EP1606328A1 - Polymeres greffes et leur utilisation dans des preparations cosmetiques - Google Patents

Polymeres greffes et leur utilisation dans des preparations cosmetiques

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Publication number
EP1606328A1
EP1606328A1 EP04717606A EP04717606A EP1606328A1 EP 1606328 A1 EP1606328 A1 EP 1606328A1 EP 04717606 A EP04717606 A EP 04717606A EP 04717606 A EP04717606 A EP 04717606A EP 1606328 A1 EP1606328 A1 EP 1606328A1
Authority
EP
European Patent Office
Prior art keywords
graft
alkyl
phase
polymers according
graft polymers
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.)
Ceased
Application number
EP04717606A
Other languages
German (de)
English (en)
Inventor
Lysander Chrisstoffels
Peter Hössel
Claudia Wood
Maximilian Angel
Klemens Mathauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1606328A1 publication Critical patent/EP1606328A1/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3788—Graft 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
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0212—Face masks
    • 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
    • A61K8/91—Graft copolymers
    • 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
    • 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
    • C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
    • C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
    • 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
    • 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
    • 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
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/28—Rubbing or scrubbing compositions; Peeling or abrasive compositions; Containing exfoliants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
    • A61Q1/06—Lipsticks
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • A61Q1/02—Preparations containing skin colorants, e.g. pigments
    • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • 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
    • A61Q19/001—Preparations for care of the lips
    • 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
    • A61Q19/002—Aftershave preparations
    • 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
    • A61Q19/005—Preparations for sensitive skin
    • 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
    • A61Q19/007—Preparations for dry skin
    • 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
    • A61Q19/10—Washing or bathing preparations
    • 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
    • A61Q5/006—Antidandruff preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q9/00—Preparations for removing hair or for aiding hair removal
    • A61Q9/02—Shaving preparations

Definitions

  • the invention relates to the graft polymers and their use as a constituent in cosmetic products.
  • the graft polymers are formed by grafting monoethylenically unsaturated, open-chain monomers containing N-vinylamide units onto a polymeric graft base consisting of at least 2 compounds.
  • Polymers are widely used in cosmetics and medicine. In soaps, creams and lotions, for example, they usually serve as formulating agents, e.g. as a thickener, foam stabilizer or water absorbent or to alleviate the irritating effects of other ingredients or to improve the dermal application of active ingredients. In contrast, your task in hair cosmetics is to influence the properties of the hair.
  • Conditioners are used to improve dry and wet combability, feel, shine and appearance, as well as to give the hair antistatic properties.
  • Water-soluble polymers with polar, frequently cationic functionalities are preferred which have a greater affinity for the structurally determined 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 hydroxyethyl cellulose, cationic polymers based on N-vinylpyrrolidone, e.g. Copolymers of N-vinylpyrrolidone and quaternized N-vinylimidazole, acrylamide and diallyldimethylammonium chloride or silicones.
  • Vinyl lactam homo- and copolymers and carboxylate-containing polymers are used to set hairstyles.
  • Requirements for hair setting resins are, for example, strong strengthening with high air humidity, elasticity, washability from the hair, compatibility in the formulation and a pleasant feel of the hair.
  • N-vinylpyrrolidone is mentioned as a concrete example of a cyclic amide.
  • Further examples of vinyl monomers are secondary, tertiary and quaternary amines, such as dimethyldiallylammonium chloride, dimethylaminoethyl methacrylate or dimethylaminopropyl methacrylate.
  • DE 19907587.5 describes the use of polymers which are obtainable by free-radical polymerization of at least one vinyl ester in the presence of polyether-containing compounds and optionally one or more copolymerizable monomers and subsequent at least partial saponification of the ester function in hair cosmetic formulations.
  • the copolymerizable monomers include Called vinylformamide.
  • DE-A1-4409 903 describes graft polymers containing N-vinyl units, processes for their preparation and their use.
  • a graft base which is a polymer, each have at least 5% by weight of units of the formulas
  • Suitable monoethylenically unsaturated monomers are all ethylenically unsaturated monomers whose polymerization is not inhibited by the amine groups in free or in salt form, such as, for example, monoethylenically unsaturated mono- and dicarboxylic acids, their salts and esters with C to C 30 alcohols. A suitability of these graft copolymers as an active ingredient in cosmetic formulations is not mentioned.
  • WO 96/34903 describes graft polymers containing N-vinyl units, processes for their preparation and their use.
  • a graft base ge which is a polymer containing at least 3 units of a C 2 - to C 4 -alkylene oxide and / or containing polytetrahydrofuran, grafted monoethylenically unsaturated monomers and then at least partially saponified.
  • a suitability of these graft copolymers as an active ingredient in cosmetic formulations is not mentioned.
  • US Pat. No. 5,334,287 discloses graft polymers which are obtained by radical-initiated polymerization of N-vinylcarboxamides, preferably N-vinylformamide, and, if appropriate, other monomers in the presence of monosaccharides, oleosaccharides, polysaccharides or in each case their derivatives and, if appropriate, hydrolysis of the polymerized group N-vinylcarboxamides are obtainable to form vinylamine units.
  • a suitability of these graft copolymers as an active ingredient in cosmetic formulations is not mentioned.
  • WO 9825981 describes amphiphilic graft polymers by grafting hydrophobic monomers such as e.g. Styrene, synthesized on polymers containing structural elements of the formula (IV) and / or (V).
  • the graft polymers obtained are, inter alia, used as additives to cosmetic formulations.
  • radicals R 17 independently of one another represent H, alkyl, cycloalkyl, aryl or aralkyl and R 8 represents H, alkyl or aralkyl.
