WO2004056885A1 - Polymeres contenant des groupes acide pyrrolidone-4-carboxylique et utilisation - Google Patents

Polymeres contenant des groupes acide pyrrolidone-4-carboxylique et utilisation Download PDF

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WO2004056885A1
WO2004056885A1 PCT/EP2003/014549 EP0314549W WO2004056885A1 WO 2004056885 A1 WO2004056885 A1 WO 2004056885A1 EP 0314549 W EP0314549 W EP 0314549W WO 2004056885 A1 WO2004056885 A1 WO 2004056885A1
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agents
polymer
water
polymers
acid
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PCT/EP2003/014549
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German (de)
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Son Nguyen-Kim
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Basf Aktiengesellschaft
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups

Definitions

  • the present invention relates to water-soluble or water-dispersible polymers which contain groups bonded to the polymer backbone which are formally derived from pyrrolidone-4-carboxylic acids and their esters and amides, processes for their preparation, cosmetic or pharmaceutical compositions which do such Contain polymer and other uses of these polymers.
  • N-vinylpyrrolidone Polymers based on N-vinylpyrrolidone have found widespread use in a large number of fields of application. These include, for example, use in pharmacy, cosmetics, in food production, as adhesives, in the textile industry, etc. An overview of the use of N-vinylpyrrolidone polymers can be found, for example, in F. Haaf et al., Polymer Journal, Vol. 17, No. 1, pp. 143-152 (1985). The high production costs of N-vinylpyrrolidone, which economically disadvantage such uses, are disadvantageous.
  • water-soluble or dispersible polymers which have good pharmaceutical or cosmetic compatibility and biodegradability as well as film-forming properties.
  • Cosmetically and pharmaceutically acceptable water-soluble polymers serve, for example, as formulating agents in soaps, creams and lotions, e.g. B. as a thickener,
  • Your task in hair cosmetics is to influence the properties of the hair.
  • So film-forming polymers such. B. used for strengthening, structural improvement and shaping of the hair. In pharmacy, for example, they serve as coating agents or binders for solid pharmaceutical forms.
  • DE-A-196 31 379 and DE-A-196 31 380 describe polyasparic acid derivatives and their use in cosmetics.
  • WO 95/09194 describes pyrrolidone group-containing polyesters and polyamides and their use, inter alia, as film formers and conditioners in hair cosmetic preparations.
  • No. 4,418,189 describes bis-N-substituted pyrrolidinones in which the ring nitrogen atoms are connected to one another via a bridging group. These can be obtained by reacting itaconic diesters with diamines. Use in cosmetics is not described.
  • the object of the present invention is to provide new water-soluble or water-dispersible polymers. These should be suitable for areas of application in which polymers based on N-vinylpyrrolidone are usually used and in particular are pharmaceutically and / or cosmetically compatible. The production costs should be lower than those of polymers based on N-vinylpyrrolidone in order to enable economical use. These polymers should preferably be distinguished by good film-forming properties and / or good biodegradability.
  • water-soluble or water-dispersible polymers which contain groups bonded to the polymer backbone which are formally derived from pyrrolidone-4-carboxylic acids and their esters and amides.
  • groups bonded to the polymer backbone which are formally derived from pyrrolidone-4-carboxylic acids and their esters and amides.
  • monomers with N-vinylpyrrolidone structural elements can advantageously be dispensed with.
  • these polymers can be prepared in a simple manner from prepolymers and polymers with primary amino groups by reaction with itaconic acid or an itaconic acid derivative.
  • a first object of the invention is therefore a water-soluble or water-dispersible polymer containing at least four pyrrolidone-4-carboxylic acid units bound to a polymer backbone, which are selected independently of one another from groups of the general formula I.
  • X represents O or NR 2 , where R 2 represents hydrogen or alkyl
  • R 1 represents hydrogen or alkyl.
  • the polymers according to the invention preferably have at least 5, in particular at least 6, groups of the formula I bonded to the polymer backbone. Their maximum proportion is usually not critical and is for example up to about 100, such as. B. to 50.
  • alkyl includes straight-chain and branched alkyl groups. Suitable alkyl groups are e.g. B. straight-chain or branched Ci-Cg-alkyl and preferably -C-C alkyl groups.
  • the polymers according to the invention can advantageously be formulated as gels under normal conditions (20 ° C.).
  • "Gel-like consistency” means agents which have a higher viscosity than a liquid and which are self-supporting, i.e. H. which retain the shape they have been given without a shape-stabilizing covering. In contrast to solid formulations, gel-like formulations can easily be deformed using shear forces.
  • the viscosity of the gel-like agents are preferably in a range from greater than 600 to about 60,000 mPas.
  • the gels are preferably hair gels, these having a viscosity of preferably 6000 to 30,000 mPas.
  • water-soluble monomers and polymers are understood to mean monomers and polymers which dissolve at least 1 g / l in water at 20 ° C.
  • Hydrophilic monomers are water-soluble or at least water-dispersible.
  • Water-dispersible polymers are understood to mean polymers which disintegrate into dispersible particles using shear forces, for example by stirring.
  • the polymer structure of the polymers according to the invention is a hyperbranched polymer.
  • hyperbranched polymers generally encompasses polymers which are distinguished by a branched structure and high functionality.
  • the hyperbranched polymers according to the invention have at least four pyrrolidone-4-carboxylic acid groups of the formula I. The proportion of these groups is preferably 4 to 100, particularly preferably 5 to 30 and in particular 6 to 20.
  • hyperbranched polymers within the meaning of the invention also include star polymers, dendrimers (dendritic polymers) and various highly branched polymers, such as, for. B. comb polymers.
  • Star polymers are polymers in which three or more chains start from a center.
  • the center can be a single atom or a group of atoms.
  • "Dendrimers” dendritic polymers, cascade polymers, arborols, isotropically branched polymers, iso-branched polymers, starburst polymers
  • Dendrimers are molecularly uniform macromolecules with a highly symmetrical structure. Dendrimers are structurally derived from the star polymers, with the individual chains each branching in a star shape. They arise from small molecules through a constantly repeating reaction sequence, resulting in ever higher branches, at the ends of which there are functional groups, which in turn are the starting point for further branches.
  • the number of monomer end groups increases exponentially with each reaction step, resulting in a spherical tree structure at the end.
  • a characteristic feature of the dendrimers is the number of reaction stages (generations) carried out to build them up. Due to their uniform structure, dendrimers generally have a defined molar mass.
  • the hyperbranched polymers according to the invention also include both molecularly and structurally non-uniform, highly branched polymers which have side chains of different lengths and branches and have a molecular weight distribution.
