EP1863858A1 - Kationische polymere als verdicker für wässrige und alkoholische zusammensetzungen - Google Patents

Kationische polymere als verdicker für wässrige und alkoholische zusammensetzungen

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Publication number
EP1863858A1
EP1863858A1 EP06743209A EP06743209A EP1863858A1 EP 1863858 A1 EP1863858 A1 EP 1863858A1 EP 06743209 A EP06743209 A EP 06743209A EP 06743209 A EP06743209 A EP 06743209A EP 1863858 A1 EP1863858 A1 EP 1863858A1
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EP
European Patent Office
Prior art keywords
alkyl
acid
polymers
weight
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP06743209A
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German (de)
English (en)
French (fr)
Inventor
Peter Hössel
Klemens Mathauer
Claudia Wood
Matthias Laubender
Wolfgang Jahnel
Ivette Garcia Castro
Volker Wendel
Karl Kolter
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BASF SE
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BASF SE
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Priority claimed from DE102005013037A external-priority patent/DE102005013037A1/de
Priority claimed from DE200510039537 external-priority patent/DE102005039537A1/de
Application filed by BASF SE filed Critical BASF SE
Priority to EP06743209A priority Critical patent/EP1863858A1/de
Publication of EP1863858A1 publication Critical patent/EP1863858A1/de
Withdrawn legal-status Critical Current

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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
    • C08F226/00—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
    • C08F226/06—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 by a heterocyclic ring containing nitrogen
    • 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
    • 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)
    • 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
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • 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
    • A61K8/90—Block copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • 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
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • 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
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—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 of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5426—Polymers characterized by specific structures/properties characterized by the charge cationic
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to the use of a water-soluble or water-dispersible crosslinked polymer obtainable by polymerization of a mixture comprising 99.99 to 10% by weight of at least one ⁇ , ⁇ -ethylenically unsaturated compound having at least one cationogenic and / or cationic group per Molecule, 0 to 90 wt .-% of at least one of a) different monoethylenically unsaturated amide-containing compound and 0.01 to 5 wt .-% of a crosslinker for modifying the rheology of aqueous, alcoholic or aqueous / alcoholic compositions.
  • Polymers are widely used in hair cosmetics. Their task in hair cosmetics is to influence the properties of the hair, in particular to give the hair strengthening, to improve combability and to convey a pleasant grip.
  • conditioners are used to improve dry and wet combability, feel, shine, and appearance, as well as to give the hair antistatic properties. Preference is given to using water-soluble polymers having polar, frequently cationic functionalities which have a greater affinity for the structurally related negative surface of the hair.
  • the structure and mode of action of various hair treatment polymers are described in Cosmetic & Toiletries 103 (1988) 23.
  • Commercially available conditioner polymers are e.g. cationic hydroxyethylcellulose, cationic polymers based on N-vinylpyrrolidone, e.g. Copolymers of N-vinylpyrrolidone and quaternized N-vinylimidazole, acrylamide and diallyldimethylammonium chloride or silicones.
  • hair setting resins are, for example, a strong consolidation in high humidity, elasticity, leachability of the hair, compatibility in the formulation and a pleasant feel of the hair.
  • rheology-modifying agents are also used in pharmaceutical preparations.
  • preparations for topical use such as ointments, creams, gels, emulsions or drops contain viscosity-influencing agents. Also in syrups appropriate funds can be found.
  • Carbopols which must be neutralized for use with inorganic or organic bases, whereby the pH value increases. In the acid there is no sufficient thickening effect.
  • the necessary neutralization of the carbomers also causes problems in the use of active compounds, especially in topical applications.
  • the active ingredients must then be converted in the preparation into their salts, which impedes absorption through the skin resorption.
  • alkaline instable agents such as ascorbic acid tend to decompose in the presence of neutralized carbomers.
  • DD-117,326 (Jeschek, H.) describes a process for increasing the sensitivity and improving the stability of photographic gelatin-silver halide emulsion layers by means of polyethylene glycol derivatives, characterized in that the gelatin-halide silver emulsions and / or their developers graft polymers of polyethylene glycol from the middle Molecular weight 1500-6000 and vinyl compounds containing quaternary nitrogen added. A use for the rheology modification of aqueous compositions is not described.
  • WO 03/080001 (BASF) relates to cationic graft polymers which are obtainable by polymerization of quaternized cationic, free-radically polymerizable monomers and optionally further free-radically copolymerizable monomers in the presence of a polyether-containing compound with the proviso that the reaction in the presence of less than 20 wt. % Water is added to the total reaction mixture.
  • a polyether-containing compound with the proviso that the reaction in the presence of less than 20 wt. % Water is added to the total reaction mixture.
  • the use for rheology modification of aqueous compositions is not described.
  • WO 03/068834 describes the use of graft copolymers as an ingredient in cosmetic products.
  • the graft copolymers are formed by grafting of monoethylenically unsaturated, open-chain N-vinylamide units containing monomers on a polymeric graft.
  • WO 03/106522 describes the use of polyoxyalkylene-substituted alkylenediamines in cosmetic formulations. Also included are modified polyoxyalkylene-substituted alkylenediamines, in particular cationic polymers, and processes for their preparation. The polymers contain at least 40% by weight of polyoxyalkylene-substituted alkylenediamines.
  • WO 04/100910 describes cosmetic compositions which comprise at least one polymer obtainable by free-radical polymerization of ⁇ , ⁇ -ethylenically unsaturated compounds which in each case contain at least one nitrogen-containing heterocycle in the presence of a polymeric graft base.
  • vinylpyrrolidone-vinylimidazole copolymers prepared in the presence of polyethylene glycol are described.
  • water is used as the solvent, the polymers are not crosslinked and are not used for rheology modification.
  • WO 03/042262 (BASF) relates to graft polymers comprising a polymeric graft base (A) which has no monoethylenically unsaturated units, and polymeric side chains (B) formed from copolymers of two different monoethylenically unsaturated monomers (B1) and (B2), each contain at least one nitrogen-containing heterocycle, wherein the proportion of the side chains (B) in the Bac- lymerisat 35 to 55 wt .-%. In the polymerization is used as a solvent
  • WO 03/042264 differs from that of WO 03/042262 in that the proportion of side chains (B) in the overall polymer is more than 55% by weight.
  • WO 93/22380 discloses hydrogels, adhesives and coatings comprising crosslinked copolymers of 80-99% by weight of N-vinylpyrrolidone and 1 to 20% by weight N-vinylimidazole or 4-vinylpyridine prepared by solution polymerization in water.
  • hair cosmetic compositions comprising (i) polymer obtainable by free-radically initiated polymerization of (a) from 1 to 100% by weight, preferably from 2 to 95% by weight, in particular from 10 to 70% by weight .-%, at least one cationic monomer selected from N-vinylimidazoles and diallylamines, optionally in partially or completely quaternized form, (b) 0 to 99 wt .-%, preferably 5 to 98 wt .-%, in particular 30 to 90 wt.
  • US Pat. No. 4,806,345 describes crosslinked cationic thickeners for cosmetic formulations of quaternized dimethylaminoethyl methacrylate and acrylamide.
  • WO 93/25595 describes crosslinked cationic copolymers based on quaternized dialkylaminoalkyl acrylates or dialkylaminoalkylacrylamides. As an application, the use of these crosslinked copolymers as thickeners in cosmetic preparations is proposed.
  • WO 96/37525 describes the preparation of crosslinked copolymers of i.a.
  • N-vinylpyrrolidone and quaternized vinylimidazoles in the presence of polymerization regulators and their use especially in detergents.
  • US Pat. No. 4,058,491 discloses crosslinked cationic hydrogels of N-vinylimidazole or N-vinylpyrrolidone and a quaternized basic acrylate and further comonomers. These gels are proposed for the complexation and controlled release of anionic active substances.
  • WO 97/35544 describes the use of crosslinked cationic polymers with dialkylaminoalkyl (meth) acrylates or - (meth) acrylamides in shampoo compositions.
  • EP A 0 893 117 and EP 1 064 924 describe the use of high molecular weight crosslinked cationic polymers as solution polymers. These have a good conditioning effect in shampoos.
  • compositions of the active ingredient diclofenac which contain neutralized as a thickener with secondary organic amines carbomer.
  • EP-A 450 123 describes diclofenac sodium-containing compositions for topical application which contain cellosolve derivatives as thickeners in order to avoid the disadvantages associated with neutralization with secondary organic amines.
  • the polymers to be provided should furthermore ensure a high stability of the resulting compositions to salts and should also be compatible with the cosmetically customary polymers in the pH range from 5 to 8.
  • the polymers enable effective modification of the rheology even over the broadest possible pH range.
  • the polymers should be accessible inexpensively, and require as little as possible refurbishment after their preparation.
  • a further object of the invention was the provision of polymers as thickeners for pharmaceutical preparations, in particular for preparations for topical application.
  • the task was particularly concerned with the provision of polymers which have a thickening effect over a wide pH range of 1 to 10.
  • the object was also to find thickening agents for pharmaceutical preparations, which develop a sufficient effect even in small concentrations.
  • the polymers to be provided should also help to avoid the problem of salt formation in active-ingredient acids.
  • the aim of the present invention was also to find gel formulations for substances sensitive to the basic or neutral environment.
  • d) 0 to 15% by weight of at least one monoethylenically unsaturated compound d1) containing at least one group selected from the group consisting of optionally substituted C5-C30-alkyl, C5-C30-alkenyl, C5-C8-cycloalkyl, aryl, Arylalkyl and hetaryl,
  • T 0 to 70 wt .-%, based on the sum of the components a) to e) of a polyether-containing compound
  • the polymerization being conducted in the presence of less than 69% by weight of cyclohexane and less than 12% by weight of water, based on the total amount of all components present during the polymerization, and in the absence of supercritical carbon dioxide,
  • a preferred embodiment of the invention is the use of the aforementioned polymers, wherein the ⁇ , ß-ethylenically unsaturated compound a) is selected from
  • esters of .alpha.,. beta.-ethylenically unsaturated mono- and dicarboxylic acids with aminoalkoxy groups which may be mono- or dialkylated on the amine nitrogen,
  • alkyl includes straight-chain and branched alkyl groups.
  • Suitable short-chain alkyl groups are, for example, straight-chain or branched C 1 -C 7 -alkyl, preferably C -C 6 -alkyl and particularly preferably C 1 -C 4 -alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl,
  • Suitable longer-chain C 8 -C 30 -alkyl or C 8 -C 30 -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.
  • Cycloalkyl is preferably C 5 -C 8 -cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • heterocycloalkyl in the context of the present invention comprises saturated, cycloaliphatic groups having generally 4 to 7, preferably 5 or 6 ring atoms, in which 1 or 2 of the ring carbon atoms are replaced by heteroatoms selected from the elements oxygen, nitrogen and sulfur, and the optionally substituted, wherein in the case of a substitution, these heterocycloaliphatic groups 1, 2 or 3, preferably 1 or 2, particularly preferably 1 substituent selected from alkyl, aryl, COOR, COO " M + and NE 1 E 2, preferably alkyl, carrying can.
  • heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethyl-piperidinyl, imidazolidinyl, pyrazolidinyl, oxazoline lidinyl, Morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl Tetrahydrofuranyl, tetrahydropyranyl, dioxanyl.
  • 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.
  • Substituted aryl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3 substituents selected from alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, - SO 3 H, sulfonate, NE 1 E 2 , alkylene NE 1 E 2 , nitro, cyano or halogen.
  • Hetaryl preferably represents pyrrolyl, pyrazolyl, imidazolyl, indolyl, carbazolyl, pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.
  • Arylalkyl represents groups which contain both alkyl and aryl radicals, these arylalkyl groups being linked either via the aryl or via the alkyl radical to the compound carrying them.
  • Suitable cationogenic monomers a) are ai) the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with aminoalcohols.
  • Preferred amino alcohols are C 2 -C 2 -aminoalcohols which are C 1 -C 8 -IDOnO- or -dialkylated on the amine nitrogen.
  • Suitable acid components of these esters are, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof.
  • Suitable monomers a) are furthermore aii) the amides of the abovementioned ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group.
  • diamines having a tertiary and a primary or secondary amino group.
  • Preferred acid components are acrylic acid, methacrylic acid and mixtures thereof.
  • esters ai) or amides aii) of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols or diamines are therefore aminoalkyl (meth) acrylates and aminoalkyl (meth) acrylamides of the general formula I:
  • R 14 and R 15 are independently selected from the group consisting of hydrogen, C 1 -C 8 linear or branched chain alkyl, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl. Preference is given to hydrogen, methyl or ethyl, R 17 is hydrogen or methyl, R 18 is alkylene or hydroxyalkylene having 1 to 24 C atoms, optionally substituted by alkyl, preferably C 2 H 4 , C 3 H 6 , C 4 H 8 , CH 2 is -CH (OH) -CH 2 , g is 0 or 1,
  • R 25 and R 26 are each and independently selected from the group consisting of hydrogen, C 1 -C 40 linear or branched chain alkyl,
  • Preferred as monomers ai) are in particular
  • the monomers used are ai) N- (tert-butyl
  • the amides may be unsubstituted, N-alkyl or N-alkylamino monosubstituted or N, N-dialkyl substituted or N, N-dialkylamino-disubstituted wherein the alkyl or alkylamino groups are C 1 -C 40 linear, C 3 -C 40 branched chain, or C 3 -C 40 carbocyclic units are derived.