  • Copolymers which are used, for example, as hair setting agents and are composed of N-vinylamide monomers of the formula wherein R1 and R2 are H or CC 5 alkyl and the comonomer is selected from vinyl ethers, vinyl lactams, vinyl halides, vinyl esters of monobasic saturated carboxylic acids, (meth) acrylic esters, amides and nitriles and esters, anhydrides and imides of maleic acid are from DE 14 95692 known.
  • US 4713 236 describes hair conditioners based on polymers containing vinylamine units.
  • polyvinylamine and its salts ⁇ -substituted polyvinylamines such as e.g. Poly- ( ⁇ -aminoacrylic acid) or copolymers which, in addition to vinylamine, contain comonomers such as vinyl alcohol, acrylic acid, acrylamide, maleic anhydride, vinyl sulfonate and 2-acrylamido-2-methylpropane sulfonic acid in copolymerized form.
  • WO 02/15854 A1 describes the use of hydrophilic graft copolymers with N-vinylamine and / or open-chain N-vinylamine units in cosmetic formulations. Graft polymers which are formed by grafting onto a polymeric graft base which consists of at least 2 compounds are not described.
  • the object of the present invention was to find polymers which are well suited for cosmetic applications and, for example in the field of hair cosmetics, have good application properties such as a pleasant grip and at the same time have good conditioning action or good setting action.
  • polymers which are suitable as conditioning agents for cosmetic preparations and which are produced with a high solids content can be.
  • R 1 , R 2 , R 3 H or C to C 6 alkyl
  • a polymeric graft base c) which contains at least one compound from group d) and at least one compound from group c2), wherein.
  • the polymers used according to the invention include both pure graft polymers and mixtures of the above graft polymers with ungrafted compounds d) and c2) and homo- or copolymers of the monomers a) and b).
  • the graft polymers are water-soluble or water-dispersible.
  • Water-soluble polymers are to be understood here as meaning polymers which dissolve in water at least 1 g / l at 20 ° C.
  • Water-dispersible polymers are understood here to mean polymers which disintegrate into dispersible particles with stirring.
  • N-vinyl-containing monomers a) are N-vinylamides and / or N-vinyllactams.
  • Suitable N-vinyl-containing monomer a) are, for example, N-vinylamides of the general formula (I)
  • R 1 , R 2 , R 3 H or C to C 6 alkyl
  • the following monomers are used, for example, as the open-ended N-vinylamide compound a) of the general formula (I): N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-is! methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide and N-vinyl-butyramide.
  • N-vinyl-containing monomers a) are N-vinyl lactams of the general formula (II)
  • an N-vinylamide in particular N-vinylformamide, is used as monomer a).
  • mixtures of the respective monomers from group a), such as Mixtures of N-vinylformamide and N-vinylacetamide can be copolymerized.
  • N-vinylformamide N-vinyl-N-methylformamide
  • N-vinylacetamide N-vinyl-N-methylacetamide
  • N- Vinyl-N-ethyl acetamide N-vinyl propionamide
  • N-vinyl-N-methyl propionamide N-vinyl-N-methyl propionamide
  • N-vinyl butyramide N-vinyl butyramide
  • the graft polymers can contain one or more further monomers b).
  • the preferred additionally used copolymerizable monomers b) can be described by the following general formula:
  • X is selected from the group consisting of -OH, -OM, -OR 21 , NH 2 , -NHR 21 , N (R 2 ) 2 ;
  • M is a cation selected from the group consisting of: Na + , K + , Mg ++ , Ca ++ , Zn ++ , NH 4 + , alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium;
  • the radicals R 21 can be selected identically or differently from the group consisting of -H, -C-C 40 linear or branched chain alkyl radicals, N, N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, hydroxypropyl, methoxypropyl or ethoxypropyl.
  • R 20 and R 19 are independently selected from the group consisting of: -H, Ci-Cs linear or branched chain alkyl chains, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl.
  • Suitable monomers b) are, for example, acrylic acid or methacrylic acid and their salts, esters and amides.
  • the salts can be derived from any non-toxic metal, ammonium or substituted ammonium counterions.
  • the esters can be derived from C ⁇ C 40 linear, C 3 -C 0 branched or C 3 - C 40 carbocyclic alcohols, from polyfunctional alcohols with 2 to about 8 hydroxyl groups such as ethylene glycol, hexylene glycol, glycerol and 1,2,6-hexanetriol Amino alcohols or alcohol ethers such as methoxyethanol and ethoxyethanol, (alkyl) polyethylene glycols, (alkyl) polypropylene glycols or ethoxylated fatty alcohols, for example C 2 -C 24 fatty alcohols reacted with 1 to 200 ethylene oxide units.
  • N, N-dialkylaminoalkyl acrylates and methacrylates and N-dialkylamino alkyl acrylates and methacrylamides of the general formula (VII)
  • R 22 H, alkyl with 1 to 8 C atoms
  • R 23 H, methyl
  • R 24 alkylene with 1 to 24 carbon atoms, optional
  • the amides can be unsubstituted, N-alkyl or N-alkylamino monosubstituted or N, N-dialkyl-substituted or N, N-dialkylamino-substituted, in which the alkyl or alkylamino groups of CrC 0 linear, C 3 -C 40 branched chain, or C 3 -C 40 carbocyclic units are derived.
  • the alkylamino groups can be quaternized.
  • Preferred comonomers of the formula VII are N, N-dimethylaminomethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N- [ 3- (dimethylamino) propyl] methacrylamide and N- [3- (Dimethylamino) propyl] acrylamide.