  • So-called AB x monomers are particularly suitable for the synthesis of the hyperbranched polymers according to the invention. These have two different functional groups A and B, which can react with one another to form a link.
  • the functional group A is contained only once per molecule and the functional group B twice or more, x preferably stands for an integer from 2 to 8.
  • the reaction of the said AB X monomers with one another results in uncrosslinked polymers with regularly arranged branching sites.
  • the polymers have almost exclusively B groups at the chain ends.
  • the hyperbranched polymers according to the invention can be obtained in a polymer-analogous reaction with itaconic acid or an itaconic acid derivative.
  • the hyperbranched polymers used according to the invention preferably have a degree of branching (DB) corresponding to an average number of dendritic linkages and terminal units per molecule of 10 to 100%, preferably 10 to 90% and in particular 10 to 80%.
  • DB degree of branching
  • the hyperbranched polymers according to the invention are preferably produced by a process in which
  • step b) subjecting the compound obtained in step a) to a condensation reaction.
  • the compound used in step a), which has at least two primary amino groups and at least one further functional group capable of a condensation reaction with carboxylic acids and carboxylic acid derivatives, is preferably selected from diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, bis- (3-aminopropyl) amine , Bis (4-aminobutyl) amine, N, N'-bis (3-aminopropyl) -l, 4-diaminobutane and mixtures thereof. Itaconic acid is preferably used for the reaction in step a).
  • the molar ratio of primary amino groups to itaconic acid or itaconic acid derivative depends on the desired degree of conversion with respect to the primary amino groups. It is chosen so that compounds are obtained which contain at least two pyrrolidone-4-carboxylic acid units of the formula I.
  • the reaction in step a) is preferably carried out in water or in a mixture of water and at least one water-miscible solvent.
  • Suitable water-miscible solvents are, for example, C ⁇ -C alkanols, such as ethanol.
  • Water is preferably used as the solvent in step a).
  • the reaction in step a) is preferably carried out at a temperature of about 60 to 100 ° C., particularly preferably 80 to 100 ° C.
  • the solvent is preferably prepared by customary methods known to those skilled in the art, eg. B. completely removed by distillation under reduced pressure.
  • step b) there is an intermolecular reaction of the compounds obtained in step a) with the reaction of the functional groups capable of a condensation reaction with carboxylic acids and carboxylic acid derivatives on the one hand and part of the carboxylic acid, carboxylic ester or carboxylic acid amide units of the Groups of the general formula I introduced in step a).
  • the products obtained in this way have at least four groups of the general formula I which have not been subjected to the condensation reaction.
  • the condensation in step b) is preferably carried out at a temperature in the range from about 100 to 350 ° C., particularly preferably 150 to 300 ° C.
  • the condensation is preferably carried out with removal of the resulting condensation products, e.g. B. the water of reaction formed.
  • the reaction in step b) takes place under an inert gas atmosphere, such as. B. under nitrogen.
  • the reaction in step b) can take place in the presence of at least one further compound which comprises at least two condensation reactions with carboxylic acids and carboxylic acid derivatives. capable functional groups.
  • These are preferably selected from diols, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, diamines, such as. B. 1,2-diaminoethane, 1,3-diamino-propane, 1,4-diaminobutane, amino alcohols, etc.
  • Preferred as additional compounds used for the condensation reaction are polyetheramines, such as 0.0'-bis (2-aminopropyl) - polyethylene glycol 500, 0.0'-bis (2-aminopropyl) polyethylene glycol 800, 0.0'-bis (2-aminopropyl) polyethylene glycol 1900, 0.0'-bis (2-aminopropyl) ) polypropylene glycol 130 and 0.0'-bis (2-aminopropyl) polypropylene glycol 300 are used. These are commercially available under the name Jeffamine®.
  • the water-soluble or water-dispersible polymers according to the invention contain copolymerized repeating units of the general formula 1.1
  • X represents 0 or NR 2 , where R 2 represents hydrogen or alkyl
  • R 1 represents hydrogen or alkyl.
  • These polymers can be obtained by reacting at least one polymer with vinylamine units of the general formula II
  • Suitable monomers are, for example, N-vinylformamide, N-vinylacetamide and N-vinylpropionamide.
  • the monomers mentioned can be polymerized either alone, as a mixture with one another or together with other monoethylenically unsaturated monomers.
  • homopolymers or copolymers of N-vinylformamide are used.
  • the abovementioned polymers with N-vinylcarbonamide units are subjected to partial or complete hydrolysis.
  • the degrees of hydrolysis are in a range from 0.1 to 100 mol%, preferably 10 to 99 mol% and in particular 50 to 98 mol%.
  • R 3 has the meaning given for it in formula III.a, polymers which contain vinylamine units of the formula II in copolymerized form.
  • R 3 represents hydrogen or Ci-Cg-alkyl.
  • the polymers according to the invention can additionally contain at least one radically polymerizable compound which has at least one ⁇ -ethylenically unsaturated double bond has copolymerized contained, which is selected from
  • the water-soluble or water-dispersible polymers according to the invention preferably contain 0.1 to 100% by weight, particularly preferably 1 to 99.9% by weight, in particular 5 to 99% by weight and especially 20 to 98% by weight, based on the total weight of the polymer, repeating units of the general formula I.
  • the proportion of repeating units of the general formula I at least 50% by weight, particularly preferably at least 60% by weight.
  • the polymers according to the invention preferably contain 0 to 99.9% by weight, particularly preferably 0.1 to 99% by weight, in particular 2 to 80% by weight, based on the total weight of the polymers, repeating units of the general formula II and / or the general formula III.
  • the proportion of repeating units of the general formulas II and / or III is at most 50% by weight, particularly preferably at most 40% by weight.
  • the polymers according to the invention can additionally contain at least one radically polymerizable hydrophilic nonionic compound Ml) in copolymerized form.
  • the polymer can then preferably contain up to 50% by weight, particularly preferably 0.1 to 40% by weight, in copolymerized form, based on the total weight of the polymer, of at least one free-radically polymerizable nonionic compound Ml).
  • the free-radically polymerizable nonionic compound Ml is preferably selected from primary amides ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids, N-vinyl lactams, N-vinylamides of monocarboxylic acids saturated with compounds of the formula III.a, esters, ⁇ -ethylenically unsaturated mono- and Dicarboxylic acids with C 2 -C alkanediols, esters and amides ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 4 amino alcohols which have a primary or secondary amino group, vinyl ethers, nonionic, hydrophilic vinyl and allyl-substituted heterocyclic compounds and mixtures thereof.
