WO2008053051A2 - Panthenol esters of unsaturated carboxylic acids - Google Patents

Abstract

The invention relates to esters of panthenol with α,β-monoethylenically unsaturated carboxylic acids which can be prepared by transesterification in the presence of a hydrolase. The esters are useful as comonomers in the production of copolymers which exhibit the properties of panthenol and can be used in cosmetics and pharmacy.

Description

 Panthenol esters of unsaturated carboxylic acids

description

The present invention relates to panthenol esters of unsaturated carboxylic acids and to copolymers which comprise units of these esters in copolymerized form and to the use of the copolymers in cosmetics and pharmacy.

Panthenol has advantageous cosmetic properties and is therefore often used in cosmetic products, such as creams, after-shave balm, body lotions, sun creams, hair fixatives or hair conditioners. It improves the properties and in particular the appearance of the skin and hair, because it moisturizes and improves the hair structure and the shine of the hair. Products having advantageous cosmetic properties are frequently used as constituents of polymers used in cosmetics. A prerequisite for this is that monomers are known which contain the product bound with the advantageous properties and which can be copolymerized with the customary polymers used with cosmetics, such as polyalkyl acrylates or methacrylates or poly (vinylpyrrolidones). The advantageous properties of the cosmetic product therefore remain as a rule preserved. In general, even an improvement of these properties can be noted, because the products can no longer be volatile and adhere better to the skin and hair and thus can develop their effect longer and more intensively.

(Racemic) Panthenol has the structural formula

It has two primary hydroxyl groups of different reactivity, with the sterically unshielded hydroxyl group (right in the formula) being more reactive than the other primary hydroxyl group. The secondary hydroxyl group has the lowest reactivity. When esterifying panthenol in the usual way, for example by reaction with an acid chloride or using conventional esterification catalysts, in general, the two primary hydroxyl groups and optionally also the secondary hydroxyl group esterified, ie one obtains the diester and / or the triester, see Arzneimittelforschung 1967, 17, 1 122-1125. In addition, panthenol at temperatures above 70 ⁰ C, as required for conventional esterifications, not stable. There is a decomposition in aminopropanol and pantolactone and racemization is observed when using enantiomerically pure panthenol. The production of panthenol monoesters has so far been just as such as esters of panthenol with polymerizable unsaturated carboxylic acids which would allow to copolymerize panthenol into a copolymer.

It is therefore an object of the present invention to provide panthenol esters which are copolymerizable with the monomers used to prepare conventional cosmetic polymers.

Surprisingly, it has now been found that panthenol can be esterified selectively to polymerizable monoesters or diesters by enzymatic transesterification.

The present invention therefore relates to esters of panthenol with α, ß-monoethylenically unsaturated Cs-Cs carboxylic acids. Preferably, these are the monoesters of the formula

or the diesters of the formula

wherein R ^{1 represents} the acyl radical of an α, ß-monoethylenically unsaturated Cs-Cs-carboxylic acid. Suitable α, ß-ethylenically unsaturated carboxylic acids for the preparation of monoesters or diesters of panthenol are monocarboxylic acids, dicarboxylic acids and half esters of dicarboxylic acid. The alcohol component of the half-esters of dicarboxylic acids are preferably C 1 -C -alkanols, especially C 1 -C 4 -alkanols. The α, β-ethylenically unsaturated carboxylic acids are preferably selected from acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, methylmaleic acid, methylfumaric acid, dimethylmaleic acid or methylenemalonic acid or the C 1 -C 4 -alkyl esters of the abovementioned dicarboxylic acids. Particularly preferred are acrylic acid and methacrylic acid. In the formulas Ia and Ib R ¹ therefore represents the acyl radicals of the acids mentioned.

In the context of the present invention, the term alkyl includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched Ci-Cz-alkyl, preferably Ci-Cε-alkyl and particularly preferably Ci-C4-alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,3-dimethylbutyl, 1, 1-dimethylbutyl, 2, 2-dimethylbutyl, 3,3-dimethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 2-ethylpentyl, 1-propylbutyl, octyl, etc.

Branched C3-Cs-alkyl is preferably isopropyl, isobutyl, sec-butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl,

1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl. Preference is given to tert-butyl.

Suitable longer-chain Cs-Cso-alkyl or Cs-Cso-alkenyl groups are straight-chain and branched alkyl or alkenyl groups. Preference is given to predominantly linear alkyl radicals, as also occur in natural or synthetic fatty acids and fatty alcohols and oxoalcohols, which may optionally be additionally mono-, di- or polyunsaturated. These include z. N-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl , n-tridecyl (s), n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, Arachynyl (s), behenyl (s), lignocerinyl (s), melisinyl (s), etc.

Cycloalkyl is preferably Cs-Cβ-cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Aryl includes unsubstituted and substituted aryl groups and is preferably phenyl, ToIyI, XyIyI, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl, ToIyI, XyIyI or mesityl.

Hereinafter, compounds derived from acrylic acid and methacrylic acid are sometimes abbreviated by inserting the syllable "(meth)" in the compound derived from the acrylic acid.

The esters of the panthenol according to the invention are more preferably panthenol monoacrylate of the formula

Panthenol monomethacrylate of the formula

Panthenol diacrylate of the formula

or panthenol dimethacrylate of the formula

or combinations of compounds Ic through If.

The esters according to the invention may be the esters of racemic panthenol, (R) -panthenol, (S) -benzene or of mixtures of (R) - and (S) -panthenol in which (R) - or (S ) -Panthenol is present in excess.

The preparation of the panthenol esters according to the invention can be carried out by transesterification of racemic or enantionmeren enriched or enantiomerically pure (R) - or (S) -panthenol with an ester of the aforementioned α, ß-monoethylenically unsaturated Cs-Cs carboxylic acids. Preferably, a C 1 -C 4 -alkyl ester is used for transesterification. It is expedient to use the corresponding methyl ester or ethyl ester. Dicarboxylic acids can be used in the form of their half esters or diesters.

The transesterification takes place in the presence of an enzyme, in particular a hydrolase, according to the following reaction equation, methyl acrylate being used by way of example. lipase

The hydrolases (EC3. -.-.-) used according to the invention are in particular esterases (EC3.1.-.-), lipases (EC3.1.1.3), glycolases (EC3.2.-.-) and Proteases (EC3.4.-.-) in free or on a carrier chemically or physically immobilized form. Preference is given to lipases, esterases or proteases, with esterases being particularly preferred. Especially suitable is Novozyme 435 (lipase from Candida Antarctica B) or lipase from Alkalygenes sp., Aspergillus sp., Mucor sp., Penicillium sp., Geotricum sp., Ricopus sp., Burkholderia sp., Candida sp., Pseudomonas sp. , Thermomyces sp. or porcine pancreas, lipase being obtained from Candida antarctica B or from Burkholderia sp. is particularly preferred. Further examples of useful types of enzymes are described in WO 2004/013123, the disclosure of which is fully incorporated by reference.

The enzyme content in the reaction medium is generally in the range of about 0.1 to 10 wt .-%, in particular 0.5 to 8 wt .-%, based on panthenol.

The reaction time depends, inter alia, on the temperature, the amount used and the activity of the enzyme catalyst and the desired conversion. As a rule, a reaction time in the range of 0.5 to 72 hours, preferably 1 to 36 hours and particularly preferably 2 to 12 hours is sufficient. The enzymatic transesterification is generally carried out at 0 to 80 ^° C., preferably 10 to 70 ^° C., particularly preferably 20 to 60 ^° C. and in particular 20 to 50 ^° C.