  • Comonomers b) which can also be used are substituted acrylic acids and salts, esters and amides thereof, the substituents on the carbon atoms being in the two or three positions of acrylic acid, and are selected independently of one another from the group consisting of CC 4 alkyl, -CN, COOH particularly preferably methacrylic acid, ethacrylic acid and 3-cyanoacrylic acid.
  • These salts, esters and amides of these substituted acrylic acids can be selected as described above for the salts, esters and amides of acrylic acid.
  • Suitable comonomers b) are allyl esters of C 1 -C 40 linear, C 3 -C 40 branched-chain or C 3 -C 40 carbocyclic carboxylic acids, vinyl or allyl halides, preferably vinyl chloride and allyl chloride, vinyl ethers, preferably methyl, ethyl, Butyl or dodecyl vinyl ether, vinyl lactams, preferably vinyl pyrrolidone and vinyl caprolactam, vinyl or allyl-substituted heterocyclic compounds, preferably vinyl pyridine, vinyl oxazoline and allyl pyridine.
  • N-vinylimidazoles of the general formula VIII in which R 27 to R 29 independently of one another are hydrogen, C 1 -C 4 -alkyl or phenyl:
  • Suitable comonomers b) are vinylidene chloride; and hydrocarbons with at least one carbon-carbon. Double bond, preferably styrene, alpha-methyl styrene, tert-butyl styrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene, vinyl toluene and mixtures of these monomers.
  • Particularly suitable comonomers b) are acrylic acid, methacrylic acid, ethyl acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, propyl methacrylate Butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, n-
  • vinyl ether for example: methyl, ethyl, butyl or dodecyl vinyl ether
  • methyl vinyl ketone maleimide
  • vinyl pyridine vinyl imidazole
  • vinyl furan styrene, styrene, styrenesulfonate sulfonate it.
  • acrylic acid methacrylic acid, maleic acid, fumaric acid, crotonic acid, maleic anhydride and its half esters, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutyl acrylate 2- ethylhexyl acrylate, stearyl acrylate, stearyl methacrylate, Nt-butyl acrylamide, N-octyl acrylamide, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkylene glycol (meth) acrylate, Styrene, unsaturated sulfonic acids such as acryl
  • Monomers with a basic nitrogen atom can be quaternized in the following way:
  • alkyl halides with 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 and benzyl halides, in particular benzyl chloride and benzyl bromide.
  • Other suitable quaternizing agents are dialkyl sulfates, especially dimethyl sulfate or diethyl sulfate.
  • the quaternization of the basic amines can also be carried out with alkylene oxides such as ethylene oxide or propylene oxide in the presence of acids.
  • alkylene oxides such as ethylene oxide or propylene oxide in the presence of acids.
  • Preferred center of quaternization! are: methyl chloride, dimethyl sulfate or diethyl sulfate.
  • the quaternization can be carried out before the polymerization or after the polymerization.
  • the basic monomers can also be cationized by neutralizing them with mineral acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid, or with organic acids such as formic acid, acetic acid, lactic acid or citric acid.
  • mineral acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid
  • organic acids such as formic acid, acetic acid, lactic acid or citric acid.
  • macromonomers such as, for example, silicone-containing macromonomers with one or more radical-polymerizable groups or alkyloxazoline macromonomers, as described, for example, in EP-A 408 311, can be used as comonomers b).
  • fluorine-containing monomers as described, for example, in EP-A 558 423, compounds which have a crosslinking action or regulate the molecular weight can be used in combination or alone.
  • the further copolymerizable monomers b) are preferably used in an amount of 0-40% by weight, preferably 0-25% by weight, particularly preferably 0-15%.
  • the graft polymers can be obtained by carrying out the free-radical polymerization in the presence of at least one regulator e).
  • silicone compounds containing thiol groups can also be used. Silicone-free controllers are preferably used.
  • the regulator e) is preferably used in an amount of 0 to 5% by weight, preferably 0 to 2.5% by weight, particularly preferably 0 to 1.5%.
  • the graft polymers are prepared in the presence of a crosslinking agent d).
  • Monomers d) which have a crosslinking function are compounds with at least 2 ethylenically unsaturated, non-conjugated double bonds in the molecule.
  • Suitable crosslinkers d) are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols.
  • the OH groups of the underlying alcohols can be fully or partially etherified or esterified; however, 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-en-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-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexaned
  • Examples of underlying alcohols with more than two OH groups are trimefhylolpropane, glycerol, pentaerythritol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, triethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose.
  • the polyhydric alcohols can also be used as the corresponding ethoxylates or propoxylates after reaction with ethylene oxide or propylene oxide.
  • the polyhydric alcohols can also first be converted into the corresponding glycidyl ethers by reaction with epichlorohydrin.
  • 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-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamon alcohol , Citronellol, crotyl alcohol or cis-9-octadecen-1-ol.
  • the monohydric, unsaturated alcohols can also be esterified with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • polybasic carboxylic acids for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • crosslinkers are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
  • crosslinker d) are straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated to aliphatic hydrocarbons, for example divinylbenzene, divinyltoluene, 1, 7-octadiene, 1.9 -Decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes with molecular weights from 200 to 20,000.
  • crosslinkers are acrylic acid amides, methacrylic acid amides and N-allylamines of at least divalent amines.
  • amines are for example diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1, 6-
  • Diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine are also suitable.
  • the amides of allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above, are also suitable.
  • Triallylamine and triallylmonoalkylammonium salts e.g. Triallylmethylammonium chloride or methyl sulfate, suitable as a crosslinking agent.
  • N-vinyl compounds of urea derivatives at least dihydric amides, cyanurates or urethanes, for example of urea, ethylene urea, propylene urea or tartaric acid diamide, e.g. N, N'-divinylethylene urea or N, N'-divinyl propylene urea.