  • Primary amides ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids suitable as nonionic monomers Ml are, for example, acrylic acid amide, methacrylic acid amide, ethacrylic acid amide and mixtures thereof. Acrylic acid amide and / or methacrylic acid amide are preferred.
  • Preferred hydrophilic nonionic monomers Ml) are N-vinyl lactams and their derivatives, the z. B. may have one or more Ci-C ß alkyl substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc. These include e.g. B.
  • N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-eth l-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. are preferred
  • N-vinyl pyrrolidone and / or N-vinyl caprolactam used.
  • N-vinylamides suitable as hydrophilic nonionic monomers Ml are, for example, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-N-methylpropionamide and mixtures thereof.
  • Suitable hydrophilic nonionic monomers Ml are furthermore the esters ⁇ , ⁇ -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 4 -alkanediols.
  • esters ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid etc.
  • C 1 -C 4 -alkanediols include e.g. B. 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
  • Suitable monomers are also the esters of the aforementioned acids with triols and polyols, such as. B. glycerol, erythritol, pentaerythritol, sorbitol etc.
  • Suitable hydrophilic nonionic monomers Ml are also vinyl and allyl-substituted heteroaromatic compounds, such as 2- and 4-vinylpyridine and 2- and 4-allylpyridine.
  • the water-soluble or water-dispersible polymers preferably contain at least one hydrophilic nonionic compound Ml) in copolymerized form, which is selected from acrylic acid amide, methacrylic acid amide, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide and mixtures thereof.
  • Ml hydrophilic nonionic compound
  • the water-soluble or water-dispersible polymers according to the invention preferably contain at least one free-radically polymerizable compound M2) with one, .beta.-ethylenically unsaturated double bond and at least one ionogenic and / or ionic group polymerized per molecule.
  • the polymer according to the invention can contain up to 50% by weight, preferably 0.1 to 40% by weight, in particular 1 to 20% by weight, based on the total weight of the polymer of at least one monomer M2) with at least one ionogenic and / or contain ionic group polymerized per molecule.
  • the ionogenic or ionic groups are preferably selected from carboxylic acid groups, sulfonic acid groups and / or phosphonic acid groups and their salts, which can be obtained by partially or completely neutralizing with a base, and also amino groups, which can be partially or fully protonated and quaternized.
  • the monomers M2) with anionogenic / anionic groups are preferably selected from monoethylenically unsaturated carboxylic acids, sulfonic acids, phosphonic acids and salts and mixtures thereof. These include monoethylenically unsaturated mono- and dicarboxylic acids with 3 to 25, preferably 3 to 6, carbon atoms, which can also be used in the form of their salts or anhydrides. Examples include acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid.
  • B. of maleic acid such as maleic acid monomethyl ester.
  • monoethylenically unsaturated sulfonic acids and phosphonic acids for example vinylsulfonic acid, allylsulfonic acid, sulfoethylacrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropyl sulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrene 2-methylpropanesulfonic acid, vinylphosphonic acid and allylphosphonic acid and the salts, especially the sodium, potassium and ammonium salts of these acids.
  • the monomers with anionogenic / anionic groups can be used as such or as mixtures with one
  • Monomers with anionic / anionic groups which are selected from acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid are preferably used to prepare the water-soluble or water-dispersible polymers according to the invention.
  • the monomers with anionogenic / anionic groups are particularly preferably selected from acrylic acid, methacrylic acid and mixtures which contain acrylic acid and / or methacrylic acid.
  • the monomers M2) with ionogenic / ionic groups are those with cationogenic / cationic groups.
  • the cationogenic and / or cationic groups are preferably nitrogen-containing groups, such as primary, secondary and tertiary amino groups and quaternary ammonium groups.
  • the nitrogen-containing groups are preferred tertiary amino groups or quaternary ammonium groups.
  • Charged cationic groups can be derived from the amine nitrogen either by protonation, e.g. B. with carboxylic acids, such as lactic acid, or mineral acids, such as phosphoric acid, sulfuric acid and hydrochloric acid, or by quaternization, for. B. with alkylating agents such as -CC 4 alkyl halides or sulfates. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.
  • Suitable monomers are e.g. B. the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols.
  • Preferred amino alcohols are C 2 -C 2 amino alcohols which are Ci-Cs-dialkylated on the amine nitrogen.
  • As an acid component of these esters are, for. As acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Acrylic acid, methacrylic acid and mixtures thereof are preferably used.
  • N, N-Dimethylamino-methyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, -Dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl are preferred (meth) crylate and N, N-dimethylaminocyclohexyl (meth) acrylate.
  • Suitable monomers M2 are also the amides of the abovementioned ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group. Diamines which have a tertiary and a primary or secondary amino group are preferred.
  • Preferred monomers are N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- ( dimeth lamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- ( dimethylamino) cyclohexyl] acramide, N- [4- (dimethylaminoJcyclohexyl] methacramide, etc. Particularly preferred are N- [3- (dimethylamino) propyl] acrylamide and / or N- [3- (dimethylamino)
  • Suitable monomers M2) are also N, N-diallyl-N-alkylamines and their acid addition salts and quaternization products.
  • Alkyl is preferably -CC 24 alkyl. Are preferred
  • N, N-diallyl-N-methylamine and N, N-diallyl-N, N-dimethylammonium compounds such as. B. the chlorides and bromides.
  • Suitable monomers M2) with cationogenic / cationic groups are also vinyl and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinyl-2-methylimidazole, and the salts thereof.
  • the water-soluble or water-dispersible polymers according to the invention can contain at least one crosslinker M3), ie. H. contain a compound with two or more than two ethylenically unsaturated double bonds in copolymerized form.
  • Crosslinking agents are preferably used in an amount of 0.01 to 10% by weight, particularly preferably 0.1 to 3% by weight, based on the total weight of the polymer.
  • Crosslinking monomers M3) which can be used are compounds having at least two ethylenically unsaturated double bonds, such as, for example, esters of ethylenically unsaturated carboxylic acids, such as acrylic acid or methacrylic acid and polyhydric alcohols, ethers of at least dihydric alcohols, such as vinyl ether or allyl ether.
  • Examples of the underlying alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4 -Butanediol, but-2-en-l, 4-diol, 1, 2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1, 6-hexanediol, 1, 10-decanediol, 1,2-dodecanediol , 1, 12-dodecanediol, neopentyl glycol, 3-methylpentane-l, 5-diol, 2,5-dimethyl-l, 3-hexanediol, 2,2,4-trimethyl-l, 3-pentanediol, 1,2 -Cyclohex
  • Examples of underlying alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose.