The molar ratio of α, β-monoethylenically unsaturated carboxylic acid to panthenol (based on hydroxy groups to be esterified) can be selected within a wide range. Generally, it is in the range of 100: 1 to 1: 1, preferably 50: 1 to 1: 1, more preferably 20: 1 to 1: 1, and most preferably 10: 1 to 1: 1.

The transesterification can be carried out in an organic solvent or a solvent mixture or without the addition of solvent. However, it is preferable to use a solvent.

Suitable organic solvents are in particular tertiary monoalcohols, such as Cs-Cε-alcohols, in particular t-butanol, t-amyl alcohol;

Poly-C 1 -C 4 -alkylene glycol di-C 1 -C 4 -alkyl ethers, such as polyethylene glycol di-C 1 -C 4 -alkyl ethers, for example 1, 2-dimethoxyethane, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether δOO; Ethers, such as methyl t-butyl ether, ethyl t-butyl ether, tetrahydrofuran (THF), dioxane, 1, 3-dioxolane; Ketones, such as acetone, isobutyl methyl ketone, methyl ethyl ketone; Hydrocarbons, such as toluene, xylene, hexane, heptane, cyclohexane, methylcyclohexane, or acetonitrile and their mono- or multiphase mixtures. Preferred solvents are ketones and ethers.

As a rule, the reaction is largely anhydrous (that is to say below 10, preferably below 5, more preferably below 1 and very particularly preferably below 0.5% by weight of water content).

The substrates are generally dissolved, but they may also be suspended as solids or present in emulsion in the reaction medium. Preferably, the initial concentration of reactants is in the range of about 0.1 to 20 mol / l, more preferably 0.15 to 10 mol / l or 0.2 to 5 mol / l.

The reaction can be carried out continuously, for example in a tube reactor or in a stirred reactor cascade, or batchwise using conventional reactors, such as stirred tank reactors or fixed bed reactors.

The removal of the alcohol formed in the transesterification can be carried out in a known manner continuously or stepwise, for example by applying a vacuum, azeotropic removal, absorption, pervaporation and diffusion via suitable semipermeable membranes. Preferably, the separation is carried out by absorption using molecular sieves or zeolites (pore size, for example in the range of about 3 to 10 Ä) by distilling off or using suitable semipermeable membranes. After the reaction has ended, the reaction mixture can be used further without further purification or optionally purified in a further step. For purification, in particular, the enzyme is generally separated by filtration, absorption, centrifugation or decanting. The separation of the organic solvent is generally carried out by distillation, rectification or solid insoluble reaction products by filtration.

Finally, the reaction product can still be purified by chromatography, for example on silica gel. In particular, the panthenolmonoester and the panthenol diester can be separated in this way.

Further information on carrying out the transesterification can be found in WO 2006/005491, the disclosure of which is hereby incorporated by reference in its entirety.

If desired, one can use a polymerization inhibitor in the transesterification. Examples of polymerization inhibitors are hydroquinone monomethyl ether, phenotiacin, phenols such as 2-t-butyl-4-methylphenol, 6-t-butyl-2,4-dimethylphenol or N-oxyls such as 4-hydroxy-2,2,6,6- tetramethylpiperidine-N-oxyl or

4-Oxo-2,2,6,6-tetramethylpiperidine-N-oxyl. The polymerization inhibitor is generally used in amounts of from 50 to 2000 ppm.

The panthenol monoesters or diesters according to the invention can be used as comonomers for the preparation of polymers which are used in cosmetics and pharmacy. The panthenol diesters according to the invention, which have two α, β-ethylenically unsaturated double bonds, can also be used advantageously as crosslinking agents.

Examples of comonomers with which the panthenol monoesters and panthenol diesters can be copolymerized are:

a) esters oφ-ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 20 -alkanols, in particular C ₁ -C 20 -alkyl acrylates and / or C ₁ -C 20 -alkyl methacrylates;

b) compounds having a free-radically polymerizable, α, ß-ethylenically unsaturated double bond and at least one cationogenic and / or cationic groups per molecule; c) compounds having a free-radically polymerizable, α, ß-ethylenically unsaturated double bond and at least one anionogenic and / or anionic group per molecule;

d) esters of vinyl alcohol and allyl alcohol with C 1 -C 30 monocarboxylic acids;

e) vinyl-C 1 -C 20 -alkyl ethers, such as vinyl ethyl ether, vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl octyl ether;

f) primary amides of α, β-ethylenically unsaturated monocarboxylic acids, N-alkyl and N, N-dialkylamides of α, β-ethylenically unsaturated monocarboxylic acids, N-vinylamides of saturated monocarboxylic acids and mixtures thereof;

g) vinyl aromatic compounds such as styrene, vinyl toluene, α-butylstyrene, etc .;

h) N-vinyl lactams;

i) acrylonitrile and / or methacrylonitrile;

j) esters oφ-ethylenically unsaturated mono- and dicarboxylic acids with

C 1 -C 30 -alkanediols, amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 30 -aminoalcohols which have a primary or secondary amino group;

k) non-aromatic hydrocarbons having 2 to 8 C atoms and one or two olefinic double bonds, such as ethylene, propylene, isobutylene, butadiene or isoprene.

Monomer a)

Suitable esters a) are based on α, ß-ethylenically unsaturated mono- and dicarboxylic acids, as listed as component c). Suitable comonomers b) are z. For example, methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl methacrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, n-pentyl (meth) acrylate, n- Hexyl (meth) acrylate, n-heptyl (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, arrachinyl (meth) acrylate, behenyl (meth) acrylate, lignocerenyl (meth) acrylate, cerotinyl (meth) acrylate, melissinyl (meth) acrylate, palmitoleinyl (meth) acrylate, Oleyl (meth) acrylate, linolyl (meth) acrylate, linolenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate and mixtures thereof.

Preferred monomers a) are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and mixtures thereof

The copolymers according to the invention may contain, for example, 1 to 98% by weight, preferably 2 to 90% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer a) in copolymerized form.

Monomer b)

The copolymers according to the invention may contain in copolymerized form as comonomer b) at least one compound having a free-radically polymerizable, .alpha.,. Beta.-ethylenically unsaturated double bond and at least one cationogenic and / or cationic group thereof per molecule.

The copolymers according to the invention may contain, for example, 1 to 98% by weight, preferably 2 to 90% by weight, based on the total weight of the monomers used for the polymerization, of at least one monomer b) in copolymerized form.

If desired, the monomers b) or their copolymerized repeating units can be present in partially or completely protonated and / or quaternized form. Suitable acids for protonation are, for. For example, mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid, and carboxylic acids and hydroxycarboxylic acids such as lactic acid. Suitable quaternizing agents are, for. For example, methyl chloride, methyl bromide, dimethyl sulfate or diethyl sulfate.

Preferably, component b) is selected from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols which may be mono- or dialkylated on the amine nitrogen, amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which contain 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, the quaternization products of these monomers and mixtures thereof.

Suitable compounds b) are also the esters of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols. Preferred amino alcohols are C 2 -C 12 -amino alcohols which are mono- or dialkylated on the amine nitrogen by C 1 -C 8. When Acid component of these esters are suitable for. For example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. The acid component used is preferably acrylic acid, methacrylic acid and mixtures thereof.

Preferred monomers b) are aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminocyclohexyl (meth) acrylate, aminoethyl (meth) acrylamide, aminopropyl (meth) acrylamide, aminocyclohexyl (meth) acrylamide and mixtures thereof.

Preferred monomers b) are N-tert-butylaminoethyl (meth) acrylate,

N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate. Particularly preferred are N-tert-butylaminoethyl (meth) acrylate and N, N-dimethylaminoethyl (meth) acrylate. Preferred monomers b) are, in particular, also the quaternization products of the abovementioned compounds.

Suitable monomers b) are furthermore the amides of the abovementioned α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group. Preferred are diamines having a tertiary and a primary or secondary amino group.