  • crosslinkers are divinyl dioxane, tetraallylsilane or tetravinylsilane.
  • crosslinking agents used 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 esters and acrylate of polyalkylene oxides or polyhydric alcohols, with ethylene oxide and / or propylene oxide and / or epichlorohydrin have been implemented.
  • the polymeric graft base c) contains at least one compound selected from group d) and at least one compound selected from group c2), where d) polyether-containing compounds c2) are polymers which contain at least 5% by weight of polymerized vinylpyrrolidone units ,
  • polyalkylene oxides based on ethylene oxide, propylene oxide, butylene oxide and other alkylene oxides and polyglycerol can be used as the polyether-containing compound d).
  • the polymers contain the following structural units:
  • the structural units can be both homopolymers and statistical copolymers and block copolymers.
  • Water-soluble polyether-containing compounds are particularly suitable as the graft base d). Both polyalkylene oxides based on ethylene oxide, propylene oxide, butylene oxide and other alkylene oxides and polyglycerol can be used here.
  • the structural units can be both homopolymers and statistical copolymers and block copolymers.
  • alkyl radicals for R 6 and R 30 and R 31 are branched or unbranched dC 2 alkyl chains, preferably methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 1- Dimethylethyl, n-pentyl, 1-methyl butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1- ethyl propyl, n-hexyl, 1, 1-
  • alkyl radicals branched or unbranched d -CC 2 -, particularly preferably dC B -alkyl chains may be mentioned.
  • Preferred graft base d) are polyalkylene glycols, such as, for example, polyethylene glycols and polypropylene glycols. Polyethylene glycols are particularly preferred.
  • the molecular weight of the polyether d) is in the range greater than 300 (by number average), preferably in the range from 300 to 100,000, particularly preferably in the range from 500 to 50,000, very particularly preferably in the range from 800 to 40,000.
  • Homopolymers of ethylene oxide or copolymers with an ethylene oxide content of 40 to 99% by weight are advantageously used.
  • the proportion of ethylene oxide polymerized in is therefore 40 to 100 mol% for the ethylene oxide polymers to be used with preference.
  • Propylene oxide, butylene oxide and / or isobutylene oxide are suitable as comonomers for these copolymers.
  • copolymers of ethylene oxide and propylene oxide copolymers of ethylene oxide and butylene oxide and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide are suitable.
  • the ethylene oxide content of the copolymers is preferably 40 to 99 mol%, the propylene oxide content 1 to 60 mol% and the content of butylene oxide in the copolymers 1 to 30 mol%.
  • branched homopolymers or copolymers can also be used as polyether-containing compounds d).
  • Branched polymers can be prepared, for example, by using polyalcohol residues, e.g. on pentaerythritol, glycerol or on sugar alcohols such as D-sorbitol and D-mannitol but also on polysaccharides such as cellulose and starch, ethylene oxide and optionally also propylene oxide and / or butylene oxides.
  • the alkylene oxide units can be randomly distributed in the polymer or in the form of blocks.
  • polyesters of polyalkylene oxides and aliphatic or aromatic dicarboxylic acids e.g. Oxalic acid, succinic acid, adipic acid and terephthalic acid with molecular weights from 1500 to 25000, such as described in EP-A-0 743 962 to be used as a polyether-containing compound.
  • polycarbonates can also be obtained by reacting polyalkylene oxides with phosgene or carbonates such as e.g. Diphenyl carbonate and polyurethanes can be used by reacting polyalkylene oxides with aliphatic and aromatic diisocyanates.
  • Particularly preferred polyethers d) are polymers of the general formula III with an average molecular weight of 300 to 100,000 (by number average), in which the variables have the following meaning independently of one another:
  • R 8 is hydrogen, d-dr alkyl.
  • Particularly preferred polyethers d) are polymers of the general formula III with an average molecular weight of 500 to 50,000 (based on the number average), in which the variables have the following meaning independently of one another:
  • silicone derivatives can also be used as polyether d).
  • Suitable silicone derivatives are the compounds known under the INCI name Dimethicone Copolyole or silicone surfactants such as, for example, those under the brand names Abil TM (from T. Goldschmidt), Alkasil TM (from Rhönen-Poulenc), Silicone Polyol Copolymer ⁇ (from Genesee), Belsil TM (from Wacker), Silwet TM (from Witco, Greenwich, CT, USA) or Dow Coming (from Dow Corning). These include compounds with the CAS numbers 64365-23-7; 68937-54-2; 68938-54-5; 68937- 55-3.
  • Silicones are generally used in hair cosmetics to improve the grip.
  • the use of polyether-containing silicone derivatives as polyether d) in the polymers according to the invention can therefore additionally lead to an improvement in the feel of the hair.
  • Preferred representatives of such polyether-containing silicone derivatives are those which contain the following structural elements:
  • radicals R 11 can be identical or different, and either come from the group of aliphatic hydrocarbons with 1 to 20 carbon atoms, are cyclic aliphatic hydrocarbons with 3 to 20 C atoms, are aromatic in nature or are equal to R 12 , where :
  • radicals R 11 , R 12 or R 13 are a polyalkylene oxide-containing radical as defined above, and f is an integer from 1 to 6, a and b are integers such that the molecular weight of the Polysiloxane blocks is between 300 and 30,000, c and d can be integers between 0 and 50, with the proviso that the sum of c and d is greater than 0 and e is 0 or 1.
  • Preferred radicals R 12 and R 16 are those in which the sum of c + d is between 5 and 30.
  • the groups R 11 are preferably selected from the following group: methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl, dodecyl and ocodecyl, cycloaliphatic radicals, especially cyclohexyl, aromatic groups, especially phenyl or Naphthyl, mixed aromatic-aliphatic radicals such as benzyl or phenylethyl as well as tolyl and xylyl and R 16 .