  • the polyhydric alcohols can also be used as the corresponding ethoxylates or propoxylates after reaction with ethylene oxide or propylene oxide.
  • the polyhydric alcohols can also initially by reaction be converted into the corresponding glycidyl ether using epichlorohydrin.
  • crosslinkers M3 are the vinyl esters or the 5 esters of monohydric, unsaturated alcohols with ethylenically unsaturated C 3 -C 6 -carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • examples of such alcohols are allyl alcohol, l-buten-3-ol, 5-hexen-l-ol, l-0cten-3-ol, 9-decen-l-ol, dicyclopentenyl alcohol, 10 10-undecen-l- ol, cinnamon alcohol, citronellol, crotyl alcohol or cis-9-octadecen-l-ol.
  • the monohydric, unsaturated alcohols can also be esterified with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • polybasic carboxylic acids for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • crosslinkers M3 are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
  • amides of unsaturated carboxylic acids such as. B., acrylic and methacrylic acid, itaconic acid, maleic acid, and N-allylamines of at least divalent amines, such as 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diamino-propane, 1,4-diaminobutane, 1, 6-diaminohexane, 1, 12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine.
  • amides of allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or at least dibasic carboxylic acids, as described above.
  • Triallylamine or corresponding ammonium salts for. B. triallylmethylammonium chloride or methyl sulfate, suitable as a crosslinking agent.
  • N-vinyl compounds of urea derivatives at least divalent amides, cyanurates or urethanes, for example of urea, ethylene urea, propylene urea or tartaric acid diamide, e.g. B.
  • N, N'-divinylethyleneurea or N, N'-divinylpropyleneurea can be used.
  • crosslinkers M3 are divinyldioxane, tetraallylsilane or tetravinylsilane.
  • crosslinkers M3 are, for example, methylene bisacrylamide, divinylbenzene, triallylamine and triallylammonium salts, divinylimidazole, N, N'-divinylethyleneurea, reaction products of polyhydric alcohols with acrylic acid or
  • N, N'-Methylenebisacrylamide, diallyl tartaric acid diamide, dialyl phthalate, diallyl urea, glycol di (meth) acrylate, allyl (meth) acrylate and polyallyl ether are very particularly preferred.
  • the water-soluble or water-dispersible polymers according to the invention can contain up to 15% by weight, particularly preferably 0.1 to 10% by weight, of at least one further monomer M4) in copolymerized form.
  • additional monomers are preferably selected from esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with C ⁇ -C 3 o-alkanols, esters of vinyl alcohol and allyl alcohol with C ⁇ -C 3 o-monocarboxylic acids, vinyl aromatics, vinyl halides, vinylidene halides, C 2 -C 8 monoolefins, non-aromatic hydrocarbons with at least two conjugated double bonds, siloxane macromers and mixtures thereof.
  • polymers with primary amino groups bonded to the polymer backbone are capable of polymer-analogous reaction with itaconic acid or itaconic acid derivatives.
  • This polymer-analogous reaction can be formally understood as addition of the amino group to the vinylogous group of itaconic acid and subsequent condensation of the non-vinylogous carboxylic acid group or a derivative thereof with ring closure.
  • the invention therefore furthermore relates to a process for the preparation of a polymer, as previously defined, in which a polymer comprising repeat units of the general formula II
  • the itaconic acid and its derivatives are preferably selected from compounds of the general formula IV
  • X represents 0 or NR 2 , where R 2 represents hydrogen or alkyl
  • R 1 and R 4 are independently hydrogen or alkyl.
  • X is preferably 0. According to a particularly preferred embodiment, itaconic acid is used.
  • the molar ratio of primary amino groups of the polymer to itaconic acid or itaconic acid derivative depends on the desired degree of conversion with respect to the polymer-bound amino groups. For example, it is in a range of 1: 0.01 to 1: 1.2. If the most complete conversion of the polymer-bound amino groups is aimed for, the molar ratio of primary amino groups of the polymer to itaconic acid or itaconic acid derivative is in a range from 1: 1 to 1: 1.2, preferably 1: 1.05 to 1: 1 ; 2.
  • the reaction can be carried out in water or in a mixture of water and at least one water-miscible solvent.
  • Suitable water-miscible solvents are, for example -C-C 4 alkanols, such as ethanol. Water is preferably used as the solvent.
  • the reaction is preferably carried out at a temperature of about 60 to 100 ° C, particularly preferably 80 to 100 ° C. If desired, the reaction can be carried out in two stages, the addition of the A ins to the vinylogous group of itaconic acid being carried out in a first stage at a temperature of about 30 to 40 ° C. and then the ring closure reaction at an elevated temperature in the range of about 80 to 100 ° C takes place.
  • the use of a catalyst can generally advantageously be dispensed with.
  • the number average molecular weight of the polymers according to the invention is preferably about 500 to 100,000, particularly preferably 1000 to 50,000.
  • Another object of the invention is a cosmetic or pharmaceutical composition containing
  • At least one water-soluble or water-dispersible polymer as previously defined, and
  • the cosmetically acceptable carrier B) is preferably selected from
  • water-miscible organic solvents preferably C 1 -C 4 -alkanols
  • esters of C 6 -C 3 o-monocarboxylic acids different from iii) with mono-, di- or trihydric alcohols
  • the agents according to the invention have, for. B. an oil or fat component B), which is selected from: hydrocarbons of low polarity, such as mineral oils; linear saturated hydrocarbons, preferably with more than 8 carbon atoms, such as tetra-decane, 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.
  • hydrocarbons of low polarity such as mineral oils
  • linear saturated hydrocarbons preferably with more than 8 carbon atoms, such as tetra-decane, hexadecane, octadecane, etc .
  • cyclic hydrocarbons such as decahydronaphthalene
  • branched hydrocarbons animal and vegetable oils
  • To grow Wax esters
  • Petroleum jelly Petroleum jelly
  • Esters
  • esters of C ⁇ -C stearate 24 monoalcohols with C ⁇ -C 22 monocarboxylic acids such as Isopropyliso-, n-propyl myristate, iso-propyl myristate, n-propyl palmitate, iso-propyl palmitate, Hexacosanylpalmitat, Octacosanylpalmitat, Triacontanylpalmitat, Dotriacontanylpalmitat, Tetratriacontanyl- palmitate, hexacosanyl stearate, octacosanyl stearate, triacontanyl stearate, dotriacontanyl stearate, tetratriacontanyl stearate;
  • C ⁇ -C 22 monocarboxylic acids such as Isopropyliso-, n-propyl myristate, iso-propyl myristate, n-propyl palm
  • Salicylates such as -CC salicylates, for. B. 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, Cio-Cis-alkyl lactates, etc. and mixtures thereof.
  • Suitable silicone oils B) are e.g. B. linear polydimethylsiloxanes, poly (methylphenylsiloxanes), cyclic siloxanes and mixtures thereof.
  • the number average molecular weight of the polydimethylsiloxanes and poly (methylphenylsiloxanes) is preferably in a range from about 1000 to 150,000 g / mol.
  • Preferred cyclic siloxanes have 4- to 8-membered rings.
  • Suitable cyclic siloxanes are e.g. B. commercially available under the name Cyclomethicone.