Preferred as monomers b) are z. B. N- [tert -butylaminoethyl (meth) acrylamide, 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. Particularly preferred are N- [3- (dimethylamino) propyl] acrylamide and N- [3- (dimethylamino) propyl] methacrylamide (DMAPMAM).

A specific embodiment relates to copolymers A), which

N- [3- (dimethylamino) propyl] acrylamide and N- [3- (dimethylamino) propyl] methacrylamide in copolymerized form. In a very specific embodiment, the component b) consists only of N- [3- (dimethylamino) propyl] acrylamide and / or N- [3- (dimethylamino) propyl] methacrylamide.

Suitable monomers b) are furthermore N, N-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts and quaternization products. Alkyl is preferably C 1 -C 24 -alkyl. Preference is given to N, N-diallyl-N-methylamine and

N, N-diallyl-N, N-dimethylammonium compounds, such as. As the chlorides and bromides. Particularly preferred is N, N-diallyl-N, N-dimethylammonium chloride (DADMAC). Suitable comonomers b) suitable vinyl- and allyl-substituted nitrogen heterocycles are N-vinylimidazole compounds of the general formula

wherein

R ⁸ to R ¹⁰ independently of one another represent hydrogen, C 1 -C ₄ -alkyl or phenyl.

Examples of N-vinylimidazole compounds b) are shown in the following table:

Me = methyl Ph = phenyl

Preferred monomer b) is 1-vinylimidazole (N-vinylimidazole) and are mixtures containing N-vinylimidazole.

Suitable monomers b) are also the compounds obtainable by protonation or quaternization of the abovementioned N-vinylimidazole compounds. examples for such charged monomers b) are quaternized vinylimidazoles, especially 3-methyl-i-vinylimidazolium chloride, methosulfate and ethosulfate. Suitable acids and alkylating agents are those listed above.

Suitable monomers b) are furthermore vinyl- and allyl-substituted nitrogen heterocycles, other than vinylimidazoles, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.

Preferably, component b) comprises at least one monomer selected from N-vinylimidazole, quaternized N-vinylimidazole, N, N-dimethylaminoethyl (meth) acrylate, quaternized

N, N-dimethylaminoethyl (meth) acrylate, N- [3- (dimethylamino) propyl] (meth) acrylamide, quaternized N- [3- (dimethylamino) propyl] (meth) acrylamide, and mixtures thereof.

Monomer e)

The copolymers according to the invention may contain in copolymerized form at least one comonomer c) in an amount of 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, in particular 1 to 20% by weight.

Preferably, component c) comprises at least one compound selected from monoethylenically unsaturated carboxylic acids, sulfonic acids, phosphonic acids and mixtures thereof.

The monomers c) include monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms, which can also be used in the form of their salts or anhydrides. Examples thereof are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid. The monomers c) furthermore include the half-esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, eg. B. of maleic acid such as monomethyl maleate. The monomers c) also include monoethylenically unsaturated sulfonic acids and phosphonic acids, for example vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid, Acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid and allylphosphonic acid. The monomers c) also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts and the salts with amines. The monomers c) can be used as such or as mixtures with one another. The stated proportions by weight are all based on the acid form. Component c) preferably comprises at least one compound selected from acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, 2-acrylamido-2-one methylpropanesulfonic acid, vinylphosphonic acid and mixtures thereof.

In particular, component c) comprises at least one compound selected from acrylic acid, methacrylic acid and mixtures thereof.

Monomer d)

Suitable additional comonomers d) are, for. Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate and mixtures thereof.

Monomer f)

Suitable monomers f) are furthermore acrylamide and methacrylamide.

Suitable N-alkyl and N, N-dialkylamides of .alpha.,. Beta.-ethylenically unsaturated monocarboxylic acids are, for example, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide,

N-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide, N-tert-butyl (meth) acrylamide, n-pentyl (meth) acrylamide, n-hexyl (meth) acrylamide, n-heptyl ( meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, piperidinyl (meth) acrylamide, morpholinyl (meth) acrylamide, n-octyl (meth) acrylamide, 1, 1, 3, 3-tetramethylbutyl (meth) acrylamide, ethylhexyl (meth) acrylamide, n-nonyl (meth) acrylamide, n-decyl (meth) acrylamide, n-undecyl (meth) acrylamide, tridecyl (meth) acrylamide, myristyl (meth) acrylamide, Pentadecyl (meth) acrylamide, palmityl (meth) acrylamide, heptadecyl (meth) acrylamide, nonadecyl (meth) acrylamide, arrachinyl (meth) acrylamide, behenyl (meth) acrylamide, lignocerenyl (meth) acrylamide, cerotinyl (meth) acrylamide, melissinyl ( meth) acrylamide, palmitoleinyl (meth) acrylamide, oleyl (meth) acrylamide, linolyl (meth) acrylamide, linolenyl (meth) acrylamide, stearyl (meth) acrylamide, lauryl (meth) acrylamide, N-methyl-N- (n-octyl ) (meth) acrylamide, N, N-di (n-octyl) (meth) acrylamide and mixtures thereof.

Examples of open-chain N-vinylamide compounds suitable as monomers f) are N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl N-methylpropionamide, N-vinyl-butyramide and mixtures thereof. Preference is given to using N-vinylformamide. The copolymers of the invention may, for. B. 0.1 to 99 wt .-%, preferably 0.5 to 95 wt .-%, based on the total weight of the compounds used for the polymerization, at least one monomer f) in copolymerized form.

Monomer h)

Suitable comonomers h) are N-vinyllactams and derivatives thereof, the z. Example, one or more alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. may have. These include z. 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.

Particular preference is given to using N-vinylpyrrolidone and / or N-vinylcaprolactam.

The copolymers of the invention may, for. B. 1 to 99 wt .-%, preferably 5 to 95 wt .-%, based on the total weight of the compounds used for the polymerization, at least one monomer h) in copolymerized form.

Monomer j)

Suitable comonomers j) are hydroxy-C 1 -C 20 -alkyl (meth) acrylates. These include

2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate,

3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate,

4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate,

6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate and

3-hydroxy-2-ethylhexyl methacrylate.

Suitable comonomers j) are furthermore hydroxy-C 1 -C 20 -alkyl (meth) acrylamides. These include 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide,

2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide,

2-hydroxypropylmethacrylamide, 3-hydroxypropylacrylamide, 3-hydroxypropylmethacrylamide, 3-hydroxybutylacrylamide,

3-hydroxybutylmethacrylamide, 4-hydroxybutylacrylamide,

4-hydroxybutylmethacrylamide, 6-hydroxyhexylacrylamide,

6-hydroxyhexylmethacrylamide, 3-hydroxy-2-ethylhexylacrylamide and

3-hydroxy-2-ethylhexylmethacrylamid.

The abovementioned monomers a) to k) can each be used as sole comonomers or in the form of any desired mixtures. The proportion of panthenol monoester in the monomer mixture to be polymerized is generally 0.1 to 6 wt .-%, based on the total weight of the monomers, when polymerized in an aqueous phase. On the other hand, when using a solution polymerization (precipitation polymerization), the panthenol monoester may be present in an amount of from 0.1 to 20% by weight, in particular from 0.5 to 15% by weight.

A first preferred embodiment are copolymers consisting of repeating units of

Panthenol acrylate, at least one compound selected from N, N-dimethylaminoethyl (meth) acrylate, N- [3- (dimethylamino) propyl] (meth) acrylamide, N- (tert-butyl) aminoethyl (meth) acrylate, N Vinylimidazole and mixtures thereof,

N-vinylpyrrolidone and / or N-vinylcaprolactam,

consist.