  • the cationogenic monomer a) may also be selected from aiii) N 1 N-diallylamines of the general formula II
  • R 27 is hydrogen or Ci to C 24 alkyl.
  • N 1 N-diallylamine and N, N-diallyl-N-methylamine in particular N, N-diallyl-N-methylamine.
  • N, N, -diallyl-N-methylamine which is commercially available in a quaternized form, for example under the name DADMAC (diallyldimethylammonium chloride).
  • Particularly preferred cationogenic monomers a) are further aiv) vinyl- and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinylimidazole derivatives, e.g. N-vinyl-2-methylimidazole, vinyl- and allyl-substituted heteroaromatic compounds such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine.
  • N-vinylimidazole N-vinylimidazole derivatives, e.g. N-vinyl-2-methylimidazole
  • vinyl- and allyl-substituted heteroaromatic compounds such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine.
  • N-vinylimidazoles of the general formula (III) in which R 1 to R 3 are hydrogen, C 1 -C 4 -alkyl or phenyl
  • the monomer a) is aiv) N-vinylimidazole, ie the compound of the formula III, where all radicals R 1 to R 3 are hydrogen.
  • the reaction of the compounds a) to quaternary compounds may take place during or preferably after the reaction.
  • the intermediate polymer can first be isolated and purified or reacted immediately.
  • the implementation can be complete or partial. In this case, preferably at least 10%, more preferably at least 20%, most preferably at least 30% of the incorporated monomers a) are converted into the corresponding quaternary form.
  • the proportion of conversion to quaternary compounds is preferably higher, the lower the water solubility of the monomer a).
  • the monomers a) in predominantly, ie more than 70, preferably more than 90, more preferably more than 95, most preferably more than 99 mol% in cationogenic, that is not quaternized or protonated form for the polymerization to use and only during or especially preferably after the polymerization by quaternization in the quaternized or protonated form to convert.
  • the polymer is partially or completely protonated or quaternized only during or particularly preferably after the polymerization, since the monomer a) used is preferably a non-quaternized or only partially quaternized or protonated monomer for the polymerization.
  • the monomers (a) can be used either in protonated or quaternized form or preferably be polymerized non-quaternized or non-protonated, which in the latter case either quaternized or protonated the resulting copolymer during or preferably after the polymerization for the inventive use.
  • the monomers are used in quaternized form, they can be either as a dried substance or in the form of concentrated solutions in solvents suitable for the monomers, for example in polar solvents such as water, methanol, ethanol, acetone, in the other components a ) to f), if they are suitable as solvents or use in electrolyte solutions.
  • solvents suitable for the monomers for example in polar solvents such as water, methanol, ethanol, acetone, in the other components a ) to f), if they are suitable as solvents or use in electrolyte solutions.
  • Suitable protonation are, for example, mineral acids such as HCl, H 2 SO 4 , and monocarboxylic acids such as formic acid and acetic acid, dicarboxylic acids and polyfunctional carboxylic acids, eg oxalic acid and citric acid, and all other proton-donating compounds and substances which are capable of the corresponding Protonate nitrogen atom.
  • mineral acids such as HCl, H 2 SO 4
  • monocarboxylic acids such as formic acid and acetic acid
  • dicarboxylic acids and polyfunctional carboxylic acids eg oxalic acid and citric acid
  • all other proton-donating compounds and substances which are capable of the corresponding Protonate nitrogen atom are capable of the corresponding Protonate nitrogen atom.
  • water-soluble acids are suitable for protonation.
  • Preferred inorganic acids are phosphoric acid, phosphorous acid, sulfuric acid, sulfurous acid and hydrochloric acid, with phosphoric acid being particularly preferred.
  • Possible organic acids are mono- and polyhydric, optionally substituted aliphatic and aromatic carboxylic acids, mono- and polyhydric, optionally substituted aliphatic and aromatic sulfonic acids or mono- and polyhydric, optionally substituted aliphatic and aromatic phosphonic acids.
  • Preferred organic acids are hydroxycarboxylic acids such as glycolic acid, lactic acid, tartaric acid and citric acid, with lactic acid being particularly preferred.
  • the protonation of the polymer takes place either during, immediately after the polymerization or only during the formulation of the cosmetic preparation, in which a physiologically acceptable pH is generally set.
  • protonation is meant that at least a portion of the protonatable groups of the polymer, preferably at least 20, preferably more than 50, more preferably more than 70, most preferably more than 90 mole%, is protonated so that a total cationic charge of the polymer results.
  • alkyl halides having 1 to 24 carbon atoms in the alkyl group e.g. Methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride, propyl bromide, hexyl bromide, dodecyl bromide, lauryl bromide and benzyl halides, especially benzyl chloride and benzyl bromide.
  • Preferred quaternizing agent is methyl chloride.
  • the corresponding alkyl bromides such as hexyl bromide, dodecyl bromide or lauryl bromide are preferred.
  • quaternizing agents are dialkyl sulfates, in particular dimethyl sulfate or diethyl sulfate.
  • the quaternization of the basic monomers a) can also be carried out with alkylene oxides such as ethylene oxide or propylene oxide in the presence of acids.
  • Preferred quaternizing agents are methyl chloride, dimethyl sulfate or diethyl sulfate, with methyl chloride being particularly preferred.
  • the quaternization of the monomers or polymers with one of the quaternizing agents mentioned can be carried out by generally known methods.
  • the polymers can be used according to the invention for modifying the rheology of aqueous compositions in the pH range from 1 to 12, preferably from 2 to 10.
  • the quaternizable groups of the polymers are quaternized to less than 20%, preferably less than 10%, particularly preferably less than 1%.
  • the quaternizable groups of the polymers In the range of pH 6 to pH 10, it is advantageous for the quaternizable groups of the polymers to be present at least 10%, preferably at least 20% and at most 99, preferably at most 90 quaternized.
  • the polymers can advantageously be either partially quaternized or not quaternized.
  • the polymer suitable for the use according to the invention contains at most 99.99 and at least 10, preferably at least 30 and in particular at least 60% by weight of the monomers a) in copolymerized form.
  • a proportion of at least 60, preferably at least 70 wt .-% of polymerized monomers a) is advantageous.
  • the polymer contains only monomers a) and c) in copolymerized form.
  • the polymer suitable for the use according to the invention contains from 0 to 90, preferably from 10 to 70, and particularly preferably from 30 to 60,% by weight of at least one of a) different monoethylenically unsaturated amide-containing compound b).
  • This further monomer b) is preferably selected from compounds of the general formula IV
  • the polymer used according to the invention additionally contains in copolymerized form as monomer b) at least one N-vinyllactam.
  • N-vinyl lactam b) are unsubstituted N-vinyllactams and N-vinyllactam, for example, one or more C r C 6 alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, Butyl, etc., may have.
  • N-vinylpyrrolidone N-vinylpiperidone, N-vinylcaprolactam
  • N-vinyl-5-methyl-2-pyrrolidone N-vinyl-5-ethyl-2-pyrrolidone
  • N-vinyl-6-methyl-2-piperidone N-vinyl-6-ethyl-2-piperidone
  • N-vinyl-7-methyl-2-caprolactam N-vinyl-7-ethyl-2-caprolactam, etc., and mixtures thereof.
  • N-vinylpyrrolidone N-vinylcaprolactam
  • N-vinylformamide N-vinylformamide
  • (meth) acrylamide is particularly preferred.
  • the polymer suitable for the use according to the invention comprises only monomers a) and b) incorporated, with N-vinylimidazole being preferred as a) and N-vinylpyrrolidone being preferred as b).
  • the polymer suitable for the use according to the invention contains at most 90, preferably at most 70 and in particular at most 40 wt .-% of the monomer or monomers b) in copolymerized form. In one embodiment of the invention, the polymer suitable for the use according to the invention contains at least 1, particularly preferably at least 10 and in particular at least 20% by weight of the monomer or monomers b) in copolymerized form.
  • the crosslinker c) used to prepare the polymers suitable for the use according to the invention is selected from compounds having at least 2 ethylenically unsaturated, non-conjugated double bonds per molecule.
  • Suitable crosslinkers c) are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols.
  • the OH groups of the underlying ing alcohols may be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.
  • Examples of the underlying alcohols are dihydric alcohols such as 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 2,3-butanediol, 1,4-butanediol , But-2-ene-1,4-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-methylpentan-1, 5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanedio
  • Examples of underlying alcohols having 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.
  • Preferred polyhydric alcohols in this context are also di- and trisaccharides.
  • polyhydric alcohols can also be used after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates.
  • the polyhydric alcohols can also be first converted by reaction with epichlorohydrin in the corresponding glycidyl ether.
  • crosslinkers are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C 3 - to C 6 -carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octene-3-ol, 9-decene-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamyl alcohol , Citronellol, crotyl alcohol or cis-9-octadecen-1-ol.
  • esterify the monohydric, unsaturated alcohols with polybasic carboxylic acids for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • crosslinkers are esters of unsaturated carboxylic acids with the above-described polyhydric alcohols, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
  • Suitable crosslinkers c) are also straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which may not be conjugated in aliphatic hydrocarbons, for example divinylbenzene, divinyltoluene, 1,7-octadiene, 1, 9 -Decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights from 200 to 20,000.
  • crosslinkers are the amides of (meth) acrylic acid, itaconic acid and maleic acid and also N-allylamines of at least difunctional amines.
  • Such amines are for example 1, 2-diamino-methane, 1, 2-diaminoethane, 1, 3-diaminopropane,
  • 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 and triallylmonoalkylammonium salts e.g. Triallylmethylammonium chloride or methylsulfate, suitable as a crosslinker.
  • N-vinyl compounds of urea derivatives at least difunctional amides, cyanurates or urethanes, for example of urea, ethyleneurea, propyleneurea or tartaramide, e.g. N, N'-divinylethyleneurea or N, N'-divinylpropyleneurea.
  • alkylenebisacrylamides such as methylenebisacrylamide and N 1 N'-(2,2) are suitable butane, and 1, 1 '-bis- (3,3'-vinylbenzimidazolith-2-one) -1, 4-butane.
  • crosslinkers are, for example, alkylene glycol di (meth) acrylates, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol acrylate, tetraethylene glycol dimethacrylate, diethylene glycol acrylate, diethylene glycol methacrylate, vinyl acrylate, allyl acrylate, allyl methacrylate, divinyldioxane, pentaerythritallyl ethers and mixtures of these crosslinkers.
  • alkylene glycol di (meth) acrylates such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol acrylate, tetraethylene glycol dimethacrylate, diethylene glycol acrylate, diethylene glycol methacrylate, vinyl acrylate, allyl acrylate, allyl methacrylate, divinyldioxane, pentaerythritallyl ethers and mixtures of
  • crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane.
  • Crosslinkers used with particular preference are, for example, methylenebisacrylamide, triallylamine and triallylalkylammonium salts, divinylimidazole, pentaerythritol triallyl ether, N, N'-divinylethyleneurea, reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic acid esters and acrylic esters of polyalkylene oxides or polyhydric alcohols which are reacted with ethylene oxide and / or propylene oxide and / or epichlorohydrin have been reacted.
  • crosslinkers are pentaerythritol triallyl ether, methylenebisacrylamide, N, N'-divinylethyleneurea, triallylamine and triallylmonoalkylammonium salts, and acrylic esters of ethylene glycol, butanediol, trimethylolpropane or glycerol or acrylic esters of glycol, butanediol, trimethylolpropane reacted with ethylene oxide and / or epichlorohydrin or glycerin.
  • pentaerythritol triallyl ether is pentaerythritol triallyl ether.
  • the crosslinker is preferably soluble in the reaction medium. If the solubility of the crosslinker in the reaction medium is low, it can be dissolved in a monomer or in a monomer mixture or else be metered in dissolved in a solvent which mixes with the reaction medium. Particularly preferred are those crosslinkers which are soluble in the monomer mixture.
  • crosslinkers c) are used for the inventive use in amounts of at least 0.01, preferably at least 0.05, more preferably at least 0.1 and at most 5, preferably at most 2 and more preferably at most 1 wt .-%.
  • pentaerythritol triallyl ether is added in an amount of from 0.1% to 0.7% by weight, most preferably in an amount of from 0.3% to 0.6% by weight. % used.
  • the weight% amount of crosslinker c) refers to the amount of the mixture of components a) to e) used to prepare the polymer.
  • the mixture to be polymerized further comprises 0 to 15% by weight of at least one monoethylenically unsaturated compound d1) containing at least one group selected from the group consisting of optionally substituted, C 5 -C 30 alkyl, C 5 -C 3 o- Alkenyl, C 5 -C 8 -cycloalkyl, aryl, arylalkyl and hetaryl and / or a reactive precursor (d2) of component d).