  • Preferred oil or fat components B) are selected from paraffin and paraffin oils; Petroleum jelly; natural fats and oils, such as castor oil, soybean oil, peanut oil, olive oil, sunflower oil, semen oil, avocado oil, cocoa butter, almond oil, peach kernel oil, castor oil, cod liver oil, pork lard, walnut, spermacet oil, sperm oil, wheat germ oil, macadamia nut oil, evening primrose oil, evening primrose oil; Fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cetyl alcohol; Fatty acids such as myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid and various saturated, unsaturated and substituted fatty acids; Waxing like beeswax, carnauba wax, Candililla wax, whale 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, Fundamentals and Recipes for Cosmetics, 2nd edition, Verlag Wegig, Heidelberg, pp. 319-355, to which reference is made here.
  • Suitable hydrophilic carriers B) are selected from water, 1-, 2- or polyhydric alcohols with preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol, etc.
  • the cosmetic agents according to the invention can be skin cosmetic, dermatological or hair cosmetic agents.
  • the agents according to the invention are preferably in the form of a (low to high viscosity) solution, a gel, wax, 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 can additionally contain cosmetically and / or dermatologically active agents and auxiliaries.
  • the cosmetic compositions according to the invention preferably contain at least one copolymer A as defined above, at least one carrier B as defined above and at least one constituent different from copolymer A, which is 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 for gelling agents, care agents, coloring agents, tinting agents, tanning agents, dyes, pigments, consistency agents, moisturizers, refatting agents, collagen, protein hydrolyzates, lipids, antioxidants, defoamers, antistatic agents, oiling agents, plasticizers.
  • Suitable cosmetically and / or dermatologically active ingredients are e.g. B. coloring agents, skin and hair pigmentation agents, tinting agents, tanning agents, bleaching agents, keratin-curing agents, antimicrobial agents, light filter agents, repellent agents, hyperemising agents, keratolytic and keratoplastic agents, antidandruff agents Substances, anti-inflammatory drugs, keratinizing substances, anti-oxidative or free radical scavengers, skin moisturizing or moisturizing substances, moisturizing active ingredients, anti-erythematous or anti-allergic active ingredients and mixtures thereof.
  • Artificially tanning agents that are suitable for tanning the skin without natural or artificial radiation with UV rays are, for. B. Dihydroxyacetone, Alloxan and walnut shell extract. Suitable keratin-curing substances are usually
  • Active ingredients such as those used in antiperspirants, such as. As potassium aluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc.
  • 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 affects the formation or intensity of body odor reduced.
  • These include e.g. B. conventional preservatives known to those skilled in the art, such as p-hydroxybenzoic acid ester, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc.
  • deodorizing substances are, for.
  • Suitable light filter agents are substances that absorb UV rays in the UV-B and / or UV-A range.
  • Suitable UV filters are e.g. B. 2,4,6-tri-ryl-l, 3,5-triazines, in which the aryl groups can each carry at least one substituent, which is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and Mixtures of these.
  • Suitable repellent agents are compounds that are able to deter or drive away certain animals, especially insects, from humans. This includes e.g. B. 2-ethyl-l, 3-hexanediol, N, N-diethyl-m-toluamide, etc.
  • Suitable hyperemising substances that stimulate the blood supply to the skin are, for. B.
  • Suitable keratolytic and keratoplastic substances are such.
  • Suitable anti-dandruff agents are, for. B. sulfur, sulfur polyethylene glycol sorbitan monooleate, sulfur ricinol polyethoxylate, zinc pyrithione, aluminum pyrithione, etc.
  • Suitable anti-inflammatory agents that counteract skin irritation are z.
  • the cosmetic compositions according to the invention can contain at least one cosmetically or pharmaceutically acceptable polymer different from compounds of component A) as a cosmetic and / or pharmaceutical active ingredient (as well as optionally as an auxiliary).
  • These generally include anionic, cationic, amphoteric and neutral polymers.
  • anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes, e.g. B. Luviset PUR® from BASF, and polyureas.
  • Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (e.g. Luvimer® 100P), copolymers of ethyl acrylate and methacrylic acid (e.g.
  • Luviumer® MAE copolymers of N-tert.-butylacrylamide, ethyl acrylate, acrylic - Acid (Ultrahold® 8, strong), copolymers of vinyl acetate, crotonic acid and optionally further vinyl esters (e.g. Luviset® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, e.g. B. carboxy-functional, t-butyl acrylate, methacrylic acid (z. B. Luviskol® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as. B.
  • anionic polymers are also vinyl acetate / crotonic acid copolymers, such as are commercially available, for example, under the names Resyn® (National Starch) and Gafset® (GAF) and vinylpyrrolidone / vinyl acrylate copolymers, available, for example, under the Trademark Luviflex® (BASF).
  • Suitable polymers are the vinyl pyrrolidone / acrylate terpolymer available under the name Luviflex® VBM-35 (BASF) and polyamides containing sodium sulfonate or polyester containing sodium sulfonate.
  • Suitable polymers are cationic polymers with the name Polyquaternium according to INCI, z. B. copolymers of vinyl pyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Gare), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ 11 N, copolymers -Vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives (polyquaternium-4 and -10), acrylamidocopolymer (polyquaternium-7) and chitosan.
  • Suitable cationic (quaternized) polymers are also Merquat® (polymer based on dimethyldiallylammonium chloride), Gafquat® (quaternary polymers, which result from the reaction of polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR (hydroxyethyl cellulose with cationic groups) and cationic plant-based polymers, for. B. guar polymers, such as the Jaguar ⁇ brands from Rhodia.
  • polystyrene resins are also 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, polyasole derivatives such as polyasol derivatives derivatives.
  • Suitable polymers include, for example, Luviflex® Swing (partially saponified copolymer of polyvinyl acetate and polyethylene glycol, from BASF).
  • Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinylcaprolactam, e.g. B. Luviskol® Plus (BASF), or polyvinylpyrrolidone and their copolymers, in particular with vinyl esters, such as vinyl acetate, for. B. Luviskol® VA 37 (BASF); Polyamides, e.g. B. based on itaconic acid and aliphatic diamines, such as z. B. are described in DE-A-43 33 238.
  • Suitable polymers are also amphoteric or zwitterionic polymers, such as the octylacrylamide / methyl methacrylate / tert available under the names Amphomer® (National Starch). -Butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers and zwitterionic polymers, such as are disclosed, for example, in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451. Acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali and ammonium salts are preferred zwitterionic polymers.
  • zwitterionic polymers are methacrylic ethyl betaine / 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, e.g. B. polyether siloxanes, such as Tegopren® (from Goldschmidt) or Belsil® (from Wacker).
  • the formulation base of pharmaceutical agents according to the invention preferably contains pharmaceutically acceptable excipients.