According to the first preferred embodiment, at least some of the cationic monomers are quaternized.

Particular preference is given to copolymers which consist of repeating units of

Panthenol acrylate, N-vinylimidazole, N-vinylpyrrolidone and / or N-vinylcaprolactam,

exist, wherein the N-vinylimidazole may be partially or completely quaternized.

A second preferred embodiment is copolymers consisting of repeating units of

Panthenol acrylate, - at least one compound chosen from

N, N-dimethylaminoethyl (meth) acrylate,

N- [3- (dimethylamino) propyl] (meth) acrylamide,

N- (tert-butyl) aminoethyl (meth) acrylate, N-vinylimidazole and mixtures thereof, at least one crosslinking monomer having two α, β-ethylenically unsaturated double bonds per molecule,

consist. In the second preferred embodiment, at least a portion of the cationic monomers are quaternized.

Particular preference is given to copolymers which consist of repeating units of

Panthenol acrylate, N-vinylimidazole, pentaerythritol triallyl ether,

exist, wherein the N-vinylimidazole may be partially or completely quaternized.

The copolymers can be prepared by customary polymerization processes, for example by free-radical solution, precipitation, suspension or emulsion polymerization. Also suitable is W / W polymerization in water with a suitable displacer, for example a polymer such as polyacrylic acid or a salt such as NaCl. The solution polymerization is advantageously carried out so that the polymer precipitates out of the chosen solvent during and / or at the end of the reaction and can be recovered, for example, by filtration. Suitable solvents are alkanols, such as methanol, ethanol, n-propanol,

Isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol; Esters, such as butyl acetate; Ethyl acetate, glycols such as ethylene glycol, propylene glycol and butylene glycol; Ethers, such as methyl or ethyl ethers of diethylene glycol, triethylene glycol, polyethylene glycol and glycerol, and dioxane.

The solution polymerization or precipitation polymerization can be carried out in the presence of at least one polyether-containing compound which has no copolymerizable double bond. Suitable polyether-containing compounds are, for example, polyalkylene glycols which generally have a number average molecular weight in the range from about 150 to 100,000, preferably 300 to 50,000, in particular 500 to 40,000. Examples of polyalkylene glycols are polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers (the alkylene oxide units may be randomly distributed or in the form of blocks). Suitable alkylene oxide copolymers are, for example, copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, etc. A suitable polyether-containing compound is, for example, Pluriol E 9000.

The polymerization temperature is generally in the range from about 30 ^° C. to about 120 ^° C., preferably from about 40 ^° C. to about 100 ^° C.

The precipitation polymerization is preferably carried out in a substantially anhydrous, aprotic solvent or solvent mixture, preferably an ester, such as Ethyl acetate and / or n-butyl acetate. Substantially anhydrous in this context means a solvent or a solvent mixture having a water content of at most 5% by weight.

The polymerization takes place with the aid of free-radical initiators. Suitable initiators are the customary peroxo and / or azo compounds, for example alkali or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, azo-bis-isobutyronitrile, azobis (2-amidinopropane) dihydrochloride or 2,2'-azo bis- (2-methylbutyronitrile). Also suitable are initiator mixtures or redox initiator systems, such as ascorbic acid / iron (II) sulfate / sodium peroxodisulfate.

The polymerization can also be carried out in the presence of customary crosslinking agents. Suitable crosslinking agents are, for example, divinylbenzene, allyl acrylate, allyl methacrylate, triallylamine, pentaerythrityl triallyl ether, tetraallylsilane, tetravinylsilane, etc. Also suitable as crosslinking agents are the panthenol diesters according to the invention. The preparation of the panthenol esters can be controlled by higher temperature and longer reaction time so that the Panthenoldiester is formed in a proportion of 0.5 to 5%. The mixture of panthenol monoester and panthenol diester can then be used as crosslinking agent-containing comonomer for the polymerization.

The copolymers obtainable according to the invention have the advantageous properties of panthenol. They improve the appearance of the skin and hair by improving the hair structure, giving it shine and moisturizing. They also help to improve the combability of the hair. The copolymers are therefore suitable as an additive to creams, after-shave balm, body lotions, hair gels, skincare emulsions, hair fixatives or hair rinses. In general, they are used in concentrations of 0.1 to 5 wt .-%, based on the total weight of the cosmetic product.

The polymers according to the invention can also be used in pharmacy. Panthenol is known to be useful in the treatment of skin conditions such as dermatoses, burns, infectious ulcer, etc. Since the copolymers of the present invention have the properties of panthenol, they can also be used as a component of pharmaceutical compositions for the treatment of said disorders.

Another object of the invention is a cosmetic or pharmaceutical agent containing

A) at least one copolymer comprising at least one panthenol ester in a polymerized form as defined above, and B) at least one cosmetically or pharmaceutically acceptable carrier.

The compositions according to the invention preferably have a cosmetically or pharmaceutically acceptable carrier B) which is selected from

i) water, ii) water-miscible organic solvents, preferably C 2 -C 4 alkanols, in particular ethanol, iii) oils, fats, waxes, iv) of iii) various esters of C 6 -C 50 monocarboxylic acids with monohydric, dihydric or trihydric alcohols , v) saturated acyclic and cyclic hydrocarbons, vi) fatty acids, vii) fatty alcohols, viii) propellants,

and mixtures thereof.

The inventive compositions have z. An oil or fat component B) selected from: low polarity hydrocarbons such as mineral oils; linear saturated hydrocarbons, preferably having more than 8 C atoms, such as tetradecane, hexadecane, octadecane, etc .; cyclic hydrocarbons, such as decahydronaphthalene; branched hydrocarbons; animal and vegetable oils; To grow; Wax esters; Petroleum jelly; Esters, preferably esters of fatty acids, such as. For example, the esters of C 1 -C 24 -monoalcohols with C 1 -C 22 -monocarboxylic acids, such as isopropyl isostearate, n-propyl myristate, isopropyl myristate, n-propyl palmitate, isopropyl palmitate, hexacosanyl palmitate, octacosanyl palmitate, triacontanyl palmitate, dotriacontanyl palmitate, tetrato- acontanyl palmitate, hexancosanyl stearate, octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, tetratriacontanyl stearate; Salicylates, such as Ci-Cio-salicylates, z. Octyl salicylate; Benzoate esters, such as cio-cis alkyl benzoates, benzyl benzoate; other cosmetic esters, such as fatty acid triglycerides, propylene glycol monolaurate, polyethylene glycol monolaurate, C 10 -C 16 -alkyl lactates, etc., and mixtures thereof.

Suitable silicone oils B) are z. As 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 of about 1,000 to 150,000 g / mol. Preferred cyclic siloxanes have 4- to 8-membered rings. Suitable cyclic siloxanes are, for. B. under the name cyclomethicone commercially available.

Preferred oil or fat components B) are selected from paraffin, isoparaffin, paraffin oils and isoparaffin oils; Petroleum jelly; natural fats and oils, such as castor oil, Soybean oil, peanut oil, olive oil, sunflower oil, sesame oil, avocado oil, cocoa butter, almond oil, peach kernel oil, castor oil, cod liver oil, lard, spermaceti, sperm oil, sperm oil, wheat germ oil, macadamia nut oil, evening primrose oil, jojoba oil; Fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cetyl alcohol; Fatty acids 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, spermaceti and mixtures of the aforementioned oil or fat components.

Suitable cosmetically and pharmaceutically acceptable oil or fat components B) are described in Karl-Heinz Schrader, Grundlagen und Rezepturen der Kosmetika, 2nd edition, Verlag Hüthig, Heidelberg, pp. 319-355, to which reference is made here.

Suitable hydrophilic carriers B) are selected from water, mono-, di- or polyhydric alcohols having preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol, etc.