  • R denotes any alkyl, cycloalkyl or aryl radical which has between 1 and 40 carbon atoms and which can carry further ionogenic groups such as NH 2 , COOH, SO 3 H.
  • Particularly preferred polyether-containing silicone derivatives c-1) are those of the general structure:
  • homopolymers and copolymers of polyalkylene oxide-containing ethylenically unsaturated monomers such as, for example, polyalkylene oxide (meth) acrylates, polyalkylene oxide vinyl ethers, polyalkylene oxide (meth) acrylamides, polyalkylene oxide allyamides or polyalkylene oxide vinyl amides, can also be used as polyether (d).
  • polyether (d) polyether (ethylenically unsaturated monomers
  • Copolymers of such monomers with other ethylenically unsaturated monomers can of course also be used.
  • reaction products of polyethyleneimines with acylene oxides can also be used as polyether-containing compounds d).
  • the alkylene oxides used are preferably ethylene oxide, propylene oxide, butylene oxide and mixtures of these, particularly preferably ethylene oxide.
  • Polymers with number average molecular weights of 300 to 20,000, preferably 500 to 10,000, very particularly preferably 500 to 5,000, can be used as polyethyleneimines.
  • the weight ratio between the alkylene oxide and polyethyleneimine used is in the range from 100: 1 to 0.1: 1, preferably in the range 50: 1 to 0.5: 1, very particularly preferably in the range 20: 1 to 0.5: 1 , Graft base c2)
  • the graft base c) contains at least one compound from the group of the polymers c2) which contain at least 5% by weight of vinylpyrrolidone units.
  • These polymers used as the graft base preferably contain a vinyl pyrrolidone content of at least 10% by weight, very particularly preferably at least 30% by weight, in particular at least 50% by weight, preferably at least 80% by weight.
  • Polyvinylpyrrolidone homopolymers are particularly preferred as the graft base c).
  • Comonomers of vinylpyrrolidone for the synthesis of the graft base c2) are, for example, N-vinylcaprolactam, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl- 4-methylimidazole, 3-methyl-1-vinylimidazolium chloride, 3-methyl-1- vinylimidazolium methyl sulfate, diallyldimethylammonium chloride, styrene, alkylstyrenes in question.
  • Suitable comonomers for the preparation of the graft base c2) are, for example, monoethylenically unsaturated C 3 -C 6 -carboxylic acids, such as, for example, acrylic acid, methacrylic acid, crotonic acid, fumaric acid, and their esters, amides and nitriles, such as, for example, methyl methylester, ethyl acrylate, methyl methacrylate, methyl thacrylkladoethylester, stearyl methacrylate, hydroxyethyl acrylate, hydroxypropyl pylacrylat, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, Hydroxyisobutylacrylat, Hydroxyisobutylmethacrylat, maleic acid monomethyl ester, maleic acid di ethyl ester, monoethyl maleate, ethyl maleate, 2-eth
  • the graft base c2) is prepared by known processes, for example solution, precipitation, suspension or emulsion polymerization, using compounds which form free radicals under the polymerization conditions.
  • the polymerization temperatures are usually in the range from 30 to 200, preferably 40 to 110 ° C.
  • Suitable initiators are, for example, azo and peroxy compounds and the customary redox initiator systems, such as combinations of Hydrogen peroxide and reducing compounds, for example sodium sulfite, sodium bisulfite, sodium formaldehyde sulfoxylate and hydrazine. These systems can optionally also contain small amounts of a heavy metal salt.
  • the homo- and copolymers have K values of at least 7, preferably 10 to 250. However, the polymers can have K values up to 300.
  • the K values are determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932) in aqueous solution at 25DC, at concentrations which, depending on the K value range, between 0.1% and 5%.
  • Component c) (sum of components d and c2) is preferably used in an amount of 10 to 90% by weight, in particular 20 to 70% by weight, preferably 30 to 60% by weight.
  • graft base c a mixture comprising at least one compound d) polyalkylene glycols and at least one compound c2) polymers which contain at least 50% by weight of vinylpyrrolidone units is used as the graft base c).
  • the mixture used as the graft base c) is a mixture comprising at least one compound d) polyalkylene glycols and at least one compound c2) polymers which contain at least 50% by weight of vinylpyrrolidone units and the polymerization is carried out in the presence of a crosslinking agent d) carried out.
  • graft base c a mixture comprising at least one compound d) polyalkylene glycols and at least one compound c2) polymers containing at least 80% by weight of vinylpyrrolidone units is used as the graft base c).
  • the mixture used as the graft base c) is a mixture comprising at least one compound d) polyalkylene glycols and at least one compound c2) polymers which contain at least 80% by weight of vinylpyrrolidone units and the polymerization is carried out in the presence of a crosslinking agent d) carried out.
  • a mixture comprising at least one compound d) polyalkylene glycols and at least one compound c2) polyvinylpyrrolidone homopolymer is used as the graft base c).
  • a mixture comprising at least one compound d) polyalkylene glycols and at least one compound c2) polyvinylpyrrolidone homopolymer is used as the graft base c) and the polymerization is carried out in the presence of a crosslinking agent d).
  • Component d) is preferably used in an amount of 0 to 10% by weight, in particular 0.01 to 10, in particular 0.05 to 5% by weight, preferably 0.1 to 1.5% by weight.
  • mixtures of the respective monomers from group a), such as Mixtures of N-vinylformamide and N-vinylacetamide can be copolymerized.
  • Component a) is preferably used in an amount of 10 to 90% by weight, in particular 20 to 70% by weight, preferably 30 to 60% by weight.
