanes are used, the siloxane groups polymerized included.

The agent according to the invention can be used as component e) at least one water-insoluble silicone, especially a polydimethylsiloxane, z. B. contain the Abil® types from Goldschmidt. The amount this component is then generally about 0.0001 to 0.2% by weight, preferably 0.001 to 0.1% by weight, based on the Ge total weight of the remedy.

The agent according to the invention can be used as component f) at least one non-ionic, siloxane-containing, water-soluble or dispersible yawable polymer, in particular selected from the above be written polyether siloxanes. The proportion of this com component is then generally about 0.001 to 2% by weight, be drew on the total weight of the agent.

The agent according to the invention can optionally also have a Defoamers, e.g. B. on a silicone basis included. The amount of Defoamer is generally up to about 0.001% by weight, be pulled on the total amount of the agent.

The agents according to the invention have the advantage that they ei On the one hand, give the hair the desired strength and on the other on the other hand, the polymers are easily washable (redispersible). In addition, hair treatment agents with an in VOC content of less than 85% by weight, preferably less than 60% by weight, and also produce purely aqueous formulations, even if they are formulated as a hairspray.

The invention will be based on the following non-limiting ones Examples explained in more detail.

Examples Urethane (meth) acrylate manufacture

To produce the urethane (meth) acrylates of the following Table 1, which contain hydroxyl-containing components built in (Example 2: neopentyl glycol, Example 4: dimethylolpropanoic acid), a four-necked flask equipped with a stirrer, dropping funnel, thermometer, reflux condenser and a device for working Was equipped under nitrogen, the hydroxyl-containing component in an amount according to Table 1 in acetone (Solid content of the resulting reaction solution about 80%) and heated to a temperature of 60 ° C with stirring. Isophorone diisocyanate was then added dropwise with stirring in an amount according to Table 1, the reaction temperature rising. The reaction mixture was then stirred at reflux until the isocyanate group content of the mixture remained practically constant and then cooled to room temperature with stirring. _{A polysiloxane diamine (M n} = 900 g / mol, Tegomer® A Si 2122 from Goldschmidt) and tert-butylaminoethyl methacrylate (in the form of a 50% strength by weight solution in acetone) were then added at a temperature of about 30.degree ) in an amount according to Table 1 to the polyurethane prepolymers prepared as described above. The mixture was then stirred for a further 20 minutes at about 50 ° C. and then a polyethylene glycol diamine (O, O'-bis (2-aminopropyl) polyethylene glycol 800, M _n = 900 g / mol from Fluka, in the form of a 70% solution in ethanol) was added. The reaction mixture was then stirred at 30 ° C. for a further 30 minutes.

To produce the urethane (meth) acrylates which do not contain any hydroxyl group-containing components incorporated (Examples 1, 3 and 5), a mixture of a polysiloxane diamine (Examples 1 and 3: M _n = 900 g / mol; Example 5: M _n = 2800 g / mol), tert-butyla minoethyl methacrylate (in the form of a 50% strength by weight solution in acetone) and optionally N-methyldipropylenetriamine (Example 3) in an amount according to Table 1 in the apparatus described above and heated to about 30 ° C with stirring. Isophorone diisocyanate was then added dropwise with stirring in an amount according to Table 1, and the reaction mixture was then stirred at a temperature of about 30 ° C. until the isocyanate group content remained practically constant. Then a polyethylene glycol was also added in an amount according to Table 1 at room temperature and the reaction mixture was stirred for a further 30 minutes at about 30.degree. Finally, the reaction mixture was diluted to 50% by weight with ethanol in all cases.