The cosmetic agents according to the invention may be skin-cosmetic, hair-cosmetic, dermatological, hygienic or pharmaceutical agents. The copolymers described above are particularly suitable as additives for hair and skin cosmetics.

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

The cosmetically or pharmaceutically active agents according to the invention may additionally contain cosmetically and / or dermatologically active agents as well as excipients.

The cosmetic compositions according to the invention preferably comprise at least one copolymer A) as defined above, at least one carrier B as defined above and at least one different constituent 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, gelling agents, care products, colorants, tinting agents, tanning agents, dyes, pigments, bodying agents, moisturizers, backfats, collagen, protein hydrolysates, lipids, antioxidants, defoamers, antistatic agents , Emollients and plasticisers. Typical thickeners in such formulations are crosslinked polyacrylic acids and their derivatives, polysaccharides and their derivatives, such as xanthan gum, agar-agar, alginates or tyloses, cellulose derivatives, eg. As carboxymethylcellulose or hydroxy-carboxymethylcellulose, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinylpyrrolidone. Nonionic thickeners are preferably used.

Suitable cosmetically and / or dermatologically active agents are, for. As coloring agents, skin and hair pigmentation agents, tinting agents, tanning agents, bleach, keratin-hardening substances, antimicrobial agents, light filtering agents, repellent, hyperemic substances, keratolytic and keratoplastic substances, antidandruff, antiphlogistics, keratinizing substances, antioxidant or as Radical scavengers active ingredients, skin moisturizing or moisturizing substances, moisturizing agents, antierythimatös or antiallergically active ingredients and mixtures thereof.

Artificial skin tanning agents that are suitable for tanning the skin without natural or artificial irradiation with UV rays, z. Dihydroxyacetone, alloxan and walnut shell extract. Suitable keratin-hardening substances are generally active ingredients, as used in antiperspirants, such as. Antimicrobial agents are used to destroy microorganisms or to inhibit their growth and thus serve both as a preservative and as a deodorizing substance, which reduces the formation or intensity of body odor. These include z. As usual preservatives known in the art, such as p-hydroxybenzoic acid, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are, for. Zinc ricinoleate, triclosan, undecylenic acid alkylolamides, triethyl citrate, chlorhexidine, etc. Suitable light filtering agents are substances that absorb UV rays in the UV-B and / or UV-A range. Suitable UV filters are z. B. 2,4,6-triaryl-1, 3,5-triazines in which the aryl groups may each bear at least one substituent, which is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and mixtures thereof , Also suitable are p-aminobenzoic acid esters, cinnamic acid esters, benzophenones, camphor derivatives and UV-radiation-stopping pigments, such as titanium dioxide, talc and zinc oxide. Suitable repellent agents are compounds capable of preventing or repelling certain animals, particularly insects, from humans. This includes z. B. 2-ethyl-1, 3-hexanediol, N, N-diethyl-m-toluamide, etc. Suitable hyperemic substances which stimulate the circulation of the skin are, for. For example, essential oils such as mountain pine, lavender, rosemary, juniper berry, horse chestnut extract, birch leaf extract, hay flower extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil, etc. Suitable keratolytic and keratoplastic substances are, for. Salicylic acid, calcium thioglycolate, thioglycol acid and its salts, sulfur, etc. Suitable anti-dandruff agents are, for. As sulfur, Schwefelpolyethylenglykolsorbitanmonooleat, Schwefelricinolpolyethoxylat, Zinkpyrithion, Aluminiumpyrithion, etc. Suitable antiphlogistics, which counteract skin irritation, z. Allantoin, bisabolol, dragosantol, chamomile extract, panthenol, etc.

The compositions of the invention may be used as active ingredient, for. B. as a cosmetic and / or pharmaceutical active ingredient at least one polymer, which differs from the novel copolymers A). These include, in general, anionic, cationic, amphoteric and neutral polymers.

Examples of anionic polymers are homo- and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes, eg. B. Luviset PUR® Fa. BASF, and polyureas. Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example Luvimer® 100P), copolymers of ethyl acrylate and methacrylic acid (for example Luvimer® MAE), copolymers of N-tert-butylacrylamide, ethyl acrylate , Acrylic acid (Ultrahold® 8, strong), copolymers of vinyl acetate, crotonic acid and optionally further vinyl esters (eg Luviset® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, eg. Carboxy-functional, t-butyl acrylate, methacrylic acid (eg Luviskol® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as e.g. B. C4-C3o-alkyl esters of (meth) acrylic acid, C4-C3o-alkyl vinyl esters, C4-C3o-alkyl vinyl ethers and hyaluronic acid. Examples of anionic polymers are also vinyl acetate / - crotonic acid copolymers, such as those under the names Resyn® (National Starch) and Gafset® (GAF) in the trade and vinylpyrrolidone / vinyl acrylate copolymers, available for example under the trademark Luviflex® (BASF ). Further suitable polymers are the vinylpyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF) and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyesters. Also suitable are vinylpyrrolidone / ethyl methacrylate / methacrylic acid copolymers such as those sold by Stepan under the names Stepanhold-Extra and -R1 and the Carboset® grades from BF Goodrich.

Suitable cationic polymers are, for. As cationic polymers called Polyquaternium INCI, z. B. Copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviset Clear®, Luviquat Supreme®, Luviquat® Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ 11), copolymers of

N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives (polyquaternium-4 and -10), acrylamidocopolymers (poly- quaternium-7) and chitosan. Suitable cationic (quaternized) polymers are also Merquat® (polymer based on dimethyldiallylammonium chloride), Gafquat® (quaternary polymers formed by reaction of polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR (hydroxyethylcellulose with cationic groups) and cationic polymers on vegetable Base, z. As guar polymers, such as the Jaguar® brands of Fa. Rhodia. Also suitable are cationic polyurethanes, eg. As described in WO 2006/069742.

Especially suitable polymers are neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose derivatives, Polyaspartic acid salts and derivatives. These include, for example, Luviflex® Swing (partially saponified copolymer of polyvinyl acetate and polyethylene glycol, BASF).

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

Suitable polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer® (National Starch) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers and zwitterionic polymers, as described for example in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 are disclosed. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon®).

Suitable polymers are also nonionic, siloxane-containing, water-soluble or -dispersible polymers, for. As polyether siloxanes, such as Tegopren® (Goldschmidt) or Belsil® (Wacker).

The formulation base of pharmaceutical agents according to the invention preferably contains pharmaceutically acceptable excipients. Pharmaceutically acceptable excipients which are known to be usable in the field of pharmacy, food technology and related fields, in particular those described in relevant pharmacopoeia Ehern (eg DAB Ph. Eur. BP NF) listed as well as other excipients whose properties do not preclude a physiological application.

Suitable auxiliaries may be: lubricants, wetting agents, emulsifying and suspending agents, preserving agents, antioxidants, anti-irritants, chelating agents, emulsion stabilizers, film formers, gelling agents, odor masking agents, resins, hydrocolloids, solvents, solubilizers, neutralizing agents, permeation accelerators, pigments, quaternary Ammonium compounds, lipid and superfatting agents, ointment, cream or oil bases, silicone derivatives, stabilizers, sterilants, blowing agents, drying agents, opacifiers, thickeners, waxes, plasticizers, white oils. A related embodiment is based on expert knowledge, as for example in Fiedler, H. P. Lexicon of excipients for pharmacy, cosmetics and related fields, 4th ed., Aulendorf: ECV Editio Kantor Verlag, 1996, are shown.