  • Compound d) carries a hydrophobic group in the polymer suitable for the use according to the invention.
  • the compounds d1) it may be per se hydrophobic monomers, such as esters or amides of (meth) acrylic acid with aliphatic C 5 - C 30 - or alcohols or amines such as hexyl (meth) acrylate or - ( meth) acrylamide, n-heptyl (meth) acrylate or - (meth) acrylamide, n-octyl (meth) acrylate or - (meth) acrylamide, n-nonyl (meth) acrylate or - (meth) acrylamide, n decyl (meth) acrylate or - (meth) acrylamide, n-undecyl (meth) acrylate or - (meth) acrylamide, n-dodecyl (meth) acrylate or - (meth) acrylamide, n-tridecyl (meth) acrylate or - (meth ) acryl
  • the compounds d1) may also be, for example, hydrophobic-substituted (meth) acrylates of polyalkylene glycols, for example alkyl-substituted (meth) acrylic acid-polyethylene glycol esters.
  • Suitable as d1) are also long-chain allyl or vinyl ethers such as C 5 -C 3 O-alkyl vinyl ethers or C 5 -C 3 o-alkenyl vinyl ethers.
  • Suitable as d1) are also free-radically polymerizable, olefinically unsaturated group-containing derivatives of polyisobutene.
  • Preferred compounds d1) thereof are, for example, reaction products of polyisobutene succinic anhydride (PIBSA) with hydroxyalkyl (meth) acrylates and polyisobutene succinimide (PIBSA) with hydroxyalkyl (meth) acrylates
  • WO 04/035635 page 12, Z.26 to S.27, Z.2 describes in detail processes for the preparation of polyisobutene derivatives which are then converted by conventional reactions with components containing the olefinically unsaturated groups to give suitable compounds d) can be.
  • This description is hereby incorporated by reference.
  • polyisobutene derivatives are for example the products BASF) are each commercially available under the tradenames Glissopal ® or Kerocom ® (.
  • the compounds d) used are 2 to 10% by weight of octadecyl vinyl ether and / or behenyl acrylate and / or stearyl methacrylate.
  • esters of (meth) acrylic acid with polyethylene glycol mono-C 16 -C 22 - alkylethem.
  • Preferred polyethylene glycol mono C 16 -C 22 alkyl ethers contain from 25 to 80 units of ethylene oxide per molecule.
  • acrylic acid with Lutensol ® AT 25, Lutensol ® AT 50 or Lutensol ® AT 80 are used as compounds d) esters of (meth).
  • methacrylic acid esters of ethoxylated (for example, with 25 mol of ethylene oxide) C 16 - C 18 -Fettalkoholgemischen as 0- 6877 or PLEX ® 0-6954 (Degussa) are commercially available for example as PLEX ®.
  • reactive dyestuffs d2) of component d) are understood as meaning those radically polymerizable monomers which, before or after their copolymerization, are reacted with an optionally polymer-analogous reaction with at least one group selected from the group consisting of optionally substituted C 5 - C 3 o-alkyl, C 5 -C 3 o-alkenyl, C 5 -C 8 -cycloalkyl, aryl, arylalkyl and hetaryl can be covalently linked. Examples which may be mentioned are monoethylenically unsaturated compounds which carry an epoxide group. This epoxide can, for example, by the polymerization into a polymer by reaction with C 5 -C 30 - alcohols having a C 5 -C 30 -alkyl ky I chain are covalently linked.
  • Further preferred compounds d) are selected from the group consisting of C 8 -C 30 -alkyl (meth) acrylates and C 18 -C 30 -alkyl vinyl ethers.
  • the polymer suitable for the use according to the invention contains at most 20, preferably at most 15 and more preferably at most 10 and preferably at least 1, particularly preferably at least 2 and in particular at least 4% by weight of one or more of the compounds d).
  • a proportion of at least 2, preferably at least 4% by weight of polymerized component d) is advantageous.
  • the polymer suitable for the use according to the invention is obtainable by polymerization in the presence of from 0 to 70% by weight, based on the amount of components a) to e), of a polyether-containing compound T).
  • Suitable polyether-containing compounds T) are generally water-soluble or water-dispersible, nonionic polymers which have polyalkylene glycol groups.
  • the proportion of polyalkylene glycol groups is preferably at least
  • polyether-containing compound T for example, polyalkylene glycols, polyesters based on polyalkylene glycols and polyether urethanes can be used.
  • component T) are preferably polyethers from the group of polyalkylene oxides based on ethylene oxide, propylene oxide and butylene oxides, polytetrahydro- furan and polyglycerol.
  • the polyether-containing compounds f) contain the following structural units:
  • R a is C 1 -C 24 alkyl, preferably C 1 -C 4 alkyl.
  • the compounds f) can additionally have bridging groups, which are selected, for example, under:
  • R b and R c are independently hydrogen, C r C 3 o-alkyl, preferably C 1 -C 4 -alkyl, or cycloalkyl.
  • the polyethers f) have a number average molecular weight M n of at least 300.
  • the polyethers f) preferably have the general formula Va or Vb
  • R 7 is hydroxy, amino, C r C 24 alkoxy, R, R 13 -NH-COO- or a polyalkylene stands 13 -COO- koholrest,
  • R 12 is a C 1 -C 2 o-alkylene group whose carbon chain may be interrupted by 1 to 10 non-adjacent oxygen atoms;
  • R 13 is C r C 24 -alkyl
  • R 14 is hydrogen, C r C 24 -alkyl or R 13 -CO-,
  • B is - (CH 2 ) r, if desired substituted cycloalkylene, if desired substituted heterocycloalkylene or optionally substituted arylene,
  • n 1 or, if R 7 is a polyalcohol radical, 1 to 8,
  • s is 0 to 500, preferably 0 to 100,
  • t is 1 to 12, preferably 2 to 6,
  • each independently of one another represents from 1 to 5,000, preferably from 1 to 1,000,
  • Preferred components f) are the polyethers of the formula Va.
  • terminal primary hydroxyl groups of the polyethers prepared on the basis of alkylene oxides, tetrahydrofuran or glycerol and the secondary OH groups of polyglycerol can be present both free etherified 24 alcohols with C r C esterified with C r C 24 carboxylic acids or with Isocyanates be converted to urethanes.
  • suitable alcohols for this purpose are: primary aliphatic alcohols, such as methanol, ethanol, propanol and butanol, primary aromatic alcohols, such as phenol, isopropylphenol, tert-butylphenol, octylphenol, nonylphenol and naphthol, secondary aliphatic alcohols, such as isopropanol, tertiary aliphatic alcohols Alcohols, such as tert-butanol and polyhydric alcohols, for example diols, such as ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol and butanediol, and triols, such as glycerol and trimethylolpropane.
  • primary aliphatic alcohols such as methanol, ethanol, propanol and butanol
  • primary aromatic alcohols such as phenol, isopropylphenol, tert-butylphenol, octylphenol,
  • the hydroxyl groups can also be replaced by reductive amination, for example with hydrogen-ammonia mixtures under pressure against primary amino groups or be converted by cyanethylation with acrylonitrile and hydrogenation in Aminopropylenendgrup- pen.
  • the closure of the hydroxyl end groups can be carried out not only subsequently by reaction with the alcohols or with alkali metal, amines and hydroxylamines, but these compounds can be used as Lewis acids, such as boron trifluoride, even at the beginning of the polymerization as a starter.
  • the hydroxyl groups can also be closed by reaction with alkylating agents, such as dimethyl sulfate.
  • alkyl radicals in the formulas Va and Vb can be branched or unbranched C 1 -C 24 -alkyl radicals, as defined above, where preferred and C ⁇ Ce-alkyl radicals are particularly preferred.
  • the average molecular weight M n of the polyethers is at least 300 and at most 100,000. It is preferably 500 to 50,000, more preferably 2,000 to 35,000, and most preferably 2,000 to 10,000.
  • polytetrahydrofurans homo- and copolymers of ethylene oxide, propylene oxide, butylene oxide and isobutylene oxide, which may be linear or branched, are advantageously used as the graft base b).
  • the term homopolymers should also include those polymers which, in addition to the polymerized alkylene oxide unit, also contain the reactive molecules which were used to initiate the polymerization of the cyclic ethers or to close the end groups of the polymer.
  • Preferred compounds f) are for example those polyether-containing compounds, BASF), Lupranol TM (Elastogran) or PolyTHF ® (BASF) are each commercially available under the trade names Pluriol TM, Pluronic TM, Lutensol TM, Pluracol TM and Plurafac TM (.
  • polyol macromers can also be used as component f).
  • Such polyol macromers are known in the art.
  • the polymerization is carried out in the presence of polyalkylene oxide-containing silicones as compounds f).
  • Suitable polyalkylene oxide-containing silicones are described, for example, in the following documents, the disclosure of which is hereby incorporated by reference:
  • DE-PS 16 94 366 It relates to polysiloxane-polyoxyalkylene block copolymers whose polysiloxane block is constructed in a conventional manner and their polyoxyalkylene block alkylene block of 25 to 70 weight percent of a polyoxyalkylene having an average molecular weight of 1600 to 4000 and an ethylene oxide content of 20 to 100 weight percent, balance propylene oxide and optionally higher alkylene oxides, and 30 to 75 weight percent of a polyoxyalkylene having an average molecular weight of 400 to 1200 and an ethylene oxide content from 65 to 100 weight percent, balance propylene oxide and optionally higher alkylene oxides exists.
  • the polysiloxane-polyoxyalkylene block copolymers are defined with respect to their Polyoxyalkylenblöcke that one polyoxyalkylene block has an average molecular weight of 900 to 1300 and to 30 to 55 wt .-% of ethylene oxide, the remainder of propylene oxide, and the other Polyoxyalkylenblock has an average molecular weight of 3800 to 5000 and consists of 30 to 50 wt .-% of ethylene oxide, the remainder of propylene oxide.
  • EP-A 0 275 563 The described block copolymer comprises three different polyoxyalkylene blocks, namely one block which contains 20 to 60% by weight of oxyethylene units, with a molecular weight of 3,000 to 5,500, another block of 20 to 60% by weight. % Oxyethylene units and a molecular weight of 800 to 2900 and a third block only of polyoxypropylene units and having a molecular weight of 130 to 1200.
  • EP-A 0 670 342 describes on p. 3, Z.22 to p.4, Z.56 polysiloxanes having 1) at least two polyether radicals A and B, where the polyoxyalkylene radical A having a mean molecular weight of 600 to 5500 from 20 to 100 wt .-% oxyethylene units and 80 to 0 wt .-% of oxypropylene units, and the polyoxyalkylene radical B having an average molecular weight of 700 to 5000 from 0 to ⁇ 20 wt .-% of oxyethylene units and 100 to 80 wt .-% of oxypropylene units and 2) Si-bonded hydrocarbon radicals of 6 to 30 carbon atoms.
  • silicone derivatives are the compounds known polyols under the INCI-name Dimethicone copolymer or silicone surfactants such as those available under the trade names Abil ® (Goldschmidt), Alkasil ® (Rhone-Poulenc), Silicone Polyol copoly mer ® (Genesee), Belsil ® (Wacker), Silwet ® (Witco) or Dow Corning ® (Dow Corning) available These include compounds with CAS numbers 64365-23-7; 68937-54-2; 68938-54-5; 68937-55-3.
  • Particularly suitable silicone derivatives are the compounds described in WO 99/04750 p. 10, Z.24 to P.12, Z.8 and P.13, Z.3 to Z.34.
  • WO 01/013884 p. 24, Z.22 to p. 26, Z.41 describes further particularly preferred polyalkylene oxide-containing silicones.
  • the prior art references and citations are fully incorporated by reference.
  • Particularly preferred is the polymerization of the mixture of components a) to e) in the presence of, based on the total amount of components a) to e), 5 to 25 wt .-% polyethylene glycol having molecular weight M n of at least 2000 to at most 35000, preferably at most 10,000 and / or 5 to 25 wt .-% esters of (meth) acrylic acid with polyethylene glycol mono-C 6 -C 22 -alkyl ethers.
  • the polymerization of the mixture of components a) to e) is preferably carried out in the presence of at most 50, more preferably at most 40 wt .-% of component f), based on the sum of the amounts of components a) to e).
  • the polymerization of the mixture of the components a) to e) is in the presence of 5 to 70, preferably 10 to 50, particularly preferably 20 to 40 wt .-% of component f) based on the sum of Amounts of components a) to e) performed.
  • the polymers suitable for the use according to the invention may contain, in copolymerized form, from 0 to 30% by weight of further monoethylenically unsaturated compounds which are different from a) to d).