Table 1

Examples 6-19

Inlet 1
220 g of monomer mixture according to Table 2

Inlet 2
0.5 g of tert-butyl perpivalate
100 g of ethanol

Inlet 3
1.5 g tert-butyl perpivalate
82 g of ethanol

In a stirred apparatus with a reflux condenser and two separate feed Running devices were 44 g of feed 1 under a nitrogen atmosphere and 12 g of feed 2 in 120 g of ethanol and stirred up heated to about 80 ° C. After the initial polymerization, recognizable by a incipient increase in viscosity, the remainder of feed 1 in within 4 hours and the rest of feed 2 within 5 Hours added, the internal temperature to about 70 to 80 ° C was held. Then left for a further 2 hours React temperature of about 75 to 80 ° C and then added 3 within 2 hours. After the addition was finished polymerized for about 4 hours at this temperature. Then The acid group-containing polymers were ßend with a base according to Table 2 and the amine group-containing polymers with a Acid neutralized. The K values and degrees of neutralization of the Po Polymers are also given in Table 2.

Polymers based on nonionic components or based on urethane (meth) acrylates which already have neutralized or quaternized groups can generally be used directly for the formulation of hair preparations.

Application examples Examples 20 to 33

Aerosol hairspray formulations with a VOC content of 97% by weight:

Polymer according to Example 6-19 3.00 wt% Ethanol 62.00 wt% Dimethyl ether 34.96 wt% Perfume, additives q.s.

Examples 34 to 40

Compact aerosol hairspray formulations with a VOC content of 90% by weight:

Polymer according to Example 7, 8, 13, 16-19 10.00 wt% Ethanol 55.00 wt% Dimethyl ether 34.96 wt% Perfume, additives q.s.

Examples 41 to 54

Hairspray formulations with a VOC content of 80% by weight:

Polymer according to Example 6-19 5.00 wt% Ethanol 45.00 wt% water 15.00 wt% Dimethyl ether 34.96 wt% Perfume, additives q.s.

Examples 55 to 68

Hairspray formulations with a VOC content of 55% by weight:

Polmer according to Example 6-19 3.00 wt% Ethanol 20.00 wt% water 42.00 wt% Dimethyl ether 34.96 wt% Perfume, additives q.s.

Examples 69 to 75

Pump hairspray formulations with a VOC content of 55% by weight:

Polymer according to Example 7, 8, 13, 16-19 10.00 wt% water 37.00 wt% Ethanol 55.00 wt% Perfume, additives q.s.

Claims (11)

1. Radically polymerizable, siloxane-containing urethane (meth) acrylates, the

• a) at least one compound which contains at least one active hydrogen atom and at least one radically polymerizable, α, β-ethylenically unsaturated double bond per molecule,
• b) at least one diisocyanate,
• c) at least one compound which contains two active hydrogen atoms per molecule,
• d) at least one compound which contains at least one active hydrogen atom and at least one siloxane group per molecule,

incorporated, and the salts thereof. 2. Urethane (meth) acrylates according to claim 1, which additionally have at least one component selected from

• a) compounds which contain two or more active hydrogen atoms and at least one ionogenic and / or ionic group per molecule,
• b) monohydric alcohols, amines with a primary or secondary amino group, aliphatic, cycloaliphatic or aromatic monoisocyanates and mixtures thereof,
• c) α, β-ethylenically unsaturated compounds which additionally contain at least one isocyanate group per molecule,

and mixtures thereof incorporated therein. 3. Urethane (meth) acrylates according to one of claims 1 or 2, where in component d) is selected from:

• 1. Polysiloxanes of the general formula I.1
  wherein
  a and b independently represent 2 to 8,
  c stands for 3 to 100,
  R ¹ and R ² independently of one another represent C ₁ - to C ₈ -alkyl, benzyl or phenyl,
  Z ¹ and Z ² independently of one another represent OH, NHR ³ or a radical of the formula II
  - (CH ₂ CH ₂ O) _v (CH ₂ CH (CH ₃ ) O) _w -H (II)
  stand, where
  in formula II, the sequence of the Alkylenoxidein units is arbitrary and
  v and w independently represent an integer from 0 to 200, where the sum of v and w <0,
  R ^{3 represents} hydrogen, C ₁ to C ₈ alkyl or C ₅ to C ₈ cycloalkyl;
• 2. Polysiloxanes of the general formula I.2
  wherein
  the order of the siloxane units is arbitrary,
  d and e stand independently of one another for 0 to 100, where the sum of d and e is at least 2,
  f stands for an integer from 2 to 8,
  Z ^{3 represents} OH, NHR ³ or a radical of the formula II,

and mixtures thereof. 4. Water-soluble or water-dispersible polymer that we At least one urethane (meth) acrylate according to one of Claims 1 up to 3 and at least one radically polymerizable, α, β- ethylenically unsaturated monomer M) polymerized ent holds. 5. Polymer according to claim 4, wherein the monomer M) is selected from