To prepare the dermatological agents of the invention, the active ingredients may be mixed or diluted with a suitable excipient (excipient). Excipients may be solid, semi-solid or liquid materials which may serve as a vehicle, carrier or medium for the active ingredient. If desired, the admixing of further auxiliaries takes place in the manner known to the person skilled in the art. Furthermore, the polymers and polyelectrolyte complexes are suitable as auxiliaries in pharmacy, preferably as or in coating agent (s) or binder (s) for solid dosage forms. They can also be used in creams and as tablet coatings and tablet binders.

According to a preferred embodiment, the agents according to the invention are a skin cleanser.

Preferred skin cleansing agents are soaps of liquid to gel consistency, such as transparent soaps, luxury soaps, deep soaps, cream soaps, baby soaps, skin soaps, abrasive soaps and syndets, pasty soaps, greases and washing pastes, liquid detergents, shower and bath preparations such as washing lotions, shower gels and gels , Bubble baths, oil baths and scrub preparations, shaving foams, lotions and creams.

According to a further preferred embodiment, the agents according to the invention are cosmetic agents for the care and protection of the skin, nail care preparations or preparations for decorative cosmetics.

Suitable skin cosmetic agents are, for. For example, face lotions, face masks, deodorizers, and other cosmetic lotions. Means for use in the decorative Cosmetics include, for example, masking pens, theatrical paints, mascara and eye shadows, lipsticks, kohl pencils, eyeliners, rouges, powders and eyebrow pencils.

In addition, the copolymers of the invention can be used in nasal strips for pore cleansing, in anti-acne agents, repellents, shaving agents, hair removal agents, personal care products, foot care products and in baby care.

The skin care compositions according to the invention are in particular W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-wrinkle creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, skin lotions and moisturizing lotions.

Skin cosmetic and dermatological compositions based on the copolymers described above show advantageous effects. Among other things, the polymers can contribute to moisturizing and conditioning the skin and to improving the feel on the skin. By adding the polymers according to the invention, it is also possible to achieve an improvement in the skin compatibility in certain formulations.

Skin cosmetic and dermatological compositions preferably comprise at least one copolymer A) comprising at least one panthenol ester in copolymerized form

Form, in a proportion of about 0.001 to 30 wt .-%, preferably 0.01 to 20% by weight, most preferably 0.1 to 12 wt .-%, based on the total weight of the composition.

Depending on the field of application, the compositions of the invention in a form suitable for skin care, such. B. as cream, foam, gel, pen, mousse, milk, spray (pump spray or propellant spray) or lotion can be applied.

In addition to the copolymers A) and suitable carriers, the skin cosmetic preparations may contain further active ingredients and auxiliaries customary in skin cosmetics, as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaching agents, colorants, toners, tanning agents, collagen, protein hydrolysates, stabilizers, pH regulators , Dyes, salts, thickeners, gelling agents, bodying agents, silicones, humectants, moisturizers and other common additives.

Preferred oil and fat components of the skin cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as. For example, paraffins, silicone oils and aliphatic hydrocarbons having more than 8 carbon atoms, animal and vegetable oils, such. As sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as. B. triglycerides of C6-C3o fatty acids, wax esters, such as. As jojoba oil, fatty alcohols, Vaseline, hydrogenated lanolin and acetylated lanolin and mixtures thereof.

The copolymers A) according to the invention comprising at least one panthenol ester in copolymerized form can also be mixed with conventional polymers if special properties are to be set.

To set certain properties such. B. improving the feeling of touch, the spreading behavior, the water resistance and / or the binding of active ingredients and adjuvants, such as pigments, the skin-cosmetic and dermatological preparations may additionally contain conditioning substances based on silicone compounds. Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.

The preparation of the cosmetic or dermatological preparations is carried out by customary methods known to the person skilled in the art.

The cosmetic and dermatological agents are preferably in the form of emulsions, in particular as water-in-oil (W / O) or oil-in-water (O / W) emulsions. However, it is also possible to choose other types of formulations, for example hydrodispersions, gels, oils, oleogels, multiple emulsions, for example in the form of W / O / W or O / W / O emulsions, anhydrous ointments or ointment bases, etc.

Emulsions are prepared by known methods. In addition to at least one ampholytic copolymer, the emulsions generally contain customary constituents, such as fatty alcohols, fatty acid esters and, in particular, fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water. The selection of the emulsion type-specific additives and the preparation of suitable emulsions is described, for example, in Schrader, Grundlagen und Rezepturen der Kosmetika, Hüthig Buch Verlag, Heidelberg, 2nd edition, 1989, third part, to which reference is hereby expressly made.

A suitable emulsion, for. As for a skin cream, etc., generally contains an aqueous phase which is emulsified by means of a suitable emulsifier in an oil or fat phase. To provide the aqueous phase or the oil phase, a copolymer A) according to the invention can be used.

Preferred fat components which may be included in the fat phase of the emulsions are: hydrocarbon oils such as paraffin oil, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in these oils; animal or vegetable oils, such as sweet almond oil, avocado oil, calophylum oil, lanolin and derivatives thereof, castor oil, seed oil, olive oil, jojoba oil, karite oil, hoplostethus oil; Mineral oils whose beginning of distillation under atmospheric pressure at about 250 ⁰ C and their distillation end point at 410 ⁰ C, such as. Vaseline oil; Esters of saturated or unsaturated fatty acids, such as alkyl myristates, e.g. For example, i-propyl, butyl or cetyl myristate, hexadecyl stearate, ethyl or i-propyl palmitate, octanoic or Decansäuretriglyceride and Cetylricinoleat.

The fat phase may also contain other oil-soluble silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.

It can also waxes are used, such as. Carnauba wax, candililla wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.

Furthermore, an emulsion of the invention may be present as O / W emulsion. Such an emulsion usually contains an oil phase, emulsifiers that stabilize the oil phase in the water phase, and an aqueous phase that is usually thickened. Suitable emulsifiers are preferably O / W emulsifiers, such as polyglycerol esters, sorbitan esters or partially esterified glycerides into consideration.

According to a further preferred embodiment, the agents according to the invention are a shower gel, a shampoo formulation or a bathing preparation.

Such formulations contain at least one inventive copolymer A) and usually anionic surfactants as base surfactants and amphoteric and / or nonionic surfactants as cosurfactants. Other suitable active ingredients and / or adjuvants are generally selected from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants, as well as thickeners / gelling agents, skin conditioners and humectants.

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

In the washing, shower and bath preparations all anionic, neutral, amphoteric or cationic surfactants commonly used in personal care products can be used.

Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isothionates, alkyl phosphates, alkyl ether phosphates. te, Alkylethercarboxylate, alpha-olefinsulfonates, in particular the alkali and alkaline earth metal salts, z. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.

These include z. Sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecyl benzene sulfonate, triethanolamine dodecyl benzene sulfonate.

Suitable amphoteric surfactants are, for. Alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or -propionates, alkylamphodiacetates or -dipropionates.

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

Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 C atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and / or propylene oxide. The amount of alkylene oxide is about 6 to 60 moles per mole of alcohol. Also suitable are alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkylpolyglycosides or sorbitan ether esters.

In addition, the washing, showering and bathing preparations may contain conventional cationic surfactants, such as. B. quaternary ammonium compounds, such as cetyltrimethyl ammonium chloride.

Furthermore, the shower gel / shampoo formulations thickener, such. As sodium chloride, PEG-55, propylene glycol oleate, PEG-120-methyl glucose dioleate and others, as well as preservatives, other active ingredients and auxiliaries and water.

According to a particularly preferred embodiment, the agents according to the invention are a hair treatment agent.

Hair treatment agents according to the invention preferably comprise at least one copolymer A) in an amount in the range from about 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the composition.