  • these other monomers e) are selected from esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with CrC 3 o-alkanols, C 2 -C 30 -alkanediols and C 2 -C 3 o-aminoalcohols, amides ⁇ , ⁇ -ethylenic unsaturated mono- and dicarboxylic acids with C 2 -C 3 o-diamines and C 2 -C 30 -amino alcohols having a primary or secondary amino group, amides of ⁇ , ß-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, N-vinylamides of saturated monocarboxylic acids, esters of vinyl alcohol and allyl alcohol with C 1 -C 4 -monocarboxylic acids, vinyl ethers, ⁇ , ⁇ -ethylenically uns
  • Suitable additional monomers e) are methyl (meth) acrylate, methyl ethacrylate, ethyl (meth) acrylate, ethyl ethacrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, 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, hepta- decyl (meth) acrylate, nonadecyl
  • Suitable additional monomers e) are also the esters of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, preferably C 2 -C 12 - amino alcohols. These may preferably be mono-alkylated or -dialkylated on the amine nitrogen C 1 -C 8 .
  • Suitable acid components of these esters are, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Preference is given to using esters of acrylic acid, esters of methacrylic acid and mixtures thereof.
  • tert-butylaminoethyl (meth) acrylate N, N-dimethylamino-methyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N- Dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminocyclohexyl (meth) acrylate, etc.
  • Suitable additional monomers e) are also N-methyl (meth) acrylamide,
  • Suitable additional monomers e) are furthermore 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,
  • Suitable additional monomers e) are also 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.
  • Suitable additional monomers e) are furthermore acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpropionamide and mixtures thereof.
  • Also suitable as additional monomers e) are 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.
  • 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, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid , Vinylsulfuric acid, vinylphosphoric acid, 10-undecenoic acid, 4-pentenoic acid, cinnamic acid,
  • Suitable additional monomers e) are furthermore ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, o-chlorostyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, ethers of vinyl alcohol and 1 to 18 carbon atoms Monoalcohols, such as, for example, methyl vinyl ethers, esters of vinyl alcohol and monocarboxylic acids having 1 to 18 C atoms, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate and mixtures thereof. Most preferred as component e) is methyl (meth) acrylate.
  • the mixture of components a) to e) to be polymerized may optionally be polymerized in the presence of f) both by means of initiators which form free radicals and by the action of high-energy radiation, which is to be understood as the action of high-energy electrons ,
  • the peroxo and / or azo compounds customary for this purpose can be used, for example alkali metal or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert.
  • initiator mixtures or redox initiator systems such as, for example, ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate. Preference is given to using organic peroxides.
  • the polymerization can also be carried out by the action of ultraviolet radiation, if appropriate in the presence of UV initiators.
  • the photoinitiators or sensitisers which are usually suitable for this purpose are used. These are, for example, compounds such as benzoin and benzoin ethers, ⁇ -methylbenzoin or ⁇ -phenylbenzoin. So-called triplet sensitizers, such as benzyldiketals, can also be used.
  • UV radiation sources are used, for example, in addition to high-energy UV lamps, such as carbon arc lamps, mercury vapor lamps or xenon lamps and low-UV light sources, such as fluorescent tubes with high blue content.
  • the amounts of initiator or initiator mixtures used, based on the monomer used, are between 0.01 and 10% by weight, preferably between 0.1 and 5% by weight.
  • the polymerization takes place in the temperature range of 40 to 200 ° C, preferably in the range from 50 to 140 0 C, particularly preferably in the range of 60 to 110 0 C. It is usually carried out under atmospheric pressure, but can also under reduced or elevated pressure, preferably between 1 and 5 bar.
  • the polymerization can be carried out, for example, as solution polymerization, bulk polymerization, emulsion polymerization, reverse emulsion polymerization, suspension polymerization, reverse suspension polymerization or precipitation polymerization, without restricting the usable methods thereto.
  • the polymerization can also be carried out semicontinuously by initially introducing a part, for example about 10% of the mixture of component f) to be polymerized, the monomers a) to e) and initiator, heating the mixture to polymerization temperature and after starting the polymerization adds the remainder of the mixture to be polymerized after the progress of the polymerization.
  • the polymer Sate can also be obtained by initially introducing component f) in a reactor, heating to the polymerization temperature and adding the mixture of monomers a) to e) and polymerization initiator either at once, batchwise or preferably continuously, and polymerizing.
  • Suitable solvents are, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexanol and glycols such as ethylene glycol, propylene glycol and butylene glycol, and the methyl or Ethyl ethers of dihydric alcohols, diethylene glycol, triethylene glycol, glycerol, dioxane, butyl acetate, ethyl acetate and toluene, with ethyl acetate, butyl acetate and mixtures thereof are particularly preferred.
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-hexanol and cyclohexano
  • the polymerization is particularly preferably carried out as a precipitation polymerization.
  • the preferred method of preparing the polymers suitable for use in the present invention is precipitation polymerization.
  • solvents are used in which the starting materials for the polymerization soluble and the resulting polymer are insoluble.
  • Suitable solvents are, for example, aromatic hydrocarbons such as toluene, xylene, benzene or aliphatic hydrocarbons such as n-alkanes, cyclohexane, esters of acetic acid such as ethyl acetate, butyl acetate, ethers such as e.g.
  • the polymerization is carried out in the presence of less than 69% by weight of cyclohexane and less than 12% by weight of water, based on the total amount of all components present during the polymerization.
  • the polymerization is preferably carried out in the presence of less than 50, more preferably less than 40 and in particular in the range of 30 to 0 wt .-% cyclohexane.
  • the polymerization is carried out in the presence of less than 10, more preferably less than 8 and in particular in the range of 5 to 0 wt .-% water.
  • the solvent used for the polymerization consists of at least 30, preferably at least 50 and in particular at least 70 wt .-% of ethyl acetate or n-butyl acetate or mixtures thereof.
  • the solvent is 80 to 100, preferably 90 to 100 wt .-% of ethyl acetate and / or n-butyl acetate.
  • initiators all initiators can be used, as they are also used in the solution polymerization. Preferably, 0.01 to 1, 5% by weight of initiator are used based on the monomers used.
  • the precipitation polymerization is usually conducted at temperatures of 20 to 150 ° C, preferably 40 to 120 ° C, in particular 60 to 100 0 C performed.
  • the precipitation polymerization is usually carried out at pressures of 1 to 15 bar, in particular 1 to 6 bar.
  • the solvent or solvent mixture determined by the corresponding boiling temperatures, the maximum reaction temperature if polymerized under atmospheric pressure. However, polymerizations under pressure are also possible.
  • the precipitation polymerization can be carried out at solids contents of up to about 40% by weight. A range between 25 and 40 wt .-% is preferred. Especially at high solids contents, it is advisable to carry out the polymerization in the presence of a protective colloid polymer.
  • Suitable protective colloid polymers are those which dissolve well in the solvents used and do not react with the monomers. As protective colloids suitable polymers are z.b.
  • the amount of the protective colloid polymer used is usually in the range of 0.05 to 4% by weight (based on monomers), preferably 0.1 to 2% by weight. It is often advantageous to use mixtures of multiple protective colloid polymers.
  • the polymerization is carried out by initially introducing solvent, component T), protective colloid polymer and possibly crosslinker c), heating, and polymerizing by addition of initiator and monomers a), b), d) and e) (possibly dissolved in the same solvent or solvent mixture).
  • initiator and monomers a), b), d) and e) possibly dissolved in the same solvent or solvent mixture.
  • partial amounts of the monomers and the initiator for example 10%
  • heat this mixture to the polymerization temperature and, after the beginning of the reaction, add the remainder of the mixture to be polymerized after the polymerization has progressed.
  • the polymerization is carried out in the feed mode for the preparation of the polymers suitable for the use according to the invention.
  • some or all of the reactants are added in whole or in part, batchwise or continuously, together or in separate feeds to a reaction mixture.
  • Separate feeds are advantageous, for example, if the solubilities of the components a) to e) differ significantly in certain solvents.
  • a process with separate feeds advantageous because vinylimidazole and methacrylamide differ significantly in their solubilities.
  • Monomers and initiator are generally added in a time of 1 to 10 hours, preferably from 2 to 5 hours.
  • polymers suitable for the use according to the invention may optionally also be present.
  • polyamides, polyurethanes, polyesters, homopolymers and copolymers of ethylenically unsaturated monomers may optionally also be present.
  • Examples of such polymers are the commercially available Amerhold TM, Ultrahold TM, Ultrahold Strong TM, Luviflex TM VBM, Luvimer TM, Acronal TM, Acudyne TM, Stepanhold TM, Lovocryl TM, Versatyl TM, Amphomer TM or Eastma AQ TM, Luvisiqu TM brands, Sokalan TM brands, Luviquat TM brands
  • the precipitated polymer is then isolated from the reaction mixture, for which any general method for isolating the polymers in conventional precipitation polymerization can be used. Such methods are filtration, centrifugation, evaporation of the solvent or combinations of these methods. For further purification of the polymer from unpolymerized constituents, the polymer is washed. For this one can use in principle the same solvents as they are suitable for the polymerization. When the polymers are to be alkylated after polymerization, it is advantageous to use the same solvent for polymerization and alkylation.
  • the polymer is to be dried, it is advisable to carry out a solvent exchange after the polymerization or after the alkylation and to use low-boiling solvents such as acetone for the drying.
  • a solvent exchange after the polymerization or after the alkylation and to use low-boiling solvents such as acetone for the drying.
  • low-boiling solvents such as acetone for the drying.
  • regulators substances with the aid of which the molecular weight of the polymers can be controlled and which are generally referred to as regulators.
  • the radical polymerization of the monomer mixture can be carried out in the presence of at least one regulator.
  • Regulators are preferably used in an amount of from 0.0005 to 5 wt .-%, more preferably from 0.001 to 2.5 wt .-% and in particular from 0.01 to 1, 5 wt .-%, based on the total weight of the component a) to e) used.
  • Regulators are generally compounds with high transmission constants. Regulators accelerate chain transfer reactions and thus cause a reduction in the degree of polymerization of the resulting polymers without affecting the gross reaction rate.
  • regulators it is possible to distinguish between monofunctional, bifunctional or polyfunctional regulators, depending on the number of functional groups in the molecule which can lead to one or more chain transfer reactions. Suitable regulators are described, for example, in detail by K.C. Berger and G. Brandrup in J. Brandrup, E.H. Immergut, Polymer Handbook, 3rd ed., John Wiley & Sons, New York, 1989, pp. 11/81 - 11/141.
  • Suitable regulators are, for example, aldehydes, such as formaldehyde, acetaldehyde, propionic aldehyde, n-butyraldehyde, isobutyraldehyde.
  • regulators formic acid, its salts or esters, such as ammonium formate, 2,5-diphenyl-1-hexene, hydroxylammonium sulfate, and hydroxylammonium phosphate.
  • halogen compounds e.g. Alkyl halides such as carbon tetrachloride, chloroform, bromotrichloromethane, bromoform, allyl bromide, and benzyl compounds such as benzyl chloride or benzyl bromide.
  • Suitable regulators are allyl compounds, e.g. Allyl alcohol, functionalized allyl ethers such as allyl ethoxylates, alkyl allyl ethers, or glycerol monoallyl ethers.
  • Compounds of this type are, for example, inorganic hydrogen sulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides and sulfones.
  • di-n-butyl sulfide di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl trisulfide, dimethyl sulfoxide, dialkyl sulfide, Dialkyl disulfide and / or diaryl sulfide.
  • organic compounds containing sulfur in bonded form are particularly preferred.
  • Preferred compounds used as polymerization regulators are thiols (compounds which contain sulfur in the form of SH groups, also referred to as mercaptans).
  • Preferred regulators are mono-, bi- and polyfunctional mercaptans, mercaptoalcohols and / or mercaptocarboxylic acids.
  • Examples of these compounds are allyl thioglycolates, ethyl thioglycolate, cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropane-1, 2-diol, 1, 4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, thioacetic acid , Thiourea and alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan.
  • Particularly preferred thiols are cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropane-1, 2-diol, thioglycerol, thiourea.
  • bifunctional regulators containing two sulfur in bound form are bifunctional thiols such as e.g. Dimercaptopropanesulfonic acid (sodium salt), dimercaptosuccinic acid, dimercapto-1-propanol, dimercaptoethane, dimercaptopropane, dimercaptobutane, dimercaptopentane, dimercaptohexane, ethylene glycol bis-thioglycolate and butanediol bis-thioglycolate.
  • bifunctional thiols such as e.g. Dimercaptopropanesulfonic acid (sodium salt), dimercaptosuccinic acid, dimercapto-1-propanol, dimercaptoethane, dimercaptopropane, dimercaptobutane, dimercaptopentane, dimercaptohexane, ethylene glycol bis-thioglycolate and butanediol bis-thiog
  • polyfunctional regulators are compounds containing more than two sulfur in bound form. Examples of these are trifunctional and / or tetrafunctional mercaptans.