  • components a), c) and d) are used in the following amounts.
  • the details of the individual percentages by weight always relate to the total sum of components a), c) and d), which is set as 100%. If there are other possible components (e.g. components b) and e), the weight of these other components is calculated based on the sum of a) to d), which is set as 100%.
  • Component a) is preferably used in an amount of 10 to 90% by weight, in particular 20 to 70% by weight, preferably 30 to 60% by weight.
  • Component c) is preferably used in an amount of 90 to 10% by weight, in particular 70 to 20% by weight, preferably 60 to 30% by weight.
  • Component d) is preferably used in an amount of 0 to 10% by weight, in particular 0.01 to 10% by weight, in particular 0.05 to 5% by weight, preferably 0.1 to 1.5% by weight.
  • component c) 90 to 10% by weight, in particular 70 to 20% by weight, preferably 60 to 30% by weight of component c)
  • component d) 0 to 10% by weight, preferably 0.01 to 10% by weight, in particular 0.05 to 5% by weight, preferably 0.1 to 1.5% by weight, of component d)
  • the peroxo- and / or azo compounds which are customary for this purpose can be used as initiators for the radical polymerization, for example alkali metal or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert .-Butyl perpivalate, tert.-butyl peroxy-2-ethylhexanoate, tert.-butyl permaleinate, cumene hydroperoxide, diisopropyl peroxidicarbamate, bis- (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert.-butyl peroxide, tert.-butyl peroxide Di-tert-amyl peroxide, tert
  • Initiator mixtures or redox initiator systems such as e.g. Ascorbic acid / iron (II) sulfate, sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxymethanesulfinate.
  • Ascorbic acid / iron (II) sulfate sodium peroxodisulfate
  • tert-butyl hydroperoxide / sodium disulfite tert-butyl hydroperoxide / sodium hydroxymethanesulfinate.
  • Organic peroxides are preferably used.
  • the polymerization can also be carried out by exposure to ultraviolet radiation, if appropriate in the presence of UV initiators.
  • the photoinitiators or sensitizers which are usually suitable for this are used. These are, for example, compounds such as benzoin and benzoin ether, methylbenzoin or ⁇ -phenylbenzoin. So-called triplet sensitizers, such as benzyl diketals, can also be used.
  • UV radiation sources are used, for example. lamps also have low-UV light sources, such as fluorescent tubes with a high proportion of blue.
  • 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 from 40 to 200 ° C., preferably in the range from 50 to 140 ° C., particularly preferably in the range from 60 to 110 ° C. It is usually carried out under atmospheric pressure, but can also take place 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 the methods which can be used being restricted thereto.
  • the procedure can be such that the graft base c) is dissolved in at least one monomer from group a) and possibly further comonomers from group b) and the mixture is polymerized out after addition of a polymerization initiator.
  • the polymerization can also be carried out semi-continuously by first 10% of the mixture to be polymerized from the graft base c), at least one monomer from group a), possibly further comonomers from group b) and initiator, the mixture is heated to the polymerization temperature and, after the polymerization has started, the rest of the mixture to be polymerized according to the progress of the polymerization.
  • the polymers can also be obtained by placing the graft base c) in a reactor, heating to the polymerization temperature and at least one monomer from group a), possibly further comonomers from group b) and polymerization initiator either all at once, batchwise or preferably continuously adds and polymerizes.
  • the polymerization described above can also be carried out in a solvent.
  • 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 methyl - Or ethyl ether of the dihydric alcohols, diethylene glycol, triethylene glycol, glycerol and dioxane.
  • the polymerization can also be carried out in water as a solvent.
  • a solution which, depending on the amount of the monomers added to component a), is more in water or less soluble.
  • organic solvents such as monohydric alcohols having 1 to 3 carbon atoms, acetone or dimethylformamide.
  • polymerization in water can also be carried out by converting the water-insoluble polymers into a finely divided dispersion by adding customary emulsifiers or protective colloids, for example polyvinyl alcohol.
  • the emulsifiers used are, for example, ionic or nonionic surfactants whose HLB value is in the range from 3 to 13.
  • HLB value is in the range from 3 to 13.
  • the amount of surfactants, based on the polymer is 0.1 to 10% by weight.
  • water is used as the solvent, solutions or dispersions of the polymers are obtained. If solutions of the polymer are prepared in an organic solvent or in mixtures of an organic solvent and water, 5 to 2000, preferably 10 to 500 parts by weight of the organic solvent or solvent mixture are used per 100 parts by weight of the polymer ,
  • the graft copolymers according to the invention can be hydrolyzed after the polymerization. Hydrolysis creates a cationic group in the polymer. This can lead to increased water solubility and improved conditioning properties in cosmetic applications.
  • the graft base also contains comonomers which are sensitive to hydrolysis, e.g. Vinyl acetate or acrylamide, hydrolysis also takes place in the graft base. This is how vinyl acetate reacts to vinyl alcohol groups and acrylamide to acrylic acid groups.
  • Suitable hydrolysis agents are mineral acids, such as hydrogen halides, which can be used in gaseous form or in aqueous solution. Hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid and organic acids such as C to C 5 carboxylic acids and aliphatic or aromatic sulfonic acids are preferably used. 0.05 to 2, preferably 1 to 1.5 molar equivalents of an acid are required per formyl group equivalent which is to be split off from the copolymerized units (IV).
  • the hydrolysis of the polymerized units of structure (IV) can also be carried out using bases, e.g. of metal hydroxides, in particular alkali metal and alkaline earth metal hydroxides. Sodium hydroxide or potassium hydroxide is preferably used.
  • the hydrolysis can optionally also be carried out in the presence of ammonia or amines.