The hair treatment compositions according to the invention are preferably in the form of a hair spray, mousse, hair mousse, hair gel, shampoos, hair foam, Top fluids, leveling agent, hair dye and bleach or hot oil treatments. Depending on the field of application, the hair cosmetic preparations can be applied as (aerosol) spray, (aerosol) foam, gel, gel spray, cream, lotion or wax. Hairsprays include both aerosol sprays and pump sprays without propellant gas. Hair foams include both aerosol foams and pump foams without propellant gas. Hair sprays and hair foams preferably comprise predominantly or exclusively water-soluble or water-dispersible components. If the compounds used in the hair sprays and hair foams according to the invention are water-dispersible, they can be used in the form of aqueous microdispersions with particle diameters of usually from 1 to 350 nm, preferably from 1 to 250 nm. The solids contents of these preparations are usually in a range of about 0.5 to 20 wt .-%. As a rule, these microdispersions do not require emulsifiers or surfactants for their stabilization.

The hair cosmetic formulations of the invention comprise in a preferred embodiment

a) from 0.05 to 20% by weight of at least one copolymer A) according to the invention, comprising at least one panthenol ester in copolymerized form, as defined above, b) from 20 to 99.95% by weight of water and / or alcohol, c ) 0 to 50 wt .-% of at least one propellant gas, d) 0 to 5 wt .-% of at least one emulsifier, e) 0 to 3 wt .-% of at least one thickener, and f) up to 25 wt .-% further constituents ,

By alcohol, all alcohols customary in cosmetics are to be understood, for. For example, ethanol, isopropanol, n-propanol.

Further constituents are understood to include the additives customary in cosmetics, for example blowing agents, defoamers, surface-active compounds, ie surfactants, emulsifiers, foaming agents and solubilizers. The surface-active compounds used can be anionic, cationic, amphoteric or neutral. Further customary components may also be z. As preservatives, perfume oils, opacifiers, active ingredients, UV filters, care agents such as panthenol, collagen, vitamins, protein hydrolysates, alpha- and beta-hydroxycarboxylic acids, protein hydrolysates, stabilizers, pH regulators, dyes, viscosity regulators, gel formers, dyes, salts , Humectants, moisturizers, complexing agents and other common additives. Furthermore, this includes all known in cosmetics styling and Conditionerpoly- mers, which can be used in combination with the polymers of the invention, if very special properties are to be set.

To adjust certain properties, the preparations may additionally contain conditioning substances based on silicone compounds. Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes, silicone resins or dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).

The ampholytic copolymers and polyelectrolyte complexes according to the invention are suitable in particular as setting agents in hairstyling preparations, in particular hair sprays (aerosol sprays and pump sprays without propellant gas) and hair foams (aerosol foams and pump foams without propellant gas).

In a preferred embodiment, spray formulations contain

a) 0.1 to 10 wt .-% of at least one copolymer A), as defined above, b) 20 to 99.9 wt .-% of water and / or alcohol, c) 0 to 70 wt .-% of at least one blowing agent , d) 0 to 20 wt .-% further ingredients.

Blowing agents are the blowing agents commonly used for hairsprays or aerosol foams. Preference is given to mixtures of propane / butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152a), carbon dioxide, nitrogen or compressed air.

A preferred formulation for aerosol hair foams according to the invention

a) 0.1 to 10 wt .-% of at least one inventive copolymer A), as defined above, b) 55 to 99.8 wt .-% of water and / or alcohol, c) 5 to 20 wt .-% of a blowing agent , d) 0.1 to 5 wt .-% of an emulsifier, e) 0 to 10 wt .-% further constituents.

As emulsifiers all emulsifiers commonly used in hair foams can be used. Suitable emulsifiers may be nonionic, cationic or anionic or amphoteric.

Examples of nonionic emulsifiers (INCI nomenclature) are Laurethe, z. B. Laureth-4; Cetethe, z. Cetheth-1, polyethylene glycol cetyl ether; Cetearethe, z. Cethea reth-25, polyglycol fatty acid glycerides, hydroxylated lecithin, lactyl esters of fatty acids, alkylpolyglycosides.

Examples of cationic emulsifiers are cetyldimethyl-2-hydroxyethylammonium dihydrogenphosphate, cetyltrimonium chloride, cetyltrimmonium bromide, cocotrimonium methylsulfate, quaternium-1 to x (INCI).

Anionic emulsifiers may, for example, be selected from the group of alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isothionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali and alkaline earth metal salts, e.g. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.

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

a) 0.1 to 10 wt .-% of at least one inventive copolymer A), as defined above, b) 80 to 99.85 wt .-% of water and / or alcohol, c) 0 to 3 wt .-%, preferably 0.05 to 2 wt .-%, of a gelling agent, d) 0 to 20 wt .-% further ingredients.

As gel formers, all gel formers customary in cosmetics can be used. These include slightly crosslinked polyacrylic acid, for example carbomer (INCI), cellulose derivatives, eg. Hydroxypropyl cellulose, hydroxyethyl cellulose, cationic modified celluloses, polysaccharides, e.g. Xanthan gum, caprylic / capric triglyceride, sodium acrylate copolymers, polyquaternium-32 (and) paraffin liquidum (INCI), sodium acrylate copolymers (and) paraffin liquidum (and) PPG-1 trideceth-6, acrylamido propyltrimonium chloride / acrylamide copolymers, steareth-10 allyl ether acrylate copolymers, polyquaternium-37 (and) paraffinum liquidum (and) PPG-1 trideceth-6, polyquaternium 37 (and) propylene glycol dicaprate dicaprylate (and) PPG-1 trideceth-6, polyquaternium 7, Polyquaternium-44.

The copolymers A) according to the invention can be used as conditioning agents in cosmetic preparations.

The copolymers A) according to the invention, as defined above, may preferably be present in

Shampoo formulations are used as strengthening and / or conditioning. Contain preferred shampoo formulations a) from 0.05 to 10% by weight of at least one copolymer A) as defined above, b) from 25 to 94.95% by weight of water, c) from 5 to 50% by weight of surfactants, c) from 0 to 5 Wt .-% of another conditioning agent, d) 0 to 10 wt .-% further cosmetic ingredients.

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

Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isothionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, in particular the alkali metal and alkaline earth metal salts, eg. As sodium, potassium, magnesium, calcium, and ammonium and

Triethanolamine salts. The alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.

Suitable examples are sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.

Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or -propionates, alkylamphodiacetates or -dipropionates.

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

Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 C atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and / or propylene oxide. The amount of alkylene oxide is about 6 to 60 moles per mole of alcohol. Also suitable are alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters.

In addition, the shampoo formulations may contain conventional cationic surfactants, such as. For example, quaternary ammonium compounds, for example Cetyltrimethylammoni- umchlorid. The following examples illustrate the invention without limiting it.

Examples

Example 1: Preparation of Panthenyl Monoacrylate

In a 4 L round bottom flask, 1.0 mol D, L-panthenol (205 g), 10.0 mol methyl acrylate (861 g), 50 mg methoxyphenol (200 ppm), 200 g 5 A molecular sieve powder and 200 ml acetone were added for 1 h 40 ⁰ C stirred until the panthenol has largely dissolved. Thereafter, the reaction was started by adding 10.0 g of Novozym 435 and the mixture was stirred at 40 ⁰ C for 2.5 h. For work-up, after addition of 1 l of isopropanol, the molecular sieve and the enzyme were filtered off via a glass filter funnel and washed with isopropanol. The clear, colorless filtrate was concentrated on a rotary evaporator at 50 ^° C. and 10 mbar, with air being introduced into the solution for stabilization. This gave a clear yellowish oil in quantitative yield, which partially crystallized on cooling. The content determined by GC after silylation with MSTFA was 96%. The product contained 99.0% panthenol monoacrylate and 1.0% panthenol diacrylate. The structure was confirmed by GC-MS and ¹ H-NMR.