  • the excipients known to be usable in the field of pharmacy, food technology and adjacent areas are pharmaceutically acceptable, in particular those used in relevant medicinal products. neibooks (e.g. DAB Ph. Eur. BP NF) and other auxiliaries whose properties do not conflict with physiological application.
  • Suitable auxiliaries can be: lubricants, wetting agents, emulsifying and suspending agents, preservatives, anti-oxidants, anti-irritants, chelating agents, emulsion stabilizers, film-forming agents, gelling agents, odor masking agents, resins, hydrocolloids, solvents, solubilizers, neutralizing agents, permeation accelerators Pigments, quaternary ammonium compounds, refatting and superfatting agents, ointment, cream or oil base materials, silicone derivatives, stabilizers, sterilizers, blowing agents, drying agents, opacifiers, thickening agents, waxes, plasticizers, white oils.
  • a design in this regard is based on professional knowledge, such as that shown in Fiedler, H.P. Lexicon of auxiliaries for pharmacy, cosmetics and related areas, 4th ed., Aulendorf: ECV-Editio-Kantor-Verlag, 1996.
  • the active ingredients can be mixed or diluted with a suitable excipient.
  • Excipients can be solid, semi-solid or liquid materials that can serve as vehicles, carriers or media for the active ingredient. If desired, further auxiliaries are admixed in the manner known to the person skilled in the art.
  • the agents according to the invention are a skin cleanser.
  • Preferred skin cleaning agents are soaps with a liquid to gel-like consistency, such as transparent soaps, luxury soaps, deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, paste-like soaps, lubricating soaps and washing pastes, liquid washing, showering and bathing preparations, such as washing lotions, shower baths and -gels, foam baths, oil baths and scrub preparations.
  • the agents according to the invention are cosmetic agents for the care and protection of the skin, nail care agents or preparations for decorative cosmetics.
  • the skin care products 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, care lotions and moisturizing lotions.
  • the polymers can contribute, among other things, to moisturizing and conditioning the skin and to improving the feeling on the skin.
  • the polymers can also act as thickeners in the formulations. By adding the polymers according to the invention, a considerable improvement in skin tolerance can be achieved in certain formulations.
  • Skin cosmetic and dermatological agents preferably contain at least one copolymer A) in a proportion of approximately 0.001 to 30% by weight, preferably 0.01 to 20% by weight, very particularly preferably 0.1 to 12% by weight, based on the total weight of the agent.
  • Light stabilizers based on copolymers A) in particular have the property of increasing the residence time of the UV-absorbing ingredients in comparison to conventional auxiliaries such as polyvinylpyrrolidone.
  • the agents according to the invention can be used in a form suitable for skin care, such as. B. as a solution, cream, foam, gel, stick, mousse, milk, spray (pump spray or spray containing blowing agent) or lotion.
  • the skin cosmetic preparations can also contain other 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, bleaches, dyes, tinting agents, tanning agents, collagen, protein hydrolyzates, stabilizers, pH regulators , Dyes, salts, thickeners, gelling agents, consistency agents, silicones, humectants, refatting agents and other common additives.
  • 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, bleaches, dyes, tinting agents, tanning agents, collagen, protein hydrolyzates,
  • Preferred oil and fat components of the skin cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as, for. B. paraffins, silicone oils and aliphatic hydrocarbons with more than 8 carbon atoms, animal and vegetable oils, such as. B. sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as. B. triglycerides of C 6 -C 3 o-fatty acids, wax esters, such as. B. jojoba oil, fatty alcohols, petroleum jelly, hydrogenated lanolin and acetylated lanolin and mixtures thereof.
  • mineral and synthetic oils such as, for. B. paraffins, silicone oils and aliphatic hydrocarbons with more than 8 carbon atoms, animal and vegetable oils, such as. B. sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, such as. B. triglycerides of C 6
  • the polymers according to the invention can also be mixed with conventional polymers if special properties are to be set.
  • the skin cosmetic and dermatological preparations can also contain conditioning substances based on silicone compounds.
  • Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
  • the cosmetic or dermatological preparations are produced 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 / 0) or oil-in-water (0 / W) emulsions.
  • W / 0 water-in-oil
  • oil-in-water (0 / W) emulsions it is also possible to choose other types of formulation, 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.
  • 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.
  • 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.
  • suitable emulsion e.g. B. for a skin cream etc.
  • a suitable emulsion e.g. B. for a skin cream etc., generally contains an aqueous phase which is emulsified in an oil or fat phase by means of a suitable emulsifier system.
  • the proportion of the emulsifier system in this type of emulsion is preferably about 4 and 35% by weight, based on the total weight of the emulsion.
  • the proportion of the fat phase is preferably about 20 to 60% by weight.
  • the proportion of the aqueous phase is preferably about 20 and 70%, in each case based on the total weight of the emulsion.
  • the emulsifiers are those which are usually used in this type of emulsion. You will e.g. B.
  • -C ⁇ -C ⁇ g-sorbitan fatty acid esters selected from: -C ⁇ -C ⁇ g-sorbitan fatty acid esters; Esters of hydroxystearic acid and C 2 -C 30 fatty alcohols; Mono- and diesters of C 2 -C fatty acids and glycerol or polyglycerol; Condensates of ethylene oxide and propylene glycols; oxypropylenated / oxyethylated C 2 -C 8 fatty alcohols; polycyclic alcohols such as sterols; high molecular weight aliphatic alcohols such as lanolin; Mixtures of oxypropylene / polyglycerolated alcohols and magnesium isostearate; Succinic esters of polyoxyethylenated or polyoxypropylenated fatty alcohols; and mixtures of magnesium, calcium, lithium, zinc or aluminum lanolate and hydrogenated lanolin or lanolin alcohol.
  • Preferred fat components which can be contained 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, sesame oil, olive oil, jojoba oil, karite oil, hoplostethus oil; mineral oils whose distillation begins at atmospheric pressure at approx. 250 ° C and whose distillation end point is 410 ° C, e.g. B. Vaseline oil; Esters of saturated or unsaturated fatty acids, such as alkyl myristates, e.g. B.
  • the fat phase can also contain silicone oils soluble in other oils, such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
  • waxes can also be used in addition to the polymers A), such as, for example, B. carnauba wax, candililla wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.
  • the water-in-oil emulsions are prepared by placing the fat phase and the emulsifier in a batch container. It is heated at a temperature of about 50 to 75 ° C., then the oil-soluble active ingredients and / or auxiliaries are added and, with stirring, water is added which has previously been heated to about the same temperature and where appropriate the water-soluble ingredients are used beforehand has solved. The mixture is stirred until an emulsion of the desired fineness is obtained and then allowed to cool to room temperature, stirring less if necessary.