  • the hydrolysis in the acidic or in the alkaline pH range takes place e.g. at temperatures from 30 to 170, preferably 50 to 120 ° C. It is complete after about 2 to 8, preferably 3 to 5 hours. After these reaction times, degrees of hydrolysis of the units of the copolymerized monomers of the formula (I) of 1 to 100% are achieved.
  • a procedure in which the bases or acids are added in aqueous solution for hydrolysis has proven particularly useful.
  • neutralization is generally carried out, so that the pH of the hydrolyzed polymer solution is 2 to 8, preferably 3 to 7. Neutralization is necessary if the progress of the hydrolysis of partially hydrolyzed polymers is to be avoided or delayed.
  • the hydrolysis can also be carried out with the aid of enzymes.
  • the hydroxyl groups of the polyvinyl alcohol units and vinylamine units, formed by hydrolysis of vinylformamide, can preferably be reacted with the epoxides.
  • the epoxides of the formula X can also be generated in situ by reacting the corresponding chlorohydrins with bases, for example sodium hydroxide.
  • 2,3-Epoxypropyl-trimethylammonium chloride or 3-chloro-2-hydroxypropyl-trimethylammonium chloride is preferably used.
  • the K values of the polymers should be in the range from 10 to 300, preferably 25 to 250, particularly preferably 25 to 200, very particularly preferably in the range from 30 and 150.
  • the K value desired in each case can be set in a manner known per se through the composition of the starting materials.
  • the K values are determined according to Fikentscher, Cellulosechemie, Vol. 13, pp. 58 to 64, and 71 to 74 (1932) in N-methylpyrrolidone at 25 ° C and polymer concentrations, which, depending on the K value range between 0, 1% by weight and 5% by weight.
  • the polymer solutions can be steam distilled. After steam distillation, depending on the choice of components a-c, aqueous solutions or dispersions are obtained.
  • the graft polymers obtained can also be crosslinked subsequently by reacting the hydroxyl groups or amino groups in the polymer with at least bifunctional reagents. With low degrees of crosslinking, water-soluble products are obtained, with high degrees of crosslinking, water-swellable or insoluble products are obtained.
  • the polymers according to the invention can be treated with dialdehydes and dipetones, e.g. Glyoxal, glutaraldehyde, succinic dialdehyde or terephthalaldehyde can be implemented.
  • aliphatic or aromatic carboxylic acids for example maleic acid, oxalic acid, malonic acid, succinic acid or citric acid, or carboxylic acid derivatives such as carboxylic acid esters, anhydrides or halides.
  • Polyfunctional epoxides are also suitable, e.g. Epichlorohydrin, glycidyl methacrylate, ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether or 1,4-bis (glycidyloxy) benzene.
  • diisocyanates for example hexamethylene diisocyanate, isophore diisocyanate, methylene diphenyl diisocyanate, tolylene diisocyanate or divinyl sulfone.
  • boric acid or boric acid salts for example sodium metaborate, borax (disodium tetraborate), and salts of polyvalent cations, for example copper (II) salts such as copper (II) acetate or zinc, aluminum, titanium salts.
  • copper (II) salts such as copper (II) acetate or zinc, aluminum, titanium salts.
  • Boric acid or boric acid salts such as sodium metaborate or disodium tetraborate are preferably suitable for subsequent crosslinking.
  • the boric acid or boric acid salts preferably as salt solutions, can be added to the solutions of the polymers according to the invention.
  • the boric acid or boric acid salts are preferably added to the aqueous polymer solutions.
  • the boric acid or boric acid salts can be added to the polymer solutions directly after the preparation. However, it is also possible to subsequently add the boric acid or boric acid salts to the cosmetic formulations with the polymers according to the invention, or during the production process of the cosmetic formulations.
  • the proportion of boric acid or boric acid salts based on the polymers according to the invention is 0 to 15% by weight, preferably 0 to 10% by weight, particularly preferably 0 to 5% by weight.
  • the graft polymer solutions and dispersions can be dried by various drying methods such as e.g. Spray drying, fluidized spray drying, roller drying or freeze drying can be converted into powder form. Spray drying is preferably used as the drying process.
  • An aqueous solution or dispersion can be prepared from the dry polymer powder thus obtained by dissolving or redispersing it in water.
  • the transfer in powder form has the advantage of better storage stability, easier transportation and a lower tendency to germ contamination.
  • the graft copolymers according to the invention are outstandingly suitable for use in cosmetic formulations. They are particularly suitable as conditioning agents and as thickeners.
  • the graft polymers according to the invention are suitable as styling agents and / or conditioning agents in hair cosmetic preparations such as hair treatments, hair lotions, hair rinses, hair emulsions, tip fluids, leveling agents for perms, "hot oil treatment” preparations, conditioners, setting lotions or hair sprays.
  • hair cosmetic preparations can be applied as a spray, foam, gel, gel spray or mousse.
  • the hair cosmetic formulations according to the invention contain
  • Alcohol is to be understood to mean all alcohols customary in cosmetics, for example ethanol, isopropanol, n-propanol.
  • constituents are to be understood as the additives customary in cosmetics, for example blowing agents, defoamers, surface-active compounds, i.e. Surfactants, emulsifiers, foaming agents and solubilizers.
  • surface-active compounds i.e. Surfactants, emulsifiers, foaming agents and solubilizers.
  • the surface-active compounds used can be anionic, cationic, amphoteric or neutral.
  • Other common ingredients may also be e.g.
  • Preservatives perfume oils, opacifiers, active ingredients, UV filters, care substances such as panthenol, collagen, vitamins, protein hydrolyzates, alpha and beta-hydroxycarboxylic acids, protein hydrolyzates, stabilizers, pH regulators, dyes, viscosity regulators, gelling agents, dyes, salts, humectants , Refatting agents and other common additives.