Example 2:

5 mmol D, L-panthenol (1, 0 g) were shaken with 40 mmol of methyl acrylate (4.3 g), 1, 0 g of 5 Angstrom molecular sieve and 50 mg Novozym 435 without solvent for 24 h at 40 ⁰ C in a water bath. The content determined by GC after silylation with MSTFA was 95%. The product contained 90.5% panthenol monoacrylate and 9.5% panthenol diacrylate.

Example 3a: Copolymerization with vinylpyrrolidone

473.5 g of a 40% solution of Sokalan® CP 5 (maleic acid / acrylic acid)

Copolymer, Na-SaIz) are diluted with 135 g of water and 9 g of sulfuric acid (50% solution) was added. To this template is added 48 g of feed 1, 105.67 g of feed 2 and 0.75 g of triallylamine. The original is rendered inert and then heated to 65 ⁰ C. After reaching this temperature, 6 g of feed 3 are added and then polymerized for 15 minutes. Thereafter, the remainder of the feeds 1 and 2 are added within two hours and at the same time 17 g of feed 3 are metered in within 3 hours. After completion of the addition of feed 3 is allowed the reaction mixture for 4 hours at 65 ⁰ C to react further. The mixture is then heated to 70 ⁰ C and the remaining 22 g of feed 3 added within 30 minutes. Thereafter, a further 1 load, the reaction, post-polymerize for 5 hours at 70 ⁰ C. It is allowed to cool and then diluted with 80 g of water. Feed 1 consists of:

3 g of pantenol acrylate from Example 1

237 g of N-vinylpyrrolidone

Feed 2 consists of:

133.35 g of 45% solution of 3-methyl-1-vinylimidazolium dimethylsulfate 395 g of demineralized water

Feed 3 consists of:

4.50 g of Wako V50 (2,2'-azobis (2-amidinopropane) dihydrochloride) 40.5 g of demineralized water.

It is a white emulsion of the polymer with 33% solids content and a tel-quel viscosity of 10,000 mPas (at spindle 6, 20 rpm).

Example 3b: Comparative example without panthenol acrylate

The preparation is carried out as in Example 3a), wherein the feed 1 contains no panthenol acrylate.

Feed 1 consists of:

240 g of N-vinylpyrrolidone

Feed 2 consists of:

133.35 g of 45% solution of 3-methyl-1-vinylimidazolium dimethylsulfate 395 g of demineralized water

Feed 3 consists of:

4.50 g of Wako V50 (2,2'-azobis (2-amidinopropane) dihydrochloride) 40.5 g of demineralized water

It is a white emulsion of the polymer with 33% solids content and a tel-quel viscosity of 12000 mPas (at spindle 6, 20 rpm).

Example 4: Shampoo formulations The polymers from Example 3a according to the invention from Comparative Example 3a were each used in a concentration of 0.5% (polymer content) for the preparation of a shampoo, and then the wet combability and the feel of the dry hair were assessed.

Sample wet combability handle

Polymer from Example 3a 73% very good, well-kept

Polymer from Example 3b 63% good, well-kept

Formulation of the shampoo formulation

35.70 g Texapon NSO (Sodium Laureth Sulfate, Henkel)

12.50 g of Tego Betaine I_7 0.5% polymer from Example 3a or 3b

0.10 g of Euxyl K 100 ad 100 g of water

1, 00 g NaCl

For blank value determination, a hair tress was washed twice with Texapon NSO within 1 minute, rinsed with water for 1 minute, pressed on filter paper and combed. Subsequently, 5 g of the shampoo to be tested were applied, shampooed for 1 min, rinsed for 1 min, pressed on filter paper and combed (determination of the measured value).

The% of wet combability is calculated as follows:

Kämmkraftabnahme (wet) = 100 - (measured value ^* 100 / blank value) in%

Example 4a: Thickener

35 g of Pluriol® E 9000 (polyethylene glycol) and 1. 58 g of PETAE (pentaerythrityl triallyl ether) are dissolved in 350 g of n-butyl acetate. To this is added 14 g of feed 2, the template is inertized and heated to 90 ^° C. Then feed 1 is added within 4 h. In parallel, the remainder of feed 2 is added within 5 hours, and then the reaction mixture heated to 100 ⁰ C and polymerized for 2 hours. The mixture is cooled and diluted with 450 g of butyl acetate. Thereafter, the resulting suspension is filtered and washed and dried in a drying oven at 75 ⁰ C.

Feed 1 consists of: 297.5 g of vinylimidazole

27.50 g of panthenol acrylate from Example 1

262.5 g of n-butyl acetate

Feed 2 consists of:

0.56 g of tert-butyl peroctoate 310.5 g of n-butyl acetate

The resulting powder shows a viscosity in water at a polymer content of 0.5% and pH 3 (adjusted with lactic acid) of 15500 mPas.

Example 4b: Thickener (comparative example without panthenol acrylate)

The procedure is as in Example 4a, wherein the feed 1 contains no panthenol acrylate.

Feed 1 consists of:

325 g of vinylimidazole 262.5 g of n-butyl acetate

Inlet 2 consists of

0.56 g of tert-butyl peroctoate 310.5 g of n-butyl acetate

The resulting powder shows a viscosity in water at a polymer content of 0.5% and pH 3 (adjusted with lactic acid) of 15000 mPas.

Claims

claims

1. Esters of panthenol with α, ß-monoethylenically unsaturated C2-C8-carboxylic acids.

2. esters of panthenol according to claim 1, which are the monoesters of the formula

or the diesters of the formula

wherein R ^{1 represents} the acyl radical of the oφ-monoethylenically unsaturated C 2 -C 8 -carboxylic acid.

3. ester of panthenol according to claim 1 or 2 with acrylic acid or methacrylic acid.

4. An ester of panthenol according to claim 1 or 2 with itaconic acid, maleic acid, fumaric acid, methylfumaric acid, methylmaleic acid, dimethylmaleic acid, methylenemalonic acid or the C 1 -C 4 -alkyl half esters thereof.

5. An ester of panthenol according to claim 1, namely panthenol monoacrylate of the formula

or panthenol monomethacrylate of the formula

An ester of panthenol according to claim 1, namely panthenol diacrylate of the formula

or panthenol dimethacrylate of the formula

7. A process for the preparation of the esters of panthenol according to any one of claims 1 to 5, wherein esterifying a Ci-C4-alkyl ester of oφ-monoethylenically unsaturated carboxylic acid with panthenol in the presence of a hydrolase.

8. Use of the esters of panthenol according to any one of claims 1 to 5 as a comonomer.

9. Use of the esters of panthenol of the formula Ib according to claim 1 as a crosslinking agent.

10. Copolymers, comprising units of at least one panthenol ester according to any one of claims 1 to 5 and units of at least one copolymerizable with the esters of panthenol monomer.

1 1. Copolymers according to claim 10, wherein the copolymerisable monomer is selected from C 1 -C 20 -alkyl acrylates, C 1 -C 20 -alkyl methacrylates, vinyl esters of carboxylic acids having 1 to 20 carbon atoms, vinyl-C 1 -C 20 -alkyl ethers, vinylaromatic compounds , N-vinyllactams, quaternized vinyl monomers, hydroxy-C 1 -C 18 -alkyl acrylates, hydroxy-C 1 -C 18 -alkyl methacrylates, amino-C 1 -C 18 -alkyl acrylates, amino-C 1 -C 8 -alkyl methacrylates, vinylpyrrolidone, vinylimidazole, acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile and non-aromatic hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds.

12. A cosmetic or pharmaceutical composition comprising at least one copolymer according to claim 10 or 11.

13. Use of the copolymers according to claim 10 or 11 for improving the properties of the skin and hair.