  • the agents according to the invention are a shower gel, a shampoo formulation or a bath preparation.
  • Such formulations contain at least one polymer A) and usually anionic surfactants as base surfactants and amphoteric and / or nonionic surfactants as cosurfactants.
  • suitable active ingredients and / or auxiliary substances are generally selected from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants, as well as thickeners / gelling agents, skin conditioners and humectants.
  • formulations preferably contain 2 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight, of surfactants, based on the total weight of the formulation.
  • All anionic, neutral, amphoteric or cationic surfactants commonly used in personal cleansing agents can be used in the washing, showering and bathing preparations.
  • Suitable anionic surfactants include for example alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, Alkylsuc- cinate, alkyl sulphosuccinates, N-Alkoylsarkosinate, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially 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 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.
  • Suitable amphoteric surfactants are e.g. B. alkyl betaines, alkyl amido propyl betaines, alkyl sulfobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or propionates, alkyl amphodiacetates or dipropionates.
  • cocodimethylsulfopropyl betaine 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 with 6 to 20 carbon atoms in the alkyl chain, which can 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.
  • Alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkylpolyglycosides or sorbitan ether esters are also suitable.
  • washing, showering and bathing preparations can contain conventional cationic surfactants, such as. B. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • polyquaternium-7 copolymers of acrylamide and dimethyldiallylammonium chloride
  • cationic cellulose derivatives polyquaternium-4, -10
  • guar hydroxypropyltrimethylammonium chloride INCI: hydroxylpropyl guar hydroxypropyltrimonium chloride
  • copolymers of N-vinylpyrrolidone and quaternium Vinylimidazole polyquaterinium-16, -44, -46
  • copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate polyquaternium-11
  • shower gel / shampoo formulations thickeners such.
  • B table salt, PEG-55, propylene glycol oleates, PEG-120 methyl glucose dioleates and others, and preservatives, other active ingredients and auxiliaries and water.
  • the agents according to the invention are a hair treatment agent.
  • Hair treatment compositions according to the invention preferably contain 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 tonic, foaming agent, hair mousse, hair gel, shampoo, hair spray or hair foam.
  • Hair sprays include both aerosol sprays and pump sprays without propellant.
  • Hair foams include both aerosol foams and pump foams without propellant.
  • Preferred hair treatment agents are in the form of a gel.
  • Such a hair treatment composition contains, for example:
  • At least one refatting agent preferably selected from glycerol and glycerol derivatives
  • the hair treatment compositions can also be in the form of solutions, hair sprays or hair foams.
  • Solutions include, for example, formulations referred to as "forming water” or “styling water”.
  • Hair sprays and hair foams preferably comprise predominantly or exclusively water-soluble or water-dispersible components.
  • the compounds used in the hair sprays and hair foams according to the invention are water-dispersible, they can be in the form of aqueous microdispersions Particle diameters of usually 1 to 350 nm, preferably 1 to 250 nm, can be used.
  • the solids contents of these preparations are usually in a range from about 0.5 to 20% by weight.
  • These microdispersions generally do not require any emulsifiers or surfactants to stabilize them.
  • the hair treatment compositions according to the invention can generally contain customary cosmetic auxiliaries, for example plasticizers, such as glycerol and glycol; emollients; Par 10 foams; surfactants; UV absorbers; dyes; antistatic agents; Combing agents; Preservatives; and defoamers.
  • compositions according to the invention are formulated as a hairspray, they contain a sufficient amount of a blowing agent, for example a low-boiling hydrocarbon or ether, such as propane, butane, isobutane or dimethyl ether. Compressed gases such as nitrogen, air or carbon dioxide can also be used as blowing agents.
  • the amount of blowing agent can be kept low so as not to unnecessarily increase the VOC content. It is then generally not more than 55% by weight, based on the total weight of the composition. If desired, however, higher VOC contents of 85% by weight and above are also possible.
  • polymers A) described above can also be used in combination with other hair polymers in the compositions. Suitable polymers are those described above.
  • the other hair polymers are preferably contained in amounts of up to 30-10% by weight, based on the total weight of the composition.
  • a preferred hair treatment agent in the form of a hair spray or hair foam contains:
  • ren solvents preferably C 2 -Cs alcohols, especially ethanol, and mixtures thereof,
  • NEN such as. B. propane / butane mixtures, d) 0 to 10% by weight, preferably 0.1 to 10% by weight, of at least one hair polymer different from a), preferably a water-soluble or dispersible polymer,
  • the component according to the invention can contain as component e) at least one nonionic, siloxane-containing, water-soluble or water-dispersible polymer, in particular selected from the polyether siloxanes described above.
  • the proportion of this component is then generally about 0.001 to 2% by weight, based on the total weight of the composition.
  • the polymers according to the invention are notable for good biodegradability and good film-forming properties.
  • Another object of the invention is their use, as previously defined, as auxiliary agents in pharmacy, preferably as binders, coating agents and release agents for tablets, solubilizing agents for suspensions and solutions, adsorbents for disinfectants; in food production, preferably as a stabilizer in beverages; as auxiliaries in the textile industry, preferably as peeling and sizing agents; in detergents, preferably as a color transfer inhibitor; in oil production as a gas hydrate inhibitor; in polymer dispersions as protective colloid, emulsifier and / or for modifying the rheological properties; in the paper industry, preferably as or in binders, complexing agents and for modifying the rheological properties; in the agricultural industry, preferably as or in binders and coating agents and as a solubilizer; in adhesives; in membranes and plasters to improve adhesion, hydrophilicity and biocompatibility; in the electronics industry, preferably
  • reaction mixture was then stirred at 100 ° C. for two hours. After distilling off about 25% of the water (about 50 g), the reaction mixture was adjusted to a pH of about 8 with 2-amino-2-methylpropanol (AMP) at a temperature between 30 and 40 ° C. The polymer solution was then added
  • Polyvinylamine desalted polyvinylamine, made by 100% hydrolysis of polyvinylformamide
  • Foam setting agent (Examples 1-4):
  • Phases 1 and 2 are weighed in separately and homogenized. Phase 1 is slowly stirred into phase 2. A clear, pourable gel is formed.
  • Preparation Weigh in and separate phases A and B while stirring and mix. Stir phase B slowly into phase A.