• 1. Essentially hydrophobic, nonionic compounds, preferably esters of α, β-ethylenically unsaturated mono- and / or dicarboxylic acids with C ₁ -C ₃₀ alkanols, amides of α, β-ethylenically unsaturated mono- and / or dicarboxylic acids with mono- and Di-C ₁ -C ₃₀ alkylamines, esters of vinyl alcohol and allyl alcohol with C ₁ -C ₃₀ monocarboxylic acids, vinyl ethers, vinyl aromatics, vinyl halides, vinylidene halides, C ₂ -C ₈ monoolefins, non-aromatic hydrocarbons with at least 2 conjugated double bonds and mixtures of that,
• 2. Compounds with a radically polymerizable, α, β-ethylenically unsaturated double bond and at least one ionogenic and / or ionic group per mole kül,
• 3. Essentially hydrophilic, nonionic compounds, preferably N-vinylamides, N-vinyllactams, primary amides of α, β-ethylenically unsaturated monocarboxylic acids, vinyl- and allyl-substituted heteroaromatic compounds, esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₁ -C ₃₀ alkanediols, esters and amides α, β-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C ₃₀ amino alcohols which have a primary or secondary amino group, polyether acrylates, and mixtures thereof,

and mixtures thereof. 6. Polymer according to any one of claims 4 or 5, the

• 1. 0.05 to 80% by weight, preferably 0.1 to 50% by weight, at least least of a urethane (meth) acrylate, as defined in one of claims 1 to 3,
• 2. 20 to 99.95% by weight, preferably 50 to 99.9% by weight, at least one component M),

contains polymerized. 7. Polymer according to any one of claims 4 to 6, the

• 1. 0.1 to 50% by weight, preferably 0.5 to 35% by weight, at least least of a urethane (meth) acrylate, as defined in one of claims 1 to 3,
• 2. 40 to 75% by weight, preferably 45 to 73% by weight, of at least one component M1),
• 3. 10 to 35% by weight, preferably 18 to 30% by weight, of at least one component M2),
• 4. 0 to 30% by weight, at least one component M3),

contains polymerized. 8. Polymer according to any one of claims 4 to 6, the

• 1. 0.1 to 50% by weight, preferably 0.5 to 35% by weight, at least least of a urethane (meth) acrylate, as defined in one of claims 1 to 3,
• 2. 0 to 50% by weight of at least one component M1),
• 3. 0 to 20% by weight, at least one component M2),
• 4. 25 to 80% by weight, at least one component M3),

contains polymerized. 9. Cosmetic or pharmaceutical agent, preferably in the form of a hair treatment agent which contains at least one polymer according to any one of claims 4 to 8 contains. 10. Hair treatment agent according to claim 9, containing

• a) 0.5 to 20% by weight of at least one water-soluble or dispersible polymer as defined in one of claims 4 to 6,
• b) 30 to 99.5% by weight, preferably 40 to 99% by weight, at least one solvent selected from water, which is miscible solvents and mixtures thereof,
• c) 0 to 70% by weight of a propellant,
• d) 0 to 10% by weight of at least one of a) different, water-soluble or water-dispersible hair polymer,
• e) 0 to 0.3% by weight of at least one water-insoluble silicone,
• f) 0 to 1 wt .-% of at least one nonionic, siloxane-containing, water-soluble or dispersible polymer.

11. Use of the polymers as in any one of claims 4 to 8 defined, as an aid in cosmetics, preferably in the Hair cosmetics, especially as setting polymers in hair sprays, Mousse, hair mousse, hair gel and shampoos, in the Pharmacy, preferably in coating agents or binders materials for solid dosage forms, as well as in coating agents for the textile, paper, printing, leather and adhesive industry strie.