  • Preferred trifunctional regulators are trifunctional mercaptans, e.g. Trimethylolpropane tris (2-mercaptoethanoate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (4-mercaptobutanate), trimethylolpropane tris (5-mercaptopentanate), trimethylolpropane tris (6-mercaptohexanate), trimethylolpropane tris (2-mercaptoacetate), glyceryl thioglycolate, glyceryl thiopropionate, glyceryl thioethylate, glyceryl thiobutanate, 1,1,1-propanetriyl tris (mercaptoacetate), 1,1,1-propanetriyl tris (mercaptoethanoate),
  • trifunctional regulators are glyceryl thioglycolate, trimethylolpropane tris (2-mercaptoacetate), 2-hydroxymethyl-2-methyl-1,3-propanediol tris (mercaptoacetate).
  • Preferred tetrafunctional mercaptans are pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (2-mercaptoethanoate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (4-mercaptobutanate), pentaerythritol tetrakis (5-mercaptopentanate ), Pentaerythritol tetrakis (6-mercaptohexanate).
  • polyfunctional regulators are Si compounds which are formed by reacting compounds of the formula (IVa). Further suitable as polyfunctional regulator Si compounds of the formula
  • R 1 represents a C 1 -C 4 -alkyl group or phenyl group
  • R 2 is a -C - ⁇ - alkyl group, denotes the cyclohexyl or phenyl group
  • Z is a C 1 -C 18 alkyl group, C 2 -C 18 alkylene group or C 2 -C 18 alkynyl group, whose carbon atoms are replaced by non-adjacent oxygen or halogen atoms, or for one of the groups
  • N C (R 3 ) 2 or - NR 3 - CR 4 in which
  • R 3 a means and
  • R 4 denotes a C 1 -C 18 -alkyl group.
  • controllers can be used individually or in combination with each other. In one embodiment of the invention, no regulator is used.
  • component a) 99.99 to 10% by weight of component a), in particular N-vinylimidazole, b) 0 to 90% by weight of component b), in particular N-vinylpyrrolidone, c) 0.01 to 5% by weight of one Crosslinker c), in particular pentaerythritol triallyl ether, d) 0 to 20 wt .-% of a component d), in particular octadecyl vinyl ether and / or stearyl methacrylate e) 0 to 30 wt .-% of a component e) in the presence of f) 0 to 70 wt. %, based on the sum of the components a) to e) of a polyether-containing compound T), in particular polyethylene glycol,
  • polymers which are obtainable by free-radical graft copolymerization of
  • component a) 97.95 to 40% by weight of component a), in particular N-vinylimidazole, b) 1 to 60% by weight of component b), in particular N-vinylpyrrolidone, c) 0.05 to 2% by weight a crosslinker c), in particular pentaerythritol triallyl ether, d) 1 to 15 wt .-% of a component d) in particular octadecyl vinyl ether and / or stearyl methacrylate e) 0 to 20 wt .-% of a component e) in the presence of
  • component a 96.9 to 60% by weight of component a), in particular N-vinylimidazole, b) from 1 to 40% by weight of component b), in particular N-vinylpyrrolidone and / or methacrylamide c) from 0.1 to 1% by weight of a crosslinker c), in particular pentaerythritol triallyl ether, d) from 2 to 10% by weight % of a component d) in particular octadecyl vinyl ether and / or stearyl methacrylate and / or behenyl acrylate and / or esters of
  • the polymer Before the use according to the invention in aqueous or aqueous / alcoholic preparation, the polymer can be neutralized after the polymerization and before or after the filtration.
  • acids or bases may be necessary for neutralization.
  • organic or inorganic acids are used as neutralizing agents for monomers carrying basic groups.
  • Possible organic acids are monohydric and polyhydric, optionally substituted aliphatic and aromatic carboxylic acids, mono- and polyhydric, optionally substituted aliphatic and aromatic sulfonic acids or mono- and polyhydric, optionally substituted aliphatic and aromatic phosphonic acids, polymers carrying acid groups or ascorbic acid called.
  • Preferred organic acids are hydroxycarboxylic acids, i. Derivatives of carboxylic acids in which one or more H atoms are replaced by hydroxyl groups. Examples of hydroxycarboxylic acids include glycolic acid, lactic acid, tartaric acid and citric acid.
  • Preferred inorganic acids are phosphoric acid, phosphorous acid, sulfuric acid, sulfurous acid and hydrochloric acid.
  • neutralizing agents for monomers carrying acid groups for example, mineral bases such as sodium carbonate, alkali metal hydroxides such as NaOH or preferably KOH and ammonia, organic bases such as amino alcohols especially 2-amino-2-methyl-1-propanol, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, tri [( 2-hydroxy) 1-propyl] amine, 2-amino-2-methyl-1, 3-propanediol, 2-amino-2-hydroxymethyl-1, 3-propanediol and diamines, such as lysine.
  • water glass as the neutralizing agent, as described in DE-A 103 54 015, [0008] to [0010].
  • Theological properties By modifying the Theological properties is generally understood the change in the deformation and flow behavior of matter.
  • the most important theological properties are viscosity, thixotropy, intrinsic viscosity, rheoplexy and dilatancy. These terms are known to the person skilled in the art.
  • Viscosity is usually the "viscosity" of a liquid. It results from the intermolecular forces in a liquid, so it depends on cohesion (intramolecular) and adhesion (intermolecular). The viscosity characterizes the flow behavior of a liquid. High viscosity means thick liquid, while low viscosity means thin liquid.
  • Thixotropy usually refers to the property of a fluid to show a lower viscosity after shearing and to rebuild the original viscosity at standstill.
  • Rheopexy is usually the property of a fluid to show a higher viscosity after shearing. This behavior is closely related to the dilatancy, where the viscosity is higher only during shear.
  • thickening Increasing the viscosity of liquids understood, also commonly referred to as “thickening.” This increase in viscosity may extend to the formation of gels or solids.
  • Another object of the invention are cosmetic, dermatological or pharmaceutical agents containing at least one as defined above, suitable for the inventive use polymer.
  • Preferred agents are aqueous, alcoholic or aqueous / alcoholic compositions containing the at least one polymer in an amount ranging from 0.01 to 20, more preferably from 0.05 to 10, most preferably from 0.1 to 7 wt. -% used included.
  • compositions comprising at least 40, preferably at least 50 and especially at least 60% by weight of water and at the same time less than 20% by weight of alcohol.
  • alcoholic compositions are meant compositions comprising at least 40, preferably 50 wt .-% and in particular at least 60 wt .-% of one or more alcohols and at the same time less than 20 wt% water.
  • compositions containing at least 20% by weight of water and at the same time at least 20% by weight of alcohol.
  • a preferred embodiment of the invention are aqueous / alcoholic compositions containing preferably at least 50% by weight of water and preferably at most 40% by weight of alcohol.
  • the polymers which are suitable for the uses according to the invention are distinguished by the fact that they can be used as thickeners for preparations whose liquid phase comprises compounds containing essentially OH groups. These OH group-containing compounds are essentially water and alcohols.
  • the polymers suitable for the uses according to the invention are suitable for the rheology modification of alcoholic preparations.
  • Suitable alcohols for these preparations are generally all alcohols present under normal conditions. These are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, 3-methyl-1-butanol (isoamyl alcohol), n-hexanol, cyclohexanol or glycols such as ethylene glycol, propylene glycol and Butylene glycol, polyhydric alcohols such as glycerol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, alkyl ethers of these polyhydric alcohols having number average molecular weights up to about 3000.
  • the alcohol is or comprises ethanol and / or isopropanol, in particular ethanol.
  • the polymers according to the invention can act as thickening and at the same time as conditioning agents both in alcoholic and essentially anhydrous, aqueous and substantially alcohol-free and aqueous / alcoholic preparations.
  • the viscosity of the preparations according to the invention is preferably at least 1,000, more preferably at least 5,000 and in particular at least 10,000 and preferably at most 100,000, particularly preferably at most 50,000 and in particular at most 30,000 mPa * s, measured as dynamic viscosity measurement with a viscometer Brookfield DV -II + Pro, spindle 6, 20 revolutions per minute (rpm) at 25 ° C, depending on the concentration of the polymers selected from the range of 0.2 to 5.0 wt .-%.
  • One embodiment of the invention are cosmetic preparations, in particular hair gels on an aqueous, essentially alcohol-free basis containing a combination of the polymers according to the invention and optionally further ingredients, for example at least one film-forming and hair-setting polymer.
  • a further embodiment of the invention are cosmetic preparations, in particular hair gels on an alcoholic, substantially anhydrous basis with a content of a combination of the inventive polymers, at least 30 wt .-% C 1 -C 4 alcohols and optionally an alcohol-soluble, film-forming and hair-setting polymer.
  • (Hair) gels based on C 1 -C 4 alcohols can fulfill other / complementary requirements for hair gels compared to aqueous or aqueous / alcoholic gels. If, for example, a solidifier gel is to be prepared, it is then also possible to use alcohol-soluble solidifying polymers.
  • the thickening polymer described above which is suitable for the uses according to the invention, is preferably used in an amount of from 0.01 to 20, particularly preferably from 0.05 to 10, very particularly preferably from 0.1 to 7,% by weight.
  • a hair setting polymer is used, it is preferably in an amount of from 0.1 to 20, more preferably from 0.5 to 15, most preferably from 1 to 10% by weight.
  • the alcohol is preferably used in an amount of 50 to 99, more preferably from 70 to 98 wt .-%.
  • the wt .-% are each based on the total weight of the preparation.
  • alcohol-soluble polymers are understood as meaning those polymers which are soluble at 25 ° C. to at least 5% by weight in at least one alcohol having 1 to 4 C atoms.
  • Suitable liquid alcohols for the hair gels on an alcoholic, substantially anhydrous basis are monohydric or polyhydric alcohols which are included in the formula Room temperature (20 0 C) are liquid and have 1 to 4 carbon atoms.
  • the lower alcohols customarily used for cosmetic purposes such as, for example, ethanol, isopropanol, glycerol, ethylene glycol or propylene glycol.
  • monohydric alcohols having 2 to 4 C atoms in particular ethanol and isopropanol.
  • the hair gel is preferably substantially anhydrous, but it may contain small amounts of water to improve the solubility of other ingredients, but the alcohol content significantly exceeds the water content.
  • substantially anhydrous means that the water content is not greater than 10% by weight, preferably not greater than 5% by weight.
  • the alcoholic gels of the invention are characterized in the presence of a setting polymer by good conditioning properties, high degree of consolidation, rapid drying and pleasant cooling effect.
  • the preparations according to the invention can be applied to damp or dry hair.
  • the products are suitable for both straight and curly hair.
  • the polymers described above are also outstandingly suitable for the production of further cosmetic and pharmaceutical agents. They serve, for example, as polymeric film formers in preparations for personal care, which includes the use of cosmetic preparations on keratinous surfaces such as skin, hair, nails and oral care preparations. They can be used universally in a wide variety of cosmetic preparations and formulated and compatible with the usual components.
  • the polymers suitable for the uses according to the invention can exhibit particular effects. Among other things, the polymers can contribute to moisturizing and conditioning the skin and to improving the feel on the skin.
  • the polymers act in particular in the formulations both as thickener and as conditioning agent.
  • the polymers are capable of increasing the viscosity of this composition to at least 10,000 mPa * s (Brookfield viscosity) as the water-only constituent of an aqueous composition at a concentration of 0.5% by weight and increasing the viscosity of the composition Wet combability of the hair to cause at least 10% compared to hair treated with pure water.
  • a particular advantage of the invention is that it is possible, with the exclusive use of the aforementioned polymers in aqueous, alcoholic or aqueous / alcoholic compositions, to provide a hair gel (conditioner gel) suitable as conditioning agent.
  • the thickening effect necessary for hair gels and the conditioning effect necessary for conditioners can thus be provided by a single ingredient.
  • the agents according to the invention preferably have at least one cosmetically or pharmaceutically acceptable carrier B) which is selected from
  • the agents include, for example, 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 4 monocarboxylic acids, such as isopropyl isostearate, n-propylmyristate, isopropyl myristate, n-propyl palmitate, isopropyl palmitate, hexacosanyl palmitate, octacosanyl palmitate, Triacontanyl palmitate, dotriacont
  • Suitable silicone oils B) are e.g. 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 e.g. 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, 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
  • Suitable cosmetically and pharmaceutically acceptable oil or fat components B) are described in Karl-Heinz Schrader, Kunststoff und paragraphuren der Kosmetika, 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 having preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol, etc.
  • the cosmetic agents may be skin-cosmetic or hair-cosmetic agents.
  • the agents are in the form of a spray, gel, foam, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.
  • the cosmetic, dermatological or pharmaceutical agents may additionally contain cosmetically, dermatologically or pharmaceutically active agents and adjuvants.
  • compositions preferably comprise at least one polymer as defined above suitable for the use according to the invention, at least one carrier B as defined above and at least one different constituent selected from cosmetically active ingredients, emulsifiers, surfactants, preservatives, perfume oils, other thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaching agents, gelling agents, conditioners, colorants, tinting agents, tanning agents, dyes, pigments, bodying agents, moisturizers, backfats, collagen, protein hydrolysates, lipids, Antioxidants, defoamers, antistatic agents, emollients and plasticizers.