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Abstract

La présente invention concerne des polymères solubles ou dispersibles dans l'eau, comportant des groupes liés à la structure polymère, dérivés de façon formelle d'acides pyrrolidone-4-carboxyliques et de leurs esters et amides. L'invention concerne également des procédés de fabrication de ces polymères, des agents cosmétiques ou pharmaceutiques contenant de tels polymères, ainsi que d'autres utilisations de ces polymères.
PCT/EP2003/014549 2002-12-19 2003-12-18 Polymeres contenant des groupes acide pyrrolidone-4-carboxylique et utilisation WO2004056885A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003293939A AU2003293939A1 (en) 2002-12-19 2003-12-18 Polymer-containing pyrrolidone-4-carboxylic acid groups and the use thereof

Applications Claiming Priority (2)

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DE10259815.0 2002-12-19
DE2002159815 DE10259815A1 (de) 2002-12-19 2002-12-19 Polymere enthaltend Pyrrolidon-4-carbonsäuregruppen und deren Verwendung

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WO2004056885A1 true WO2004056885A1 (fr) 2004-07-08

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2028247A1 (fr) * 2007-08-06 2009-02-25 Clariant International Ltd. Utilisation d'esters d'acide de carbone 1-alkyl-5-oxo-pyrrolidine-3 en tant qu'inhibiteurs d'hydrates de gaz ayant une biodégrabilité améliorée
EP2031035A1 (fr) * 2007-08-06 2009-03-04 Clariant International Ltd. Utilisation de polyethylenimines en tant qu'inhibiteurs d'hydrates de gaz ayant une biodégrabilité améliorée
US7893009B2 (en) 2005-02-12 2011-02-22 Clariant Produkte (Deutschland) Gmbh Polymers and their production and use as gas hydrate inhibitors
US8067651B2 (en) 2007-08-06 2011-11-29 Clariant Finance (Bvi) Limited 1-alkyl-5-oxopyrrolidine-3-carboxylic esters with improved biodegradability
FR2961208A1 (fr) * 2010-06-09 2011-12-16 Oreal Poly 2-pyrrolidones fonctionnalisees par un radical ester, acide ou amide, composition cosmetique les comprenant et leur utilisation comme agent dispersant

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2977156A1 (fr) * 2011-07-01 2013-01-04 Oreal Composition cosmetique comprenant un polysiloxane supramoleculaire et un solvant, et procede de traitement cosmetique
WO2023237717A1 (fr) * 2022-06-10 2023-12-14 Basf Se Auxiliaire de séchage par atomisation pour une poudre de dispersion redispersible

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4418189A (en) * 1980-12-01 1983-11-29 Standard Oil Company (Indiana) Polyamides from itaconic acid and diamines
WO1995009194A1 (fr) * 1993-09-30 1995-04-06 Basf Aktiengesellschaft Polyesters et polyamides contenant des groupes pyrrolidone
GB2305175A (en) * 1995-09-14 1997-04-02 Hyundai Electronics Ind N-Vinyllactam derivatives and photoresist polymers thereof
EP0795567A2 (fr) * 1996-03-13 1997-09-17 Basf Aktiengesellschaft Procédé de préparation de copolymères solubles dans l'eau d'au moins un n-vinyllactam soluble dans l'eau et d'au moins un comonomère hydrophobe
WO2001021671A1 (fr) * 1999-09-20 2001-03-29 Union Carbide Chemicals & Plastics Technology Corporation Derives de poly(amine) amphoteres solubles dans l'eau

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4418189A (en) * 1980-12-01 1983-11-29 Standard Oil Company (Indiana) Polyamides from itaconic acid and diamines
WO1995009194A1 (fr) * 1993-09-30 1995-04-06 Basf Aktiengesellschaft Polyesters et polyamides contenant des groupes pyrrolidone
GB2305175A (en) * 1995-09-14 1997-04-02 Hyundai Electronics Ind N-Vinyllactam derivatives and photoresist polymers thereof
EP0795567A2 (fr) * 1996-03-13 1997-09-17 Basf Aktiengesellschaft Procédé de préparation de copolymères solubles dans l'eau d'au moins un n-vinyllactam soluble dans l'eau et d'au moins un comonomère hydrophobe
WO2001021671A1 (fr) * 1999-09-20 2001-03-29 Union Carbide Chemicals & Plastics Technology Corporation Derives de poly(amine) amphoteres solubles dans l'eau

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7893009B2 (en) 2005-02-12 2011-02-22 Clariant Produkte (Deutschland) Gmbh Polymers and their production and use as gas hydrate inhibitors
EP2028247A1 (fr) * 2007-08-06 2009-02-25 Clariant International Ltd. Utilisation d'esters d'acide de carbone 1-alkyl-5-oxo-pyrrolidine-3 en tant qu'inhibiteurs d'hydrates de gaz ayant une biodégrabilité améliorée
EP2031035A1 (fr) * 2007-08-06 2009-03-04 Clariant International Ltd. Utilisation de polyethylenimines en tant qu'inhibiteurs d'hydrates de gaz ayant une biodégrabilité améliorée
US8067651B2 (en) 2007-08-06 2011-11-29 Clariant Finance (Bvi) Limited 1-alkyl-5-oxopyrrolidine-3-carboxylic esters with improved biodegradability
US8722589B2 (en) 2007-08-06 2014-05-13 Clariant Finance (Bvi) Limited Use of 1-alkyl-5-oxopyrrolidine-3-carboxylic esters as gas hydrate inhibitors with improved biodegradability
FR2961208A1 (fr) * 2010-06-09 2011-12-16 Oreal Poly 2-pyrrolidones fonctionnalisees par un radical ester, acide ou amide, composition cosmetique les comprenant et leur utilisation comme agent dispersant

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AU2003293939A1 (en) 2004-07-14

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