  • cosmetically active ingredients emulsifiers, surfactants, preservatives, perfume oils, other thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaching agents, gelling agents, conditioners, color
  • the cosmetic, dermatological or pharmaceutical agents may contain, in addition to the polymer suitable for use according to the invention, further thickening agents / gelling agents. However, it is preferred to use no further thickening agents. Further thickeners / gelling agents are preferably present in an amount such that the total amount of thickeners / gellants ranges from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight, or from 0.5 to 3 % By weight.
  • the additional polymeric gelling agents can be synthetic homo- or copolymers, wherein at least one of the monomers carries at least one acid group, preferably a carboxylic acid, sulfonic acid or phosphoric acid group.
  • polysaccharides containing at least one type of saccharide having at least one acid group, e.g. Glucuronic.
  • Suitable additional synthetic gelling agents are e.g. composed of at least one type of monomer which is selected from acrylic acid, methacrylic acid, itaconic acid monoesters, acrylamidoalkylsulfonic acids and / or methacrylamidoalkylsulfonic acids.
  • Synthetic gellants may be, for example: crosslinked or uncrosslinked homopolymers of acrylic acid (carbomers) having a molecular weight of e.g. from 2,000,000 to
  • copolymers of acrylic acid and acrylamide for example with a MoIe- kulargwicht 2000000-6000000, AcrylateSteareth-20 Methacrylate copoly- mer, copolymers of acrylic or methacrylic acid with acrylic acid or methacrylic acid esters (acrylate copolymers), acrylates / C 10-30 alkyl acrylate crosspolymer, acrylate
  • Vinyl alcohol copolymers polystyrenesulfonic acid and mixtures thereof.
  • Natural-based gelling agents may be natural or modified natural polymers, for example: alginic acid, carrageenan, carboxymethylcellulose, carboxymethylhydroxyethylcellulose, carboxymethyldextran, carboxymethylhydroxypropylguar, cellulose sulfate, dextran sulfate, karaya gum, xanthan gum and mixtures thereof.
  • the monomer of formula (11) is acrylic acid, methacrylic acid or one of its C1 to C4 alkyl esters.
  • Suitable copolymers are, for example acrylic or methacrylic acid / acrylic or Methacrylklarepolyethoxy- alkyl ester copolymers (INCI name: Acrylates / Steareth-20 Methacrylate Copolymer, Acrylates / Palmeth-25 Acrylate Copolymer), for example, under the Bezeichun- gen Acrysol ® -22, Acrysol ICS ®, Aculyn ® -22 or Synthalen ® W-2000 sold or acrylic or methacrylic acid / Polyethoxyallylether copolymers (INCI name: Steareth-10 AllylEtherAcrylates copolymer), for example, under the designation SAI care ® SC 90 are sold.
  • Suitable gelling agents are, for example, copolymers formed from itaconic acid monoesters of the general formula CH 2 CC (COOR 1 ) CH 2 COOR 2 where one of the substituents R 1 and R 2 is hydrogen and the other is the group - (CH 2 CH 2 O) 1 R 3 stands; x is a number between 1 and 100, preferably between 10 and 40, more preferably 20; R 3 is an alkyl group having 8 to 30, preferably 12 to 20 C atoms, more preferably cetyl or stearyl and at least one second type of monomer selected from acrylate monomers.
  • the acrylate monomers are preferably selected from acrylic acid, methacrylic acid and their simple esters, in particular the acrylic acid alkyl esters and methacrylic acid alkyl esters having 1 to 10, preferably 1 to 4, carbon atoms in the alkyl group.
  • suitable copolymers are acrylic or methacrylic acid / itaconic acid polyethoxyalkyl ester copolymers (INCI names: Acrylates / Steareth-20 Itaconate Copolymer and Acrylates / Ceteth-20 Itaconate Copolymer, Acrylates / Amino Acrylates / C10-30 Alkyl PEG-20 Itaconate Copolymer ), such as those sold under the names Structure ® 2001, Structure ® 3001 and Structure ® Plus.
  • Suitable gelling agents are also homopolymers or copolymers composed of at least one type of monomer selected from acrylic or methacrylamidoalkylsulfonic acid.
  • This monomer is preferably copolymerized with at least one nonionic, radically copolymerizable monomer, in particular a vinyl lactam, more preferably vinyl pyrrolidone.
  • Such a gelling agent has, for example, the INCI name Ammonium Acryloyldimethyltaurate / VP Copolymer.
  • a suitable commercial product is Aristoflex ® AVC.
  • non-polymeric and / or non-polymeric polymeric thickeners such as hydroxyethyl cellulose may be present as co-thickeners in the composition according to the invention.
  • Suitable cosmetically and / or dermatologically active agents are e.g. coloring active ingredients, skin and hair pigmenting agents, tinting agents, suntanning agents, bleaching agents, keratin-hardening substances, antimicrobial agents, light filter active ingredients, repellent active ingredients, hyperemic substances, keratolytic and keratoplastic substances, antidandruff active ingredients, antiphlogistics, keratinizing substances, antioxidant or radical scavenger active Active substances, skin-moisturizing or moisturizing substances, moisturizing active substances, anti-erythemic or anti-allergic active substances and mixtures thereof.
  • Artificial skin tanning agents which are suitable for tanning the skin without natural or artificial irradiation with UV rays are e.g. Dihydroxyacetone, alloxan and walnut shell extract.
  • Suitable keratin-hardening substances are as a rule active substances, as are also used in antiperspirants, such as, for example, antiperspirants.
  • Antimicrobial agents are used to destroy microorganisms or 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 e.g.
  • customary preservatives known to the person skilled in the art, such as p-hydroxybenzoic acid esters, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc.
  • deodorizing substances are known, for example.
  • Suitable light filter active substances are substances which absorb UV rays in the UV-B and / or UV-A range.
  • Suitable UV filters are e.g. 2,4,6-triaryl-1,3,5-triazines in which the aryl groups can each bear at least one substituent, which is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and mixtures thereof.
  • substituent which is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and mixtures thereof.
  • p-aminobenzoic acid esters cinnamic acid esters, benzophenones, camphor derivatives and UV-radiation-stopping pigments, such as titanium dioxide, talc and zinc oxide.
  • Suitable sunscreens for use in the water-containing compositions are all the compounds mentioned in EP-A 1 084 696 in paragraphs [0036] to [0053], to which reference is made in its entirety.
  • antimicrobial agents can also be used in the compositions containing water. These generally include all suitable preservatives with specific action against gram-positive bacteria, eg triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether), chlorhexidine (1, 1'-hexamethylenebis [5- (4-chlorophenyl) - biguanide) and TTC (3,4,4'-trichlorocarbanilide).
  • triclosan 2,4,4'-trichloro-2'-hydroxydiphenyl ether
  • chlorhexidine 1, 1'-hexamethylenebis [5- (4-chlorophenyl) - biguanide
  • TTC 3,4,4'-trichlorocarbanilide
  • Quaternary ammonium compounds are also suitable in principle, but are preferably used for disinfecting soaps and washing lotions.
  • fragrances have antimicrobial properties. Special combinations with particular effectiveness against Gram-positive bacteria are used for the composition of so-called Deopfarums.
  • Clove oil (eugenol), mint oil (menthol) or thyme oil (thymol)
  • thyme oil thymol
  • the antibacterial substances are usually used in concentrations of about 0.1 to 0.3 wt .-%.
  • Suitable repellent agents are compounds which are able to prevent or expel certain animals, in particular insects, from humans. This includes e.g. 2-ethyl-1,3-hexanediol, N, N-diethyl-m-toluamide, etc.
  • Suitable hyperemic substances which stimulate the perfusion of the skin are e.g. 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.
  • 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 e.g. Salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc.
  • Suitable anti-dandruff agents are e.g. Sulfur, sulfur polyethylene glycol borate monooleate, sulfur ricinol polyethoxylate, zinc pyrithione, aluminum pyrithione, etc.
  • Suitable antiphlogistic agents which counteract skin irritation are e.g. Allantoin, bisabolol, dragosantol, chamomile extract, panthenol, etc.
  • the cosmetic, dermatological or pharmaceutical agents can be used as cosmetic and / or pharmaceutical active substance (as well as optionally as excipient) contain at least one further cosmetically or pharmaceutically acceptable polymer.
  • active substances from the following fields of application can be used: antibiotics, for example sulfonamides, antihistamines, antimycotics, antiphlogistics, antirheumatics, circulation-promoting agents, steroids such as corticoids, sex hormones, for example, progestins, wound healing agents, such as dexpanthenol.
  • antibiotics for example sulfonamides, antihistamines, antimycotics, antiphlogistics, antirheumatics, circulation-promoting agents, steroids such as corticoids, sex hormones, for example, progestins, wound healing agents, such as dexpanthenol.
  • non-steroidal, anti-inflammatory agents ibuprofen, ketoprofen, indomethacin, diclofenac, methyl salicylate, hydroxyethyl salicylate, etofenamate.
  • agents which additionally comprise at least one nonionic, one anionic, one cationic or one ampholytic polymer.
  • Suitable additional anionic polymers are copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes and polyureas. Preference is also given to agents which additionally contain a polyurethane as anionic polymer.
  • the preparations / compositions according to the invention comprise at least one of the customary setting polymers described below.
  • Particularly suitable as additional polymers are the water-soluble or water-dispersible polyurethanes described in DE 4225045 A1, to which reference is made in its entirety. Particularly suitable is Luviset PUR ® (BASF).
  • silicone-containing polyurethanes as described in the
  • Particularly suitable polymers are copolymers of (meth) acrylic acid and polyether acrylates, the polyether chain having a C 8 -C 30 -alkyl radical being terminated.
  • These include, for example, acrylate / Beheneth-25 methacrylate copolymers which are available under the name ACU lyn ® from Rohm and Haas.
  • Particularly suitable polymers are also copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (eg Luvimer ® 100P), copolymers of ethyl acrylate and methacrylic acid (eg 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 (eg Luviset ® brands), maleic anhydride, 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 C 4 -C 30 -alkyl esters of meth (acrylic acid), C 4 -C
  • anionic polymers are WEI terhin vinyl acetate / crotonic acid copolymers, such as those sold under the names Resyn ® (National Starch) and Gafset ® (GAF) are commercially available and vinylpyrrolidone / vinyl acrylate copolymers, obtainable for example under the trademark Lu - viflex ® (BASF).
  • Other suitable polymers are the commercially available as Lu- viflex ® VBM-35 (BASF) vinylpyrrolidone / acrylate terpolymer and sodium sulfonate-containing polyamides or sodium sulfonate-containing polyester.
  • the group of suitable anionic polymers comprises Balance CR ® (National Starch; Acrylate Copolymer), balance 0/55 ® (National Starch; Acrylate Copolymer), Balance ® 47 (National Starch; octylacrylamide / acrylates / butyl aminoethylmethacrylate- Copolyrner) Aquaflex ® FX 64 (ISP; isobutylene / ethyl maleimide / hydroxyethylmaleimide copolymer) Aquaflex ® SF-40 (ISP / National Starch; VP / vinyl caprolactam / DMAPA acrylates copolymer), Alliance ® LT-120 (ISP; Rohm &Haas; acrylates / C1-2 succinate / hydroxyacrylate copolymer), Aquarez ® HS (Eastman; Po lyester-1), and ® Diaformer Z-400 (Clariant; methacryloylethy
  • Suitable additional polymers are the terpolymers described in US No. 3,405,084 of vinylpyrrolidone, CRCI O -alkyl, cycloalkyl and aryl (meth) acrylates and acrylic acid. Suitable additional polymers furthermore include the terpolymers of vinylpyrrolidone, tert-butyl (meth) acrylate and (meth) acrylic acid described in EP-AO 257 444 and EP-AO 480 280.
  • Suitable additional polymers are furthermore the copolymers described in DE-A-42 23 066, which contain at least one (meth) acrylic ester, (meth) acrylic acid and also N-vinylpyrrolidone and / or N-vinylcaprolactam polymerized.
  • the disclosure of these documents is hereby incorporated by reference.
  • Suitable carboxylic acid group-containing polymers are also polyurethanes containing carboxylic acid groups.
  • EP-A-636361 discloses suitable block copolymers having polysiloxane blocks and polyurethane / polyurea blocks having carboxylic acid and / or sulfonic acid groups.
  • Suitable silicone-containing polyurethanes are also described in WO 97/25021 and EP-A-751 162.
  • Suitable polyurethanes are also described in DE-A-42 25 045, which is incorporated herein by reference in its entirety.
  • Component i) is e.g. diols, diamines, amino alcohols, and mixtures thereof.
  • the molecular weight of these compounds is preferably in a range of about 56 to 280. If desired, up to 3 mol% of said compounds may be replaced by triols or triamines.
  • Useful diols i) are e.g. Ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethylol, di-, tri-, tetra-, penta- or hexaethylene glycol and mixtures thereof. Preference is given to using neopentyl glycol and / or cyclohexanedimethylol.
  • Suitable amino alcohols i) are e.g.
  • Suitable diamines i) are, for example Ethylenediamine, propylenediamine, 1,4-diaminobutane, 1,5-diaminopentane and
  • 1,6-diaminohexane and also ⁇ , ⁇ -diaminopolyethers which can be prepared by amination of polyalkylene oxides with ammonia.
  • the component i) may also be a polymer having a number average molecular weight in the range of about 300 to 5000, preferably about 400 to 4000, in particular 500 to 3000.
  • Useful polymers i) are, for example, polyester diols, polyether roles and mixtures thereof.
  • Polyetherols are preferably polyalkylene glycols, for example polyethylene glycols, polypropylene glycols, polytetrahydrofurans, etc., block copolymers of ethylene oxide and propylene oxide or block copolymers of ethylene oxide, propylene oxide and butylene oxide, which randomly distribute the alkylene oxide units or contain them in copolymerized form in the form of blocks.
  • Suitable polytetrahydrofurans i) can be prepared by cationic polymerization of tetrahydrofuran in the presence of acidic catalysts, such as, for example, sulfuric acid or fluorosulfuric acid. Such production processes are known to the person skilled in the art.
  • Useful polyester diols i) preferably have a number-average molecular weight in the range from about 400 to 5000, preferably 500 to 3000, in particular 600 to 2000.
  • Suitable polyester diols i) are all those which are customarily used for the preparation of polyurethanes, especially those based on aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, phthalic acid, Na or K sulfoisophthalic acid, etc., of aliphatic dicarboxylic acids , such as adipic acid or succinic acid, etc., and cycloaliphatic dicarboxylic acids, such as 1, 2, 1, 3 or 1, 4-cyclohexanedicarboxylic acid.
  • aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, Na or K sulfoisophthalic acid, etc.
  • aromatic dicarboxylic acids such as terephthalic acid,
  • Suitable diols are, in particular, aliphatic diols, such as ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethylene glycols, polypropylene glycols, 1,4-dimethylolcyclohexane, etc.
  • Suitable compounds ii) having two active hydrogen atoms and at least one carboxylic acid group per molecule are e.g. Dimethylolpropanoic acid and mixtures containing dimethylolpropanoic acid.
  • the component iii) is conventional aliphatic, cycloaliphatic and / or aromatic polyisocyanates, such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, 2,4- and 2,6-toluene diisocyanate and their isomer mixtures, o- and m-xylylene diisocyanate, 1 , 5-Naphthylendiisocyanat, 1, 4-cyclohexylene diisocyanate, dicyclohexylmethane diisocyanate and mixtures thereof, in particular isophorone diisocyanate and / or dicyclohexylmethane diisocyanate. If desired, up to 3 mol% of the compounds mentioned can be replaced by triisocyanates.
  • Suitable additional polymers are furthermore cationic polymers. These include e.g. Polymers named Polyquaternium according to INCI, e.g. Copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat TM FC, Luviquat TM HM, Luviquat TM MS, Luviquat TM Care), copolymers
  • Suitable cationic (quaternized) polymers are also Merquat TM (polymer based on dimethyl diallyl ammonium chloride), Gafquat TM (quaternary polymers which are formed by reaction of polyvinyl pyrrolidone with quaternary ammonium compounds), Polymer TM JR (hydroxyethyl cellulose with cationic groups) and cationic polymers based on plants, for example guar polymers, such as the Jaguar TM brands from Rhodia.
  • Suitable additional polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer TM (National Starch) Octylac- rylamid / methyl methacrylate / tert-Butylaminoethylmethacryla ⁇ 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.
  • zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are commercially available under the name Amersete TM (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon TM).
  • Neutral polymers suitable as additional polymers are e.g. Polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethylenimines and their salts, polyvinylamines and their salts, cellulose derivatives, polyaspartic acid salts and derivatives.
  • These include, for example, Luviflex TM 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 polyvinylcaprolactam, e.g. Luviskol TM Plus (BASF), or polyvinylpyrrolidone and their copolymers, in particular with vinyl esters, such as vinyl acetate, e.g. Luviskol TM VA 37 (BASF); Polyamides, e.g. based on itaconic acid and aliphatic diamines, e.g. in DE-A-43 33 238 are described.
  • polyvinylcaprolactam e.g. Luviskol TM Plus (BASF)
  • BASF Luviskol TM VA 37
  • Polyamides e.g. based on itaconic acid and aliphatic diamines, e.g. in DE-A-43 33 238 are described.
  • Suitable polymers are also nonionic, siloxane-containing, water-soluble or -dispersible polymers, for example polyether siloxanes, such as Tegopren TM (Goldschmidt) or Belsil TM (Wacker). Means for skin cleansing and care
  • the polymers suitable for the uses according to the invention can advantageously also be used in skin cleansing compositions.
  • Skin cleansing preparations are soaps of liquid to gelatinous consistency, such as transparent soaps, luxury soaps, deep-soap soaps, cream soaps, baby soaps, skin soaps, abrasive soaps and syndets, pasty soaps, greases and washing pastes, liquid washing, showering and bathing preparations such as washing lotions, shower baths and gels, bubble baths, oil baths and scrub preparations, shaving foams, lotions and creams.
  • the polymers suitable for the uses according to the invention can also be used for the rheology modification of cosmetic agents for the care and protection of the skin, nail care preparations or preparations for decorative cosmetics.
  • skin cosmetic agents are e.g. Face lotions, face masks, deodorizers and other cosmetic lotions.
  • Means for use in decorative cosmetics include, for example, masking pens, theatrical paints, mascara and eye shadows, lipsticks, kohl pencils, eyeliners, rouges, powders, and eyebrow pencils.
  • polymers suitable for the uses according to the invention can be used in nose strips for pore cleansing, in anti-acne agents, repellents, shaving agents, hair removal agents, personal care products, foot care agents and in baby care.
  • the skin care products 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 means preferably contain 0.05 to 20 wt .-%, preferably 0.1 to 15 wt .-%, most preferably 0.1 to
  • Particularly light stabilizers for the rheology modification of which the polymers suitable for the uses according to the invention are used, have the property of increasing the residence time of the UV-absorbing ingredients in comparison with customary auxiliaries, such as polyvinylpyrrolidone.
  • the compositions can be applied in a form suitable for skin care, such as cream, foam, gel, stick, mousse, milk, spray (pump spray or propellant-containing spray) or lotion.
  • 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, other thickeners, gelling agents, bodying agents, silicones, humectants, moisturizers 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, bleaching agents, colorants, toners, tanning agents, collagen, protein hydrolys
  • Preferred oil and fat components of the skin-cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as 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 triglycerides of C 6 -C 30 fatty acids, wax esters such as jojoba oil, fatty alcohols, vaseline, hydrogenated lanolin and acetylated lanolin, and mixtures thereof.
  • mineral and synthetic oils such as 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 such as triglycerides of C 6 -C 30 fatty acids
  • wax esters such as jojoba oil, fatty alcohols, vaseline, hydrogenated lanolin
  • the skin-cosmetic and dermatological preparations may contain further 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 pharmaceutical or dermatological preparations is carried out by customary methods known to the person skilled in the art.
  • the cosmetic and dermatological preparations are in the form of gels.
  • the cosmetic and dermatological preparations are in the form of emulsions, in particular as water-in-oil (W / O) or oil-in-water (O / W) emulsions.
  • W / O water-in-oil
  • O / W oil-in-water
  • Emulsions are prepared by known methods.
  • the emulsions generally contain customary constituents, such as fatty alcohols, fatty acid esters and especially 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 especially fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
  • a suitable emulsion e.g. for a skin cream, etc., generally contains an aqueous phase which is emulsified by means of a suitable emulsifier system in an oil or fat phase.
  • 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, calophilum 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 the distillation end point at 410 0 C, such as Vaselineöl; Esters of saturated or unsaturated fatty acids, such as alkyl myristates, for example i-propyl, butyl or cetyl myristate, hexadecyl stearate, ethyl or i-propyl palmitate, octanoic or decanoic acid triglycerides and cetyl ricinoleate.
  • hydrocarbon oils such
  • 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.
  • oil-soluble silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
  • waxes may also be used, e.g. Carnauba wax, candililla, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.
  • an emulsion may be present as an 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. Washing, shower and bath preparations
  • the rheology-modifying polymers are used particularly advantageously in shower gels, shampoo formulations or bath preparations.
  • Such formulations also usually contain anionic surfactants as basic surfactants and amphoteric and / or nonionic surfactants as cosurfactants.
  • Further suitable active ingredients and / or auxiliaries are generally selected from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants, as well as thickeners / gelling agents, skin conditioners and moisturizers.
  • 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.
  • Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosylates, 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. 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 amphoteric surfactants are e.g. Alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or -propionates, alkylamphodiacetates or -dipropionates.
  • 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.
  • alkylamine oxides are also suitable.
  • mono- or dialkylalkanolamides are also suitable.
  • fatty acid esters of polyethylene glycols are also suitable.
  • ethoxylated fatty acid amides are also suitable.
  • alkylpolyglycosides are also suitable.
  • washing, showering and bathing preparations may contain conventional cationic surfactants, e.g. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • conventional cationic surfactants e.g. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • shower gel / shampoo formulations may contain further thickeners, e.g. Common salt, PEG-55, propylene glycol oleate, PEG-120 methyl glucose dioleate and others, as well as preservatives, other active ingredients and auxiliaries and water.
  • further thickeners e.g. Common salt, PEG-55, propylene glycol oleate, PEG-120 methyl glucose dioleate and others, as well as preservatives, other active ingredients and auxiliaries and water.
  • a particularly preferred embodiment of the invention are hair treatment compositions, in particular the previously described thickened preparations and hair gels.
  • Hair treatment compositions according to the invention preferably contain at least one suitable polymer for use according to the invention in an amount in the range of about 0.01 to 20, more preferably from 0.05 to 10, most preferably from 0.1 to 7 wt .-% based on the Total weight of the agent.
  • the hair treatment compositions according to the invention are preferably in the form of hair gels.
  • hair mousses can also be in the form of hair mousses, shampoos, hair sprays, hair foams, top fluids, leveling agents for hair perming, hair dyeing and - bleach or "hot oil treatments" available.
  • the hair cosmetic preparations can be applied as gel, gel spray, (aerosol) spray, (aerosol) foam, 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.
  • the compounds used in the hair sprays and hair foams according to the invention water-dispersible they can be used in the form of aqueous microdispersions having particle diameters of usually 1 to 350 nm, preferably 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.
  • compositions according to the invention contain a proportion of volatile organic components (VOC) of at most 80% by weight, particularly preferably at most 55% by weight.
  • VOC volatile organic components
  • compositions according to the invention contain in one embodiment
  • ingredients are understood to include the additives customary in cosmetics, for example propellants, defoamers, surface-active compounds, i. Surfactants, emulsifiers, foaming agents and solubilizers.
  • the surface-active compounds used can be anionic, cationic, amphoteric or neutral.
  • Further common components may also be e.g. Preservatives, perfume oils, opacifiers, active ingredients, UV filters, care ingredients such as panthenol, collagen, vitamins, protein hydrolysates, alpha and beta hydroxycarboxylic acids, protein hydrolysates, stabilizers, pH regulators, dyes, dyes, salts, humectants, moisturizers, complexing agents and other common additives.
  • the preparations may additionally contain other 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).
  • CTFA dimethicone copolyols
  • emulsifiers all emulsifiers commonly used in hair foams can be used.
  • Suitable emulsifiers may be nonionic, cationic or anionic or amphoteric.
  • Propellants particularly suitable for aerosol foams are mixtures of dimethyl ether and, optionally halogenated, hydrocarbons, such as propane, butane, pentane or HFC-152a. Depending on other solvents and the desired application, the proportions of the blowing agents are to be varied.
  • nonionic emulsifiers are Laurethe, e.g. Laureth-4; Cetethe, e.g. Cetheth-1, polyethylene glycol cetyl ether; Ceteareth, e.g. Cethetereth-25, polyglycol fatty acid glycerides, hydroxylated lecithin, lactyl esters of fatty acids, alkylpolyglycosides.
  • 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 isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha olefin sulfonates, especially the alkali and alkaline earth metal salts, e.g.
  • 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.
  • the polymers can be used according to the invention as thickeners in shampoos. Contain preferred shampoo formulations
  • Polymers which contain in copolymerized form methacrylamide as component b) are particularly suitable for use as thickeners for shampoos and other surfactant-containing compositions.
  • 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, especially the alkali and alkaline earth metal salts, e.g. 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 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.
  • 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 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.
  • alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters are also suitable.
  • the shampoo formulations may contain conventional cationic surfactants, e.g. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • conventional cationic surfactants e.g. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • protein hydrolysates can be used, as well as conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
  • silicone compounds for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
  • suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).
  • CTFA dimethicone copolyols
  • amino-functional silicone compounds such as amodimethicones
  • cationic guar derivatives such as guar hydroxypropyltrimonium chloride (INCI) can be used.
  • a preparation suitable for styling gels according to the invention can be composed, for example, as follows:
  • gel formers are particularly advantageous if special theological or other performance properties of the gels are to be established. Due to the excellent compatibility of the polymers suitable for the use according to the invention with further cosmetically customary gel formers, these gel formers can also be used in combination.
  • the thickened preparation or the cosmetic gel according to the invention is compounded in a phase containing preferably at least 20, more preferably at least 40 and especially at least 50% by weight of water and preferably at most 40% by weight of alcohol.
  • Alcohols which may be mentioned are the lower monoalcohols having 1 to 4 C atoms, which are customarily used for cosmetic purposes, e.g. Be contained ethanol and isopropanol.
  • the gel contains in particular to improve the gloss of the treated hair polyhydric alcohols, preferably those having 2 to 6 carbon atoms and having 2 to 6 hydroxy groups in an amount of 0.1 to 15, preferably from 1 to 10 wt .-% , Particular preference is given to glycerol, ethylene glycol and propylene glycol, in particular 1,2-propylene glycol and sorbitol.
  • silicone oils for improving the gloss, it is also possible to use silicone oils, in particular polydimethylsiloxanes (dimethicones) and aryl-substituted polydimethylsiloxanes (2.B., phenyltrimethicones). pigments
  • the gel according to the invention is suitable for simultaneous conditioning and temporary hair coloring and additionally contains at least one temporary hair-dyeing pigment.
  • Temporary hair dyeing is understood to mean a color change of human hair that lasts until the next hair wash and can be removed again by washing the hair with conventional shampoos.
  • the pigments are preferably present in an amount of from 0.01 to 25% by weight, more preferably in an amount of from 5 to 15% by weight.
  • the pigments are preferably not nanoparticles but micropigments.
  • the preferred particle size is 1 to 200 .mu.m, in particular 3 to 150 .mu.m, particularly preferably 10 to 100 .mu.m.
  • the pigments are practically insoluble colorants in the application medium and may be inorganic or organic. Also inorganic-organic mixed pigments are possible. Preference is given to inorganic pigments.
  • the advantage of inorganic pigments is their excellent light, weather and temperature resistance.
  • the pigments may be of natural origin, for example made of chalk, ocher, umber, green soil, terraced terraza or graphite.
  • the pigments may be white pigments, e.g. Titanium dioxide or zinc oxide to form black pigments, e.g. Iron oxide black, color pigments such as e.g.
  • Suitable are metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and molybdate and the metals themselves (bronze pigments).
  • Titanium dioxide (Cl 77891), black iron oxide (Cl 77499), yellow iron oxide (Cl 77492), red and brown iron oxide (Cl 77491), manganese violet (Ci 77742), ultramarines (sodium aluminum sulfosilicates, Cl 77007, Pigment Blue 29), Chromium Oxide Hydrate (C177289), Iron Blue (Ferric Ferrocyanide, CI7751 0), Carmine (Cochineal).
  • pigments based on mica or mica which are coated with a metal oxide or a metal oxychloride such as titanium dioxide or bismuth oxychloride and optionally further coloring substances such as iron oxides, iron blue, ultramarines, carmines, etc., and the color may be determined by varying the layer thickness.
  • a metal oxide or a metal oxychloride such as titanium dioxide or bismuth oxychloride
  • optionally further coloring substances such as iron oxides, iron blue, ultramarines, carmines, etc.
  • Organic pigments include, for example, the natural pigments sepia, rubber belt, bone charcoal, brown Kasseler, indigo, chlorophyll and other plant pigments.
  • Synthetic organic pigments are, for example, azo pigments, anthraquinoids, indigoids, dioxazine, quinacridone, phthalocyanine, isoindolinone, perylene and perinone, metal complex, alkali blue and diketopyrrolopyrrole pigments.
  • the invention further provides aqueous compositions comprising at least one polymer suitable for the uses according to the invention and at least one further polymer, in particular one which contains copolymerized N-vinyllactam.
  • N-vinyllactams are unsubstituted N-vinyllactams and N-vinyllactam derivatives which contain, for example, one or more C 1 -C 6 -alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert. Butyl, etc., may have.
  • aqueous compositions particularly preferably contain at least one polymer suitable for the uses according to the invention and polyvinylpyrrolidone.
  • polyvinylpyrrolidones having a K value of at least 30, preferably at least 60, more preferably at least 90 are particularly suitable.
  • Such polyvinylpyrrolidones are commercially available, for example, under the trade name Luviskol TM (BASF).
  • BASF Luviskol TM
  • Such compositions already show at total concentrations of polymer according to the invention and polymer which contains N-vinyllactam in copolymerized form (in particular polyvinylpyrrolidone), in the range of about 0.5-10% by weight, preferably 1-5% by weight, in particular as Gels very good properties such as high viscosity and clarity of the aqueous composition as well as very good firmness when applied to the hair.
  • Preferred polymers for pharmaceutical preparations contain N-vinyllactams, in particular N-vinylimidazole, which may also be present in quaternized form, the quaternization in particular taking place with a methyl group.
  • preparations for topical preparations may contain conventional pharmaceutical excipients in conventional amounts.
  • Suitable auxiliaries are, for example, surfactants.
  • Suitable surfactants are, for example, polyalkoxylated sorbitan acid esters, polyalkoxylated castor oils or polyalkoxylated hydrogenated castor oils, for example Cremophor® grades such as Cremophor RH 40.
  • the pharmaceutical preparations are usually essentially aqueous systems. However, the preparations may also contain organic solvents such as ethanol, isopropanol, porpylene glycol, polypropylene glycols or glycerol.
  • the polymers were washed after the polymerization with acetone.
  • PEG Polyethylene glycol VI: N-vinylimidazole
  • V-Cap N-vinylcaprolactam AS: acrylic acid
  • PETAE pentaerythritol triallyl ether
  • C18VE octadecyl vinyl ether
  • C18AC stearyl methacrylate
  • Viscosity 2 Viscosity of a 2% strength by weight aqueous solution of the polymer neutralized to 100% with acid
  • Viscosity 1 Viscosity of a 1% strength by weight aqueous solution of the polymer 100% neutralized with acid
  • Viscosity 0.5 Viscosity of a 0.5% by weight aqueous solution of the 100% acid-neutralized polymer
  • the hair tresses were washed twice with an aqueous Texapon ® NSO solution. Subsequently, the hair strands were rinsed with warm water until no more foam was visible and rinsed with deionized water, combed and placed on filter paper to dry.
  • the hair strands were placed for 15 minutes to swell in a solution of ethanol and water (1: 1).
  • the lock of hair was carefully combed before curling preparation. With a rubber band, the strand of hair was attached to a plexiglass rod. It was then combed and wound spirally. With a cotton cloth and rubber band, the lock was firmly fixed and dried overnight at 70 ° C. The cooled strands were carefully opened and stripped off the Plexiglas rod without deforming the water wave. From a distance of 15 cm from the previously prepared aerosol hair spray solution about 1, 8 g were sprayed evenly on the curl. The curl was turned evenly. In a horizontal position, the curls were dried for 1 hour at room temperature. After drying, the curls were fixed in a holder.
  • the length L 0 of the curls was read and tracked the length expansion during the wet climate storage. After storage for 5 h at 25 ° C. and 90% RH in the climatic chamber, the length L t of the lock achieved was read off and the curl retention was calculated according to the following equation:
  • L length of the hair (15.5 cm)
  • L 0 length of hair lock after drying
  • L t length of hair lock after climate treatment
  • Curl retention was the average of the 5 individual measurements.
  • the setting effect of the polymers was measured by measuring the bending stiffness of thin strands of hair (in each case about 3 g and 24 cm in length). For this purpose, the weighed, dry strands of hair were immersed in the below-mentioned polymer solution (solvent: ethanol / water 55:45 w / w), whereby a uniform wetting of the hair strand and distribution of the polymer solution was ensured by three times immersing and removing and then expressing between filter paper. The excess film former solution was then stripped between the thumb and forefinger and the strands of hair were hand-formed into strands to give a round cross-section. At 20 0 C and 65% relative humidity was dried overnight in a conditioning room.
  • the bleached hair tress (length 24cm / weight 2,7- 3.3 g) was shampooed twice, first with Texapon ® NSO total of 1 minute and 1 minute rinsed by a defined moisture and swelling to reach the.
  • the wire was fixed to the holder and combed with the fine-toothed side of the comb into the fine-toothed side of the test comb. Inserting the hair into the test comb was carried out uniformly and stress-free with each measurement. The measurement was started and evaluated with the help of the software EGRANUDO ® (Fa. Frank). The measurement was repeated 5-10 times. The measurements were carried out in a climatic chamber at about 65% relative humidity and 21 0 C.
  • the hair gel to be tested (0.5% by weight of the respective polymer in water) was filled in a cuvette and centrifuged. Care was taken that the cuvette contained no air bubbles.
  • the device Lambda 40 Fa. Perkin Eimer was used as a measuring device.
  • the measurement and evaluation of the measurement were performed using the software UV WinLab TM.
  • the measurements were carried out at a temperature of about 21 ° C with a cuvette filled with demineralized water as a reference.
  • the wavelength range for the measurements was 400 to 800 nm.
  • the measured value was the transmission value (in%) displayed at a wavelength of 600 nm.
  • the viscosities of the solutions of the polymers 1 to 13 were determined with the viscometer Brookfield DV-II under normal conditions with spindle 4 at 12 rpm in a conventional 150 ml beaker.
  • the viscosities of the solutions of the polymers 14 to 54 were determined with the viscometer Brookfield DV-II + Pro under conventional conditions with spindle 6 at 20 rpm in a conventional 250 ml beaker.
  • a mixture of water and 0.5% by weight of a commercial polyacrylic acid thickener (Carbopol® 940) neutralized with triethanolamine (TEA) was first prepared.
  • the resulting gel when applied to the hair, exhibited substantially no conditioning or setting action.
  • mixtures of water, 0.5% by weight of the commercial polyacrylic acid thickener and 3% by weight of a commercially available setting polymer were prepared.
  • the performance properties of the gels obtained are given in the table below. With good thickening, the other hair cosmetic properties are in need of improvement.
  • Oil-in-water emulsions (O / V emulsions) containing commercial thickener polymers or the copolymers 30 (Q) and 34 (Q) to be used according to the invention were prepared and their viscosity determined.
  • Oil and water phase (phase A and phase B) were heated to about 80 0 C.
  • the respective polymer was dispersed in the oil phase shortly before preparation.
  • the water phase was slowly stirred into the oil phase, then homogenized. While stirring, the mixture was cooled to 40 ° C. and the preservative (phase C) was stirred in. The mixture was then stirred until it reached room temperature and finally after-homogenized briefly.
  • the O / W emulsions were then added with saline in various amounts (see table below).
  • the common salt was stirred for 10 minutes at room temperature.
  • the viscosity was measured immediately thereafter.
  • the stability of the thickened emulsion ie the establishment and maintenance of the increased viscosity over an extended period of time in the presence of salt, is particularly advantageous also for skin cosmetic preparations.
  • the amount of crosslinker is based on the total amount of 100 wt .-% of the other components.
  • Preparation Mix all components until a homogeneous mixture is obtained. This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q).
  • Preparation Mix all components until a homogeneous mixture is obtained. This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q).
  • Preparation Mix all components until a homogeneous mixture is obtained. This example is repeated with the polymers of Examples 1 to 54 and 2 (Q) to 54 (Q).
  • the amount of crosslinking agent is based on the total amount of 100% by weight of the other components. ** the quaternization / alkylation was carried out with methyl chloride.
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • phase A and homogenize Add phase C and melt at 80 ° C. Heat phase D to 80 ° C. Add phase D to phase ABC and homogenize. Cool down to approx. 4O 0 C, add phase E and phase F, homogenize again.
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • Analogous preparations are also prepared with the polymers 1 to 54 or the quaternized derivatives 2 (Q) to 54 (Q).
  • the polymer was allowed to swell for 2 hours in the appropriate amount of water.
  • the active ingredient indomethacin was dissolved in Cremophor ⁇ RH40 (reaction product of 1 mol of hydrogenated castor oil with 45 mol of ethylene oxide) with gentle heating.
  • the pH of the swollen polymer was adjusted to pH 5.5 in the case of the polymer 27 (Q) with 1 molar hydrochloric acid and in the case of the Carbopol 971 P with 1 molar sodium hydroxide solution and the active substance-containing mixture was added.
  • the viscosity was determined at 22 ° C and 20 rpm (Brookfield viscometer).
  • the polymer was allowed to swell in the appropriate amount of water for 2 hours. Ibuprofen was dissolved in the mixture of ethanol and propylene glycol. The swollen polymer was adjusted to a pH of 5.5 with 1 molar hydrochloric acid or sodium hydroxide solution and admixed with the active substance-containing mixture. The viscosity was determined at 22 ° C and 20 rpm (Brookfield viscometer).

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KR20070118129A (ko) 2007-12-13
JP2008535954A (ja) 2008-09-04
CN101155842A (zh) 2008-04-02
CA2602323A1 (en) 2006-09-21
US20080194708A1 (en) 2008-08-14
WO2006097514A1 (de) 2006-09-21
CN101155842B (zh) 2011-08-03

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