  • this includes all styling and conditioner polymers known in cosmetics, which can be used in combination with the polymers according to the invention if very special properties are to be set.
  • Anionic polymers are suitable as conventional hair cosmetic polymers.
  • Such anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes (Luviset TM P.U.R.) and polyureas.
  • Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example Luvimer TM 100P), copolymers of N-tert-butyl acrylamide, ethyl acrylate, acrylic acid (Ultrahold TM 8, strictly), copolymers of vinyl acetate, crotonic acid and, if appropriate, others Vinyl esters (eg Luviset TM brands), maleic anhydride copolymers, possibly reacted with alcohols, anionic polysiloxanes, eg carboxy-functional, copolymers of vinyl pyrrolidone, t-butyl acrylate, methacrylic acid (e.g. Luviskol TM VBM).
  • Luvimer TM 100P copolymers of N-tert-butyl acrylamide, ethyl acrylate, acrylic acid (Ultrahold TM 8, strictly), copolymers of vinyl acetate,
  • Particularly preferred anionic polymers are acrylates with an acid number greater than or equal to 120 and copolymers of t-butyl acrylate, ethyl acrylate and methacrylic acid.
  • Suitable hair cosmetic polymers are cationic polymers with the designation polyquaternium according to INCl, for example copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat TM FC, Luviquat TM HM, Luviquat TM MS, Luviquat TM Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate with diethyl sulfate (Luviquat TM PQ 11), copolymers of N-vinylcaprolactam N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat TM Hold); cationic cellulose deri vate (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7).
  • Neutral polymers such as polyvinyl pyrrolidones, copolymers of N-vinyl pyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinyl caprolactam and copolymers with N-vinyl pyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts are also suitable as further hair cosmetic polymers , Cellulose derivatives, polyaspartic acid salts and derivatives.
  • the preparations can also contain conditioning substances based on silicone compounds.
  • Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes, silicone resins or dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).
  • the graft polymers according to the invention are particularly suitable as setting agents in hair styling preparations, in particular hair sprays (aerosol sprays and pump sprays without propellant gas) and hair foams (aerosol foams and pump foams without propellant gas).
  • these preparations contain
  • Blowing agents are the blowing agents commonly used for hair sprays or aerosol foams. Mixtures of propane / butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152 a), carbon dioxide, nitrogen or compressed air are preferred.
  • a formulation according to the invention for aerosol hair foams contains
  • nonionic emulsifiers are Laurethe, e.g. Laureth-4; Cetethe, e.g. Cetheth-1, polyethylene glycol cetyl ether; Cetearethe, e.g. Cetheareth-25, polyglycol fatty acid glycerides, hydroxylated lecithin, lactyl esters of fatty acids, alkyl polyglycosides.
  • cationic emulsifiers are cetyldimethyl-2-hydroxyethylammonium dihydrogen phosphate, cetyltrimonium chloride, cetyltrimmonium bromide, cocotrimonium methyl sulfate, quaternium-1 to x (INCI).
  • Anionic emulsifiers can be selected, for example, from the group of alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, in particular alkali metal alkali metal sulfates, for example alkali metal alkali metal sulfates, such as, for example, alkali metal alkali metal sulfates, Sodium, potassium, magnesium, calcium, as well as ammonium and triethanolamine salts.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1
  • a preparation suitable according to the invention for styling gels can be composed, for example, as follows:
  • gel formers customary in cosmetics can be used as gel formers. These include slightly cross-linked polyacrylic acid, for example carbomer (INCI), cellulose derivatives, for example hydroxypropyl cellulose, hydroxyethyl cellulose, cationically modified celluloses, polysaccharides, for example xanthum gum, caprylic / capric triglycerides, sodium acrylate copolymer, polyquaternium-32 (and) paraffin liquid (INCI ), Sodium Acrylates Copolymer (and) Paraffinum Liquidum (and) PPG-1 Trideceth-6, Acrylamidopropyl Trimonium Chloride / Acrylamide Copolymer, Steareth-10 Allyl Ether Acrylates Copolymer, Polyquaternium-37 (and) Paraffinum Liquidum (and) PPG-1 Tri - deceth-6, Polyquaternium 37 (and) Propylene Glycole Dicaprate Dicaprylate (and) PPG-1 Tri
  • Suitable anionic surfactants include for example alkyl sulfates, alkyl ether sulfates, Al kylsulfonate, metal salts of alkylarylsulfonates, alkyl succinates, alkyl sulphosuccinates, N- Alkoylsarkosinate, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali metal and alkaline earth metal, e.g. Sodium, potassium, magnesium, calcium, as well as ammonium and triethanolamine salts.
  • alkali metal and alkaline earth metal e.g. Sodium, potassium, magnesium, calcium, as well as ammonium and triethanolamine salts.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 and 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units, in the molecule.
  • sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine deconyl sulfonate are suitable.
  • Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or propionates, alkylamphodiacetates or dipropionates.
  • cocodimethylsulfopropylbetaine laurylbetaine, cocamidopropylbetaine or sodium cocamphopropionate can be used.
  • Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols with 6 to 20 carbon atoms in the alkyl chain, which can be linear or branched, with ethylene oxide and / or propylene oxide.
  • the amount of alkylene oxide is about 6 to 60 moles per mole of alcohol.
  • Alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters are also suitable.
  • the shampoo formulations can contain customary cationic surfactants, such as quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • customary conditioning agents can be used in combination with the polymers according to the invention in the shampoo formulations.
  • These include, for example, cationic polymers with the designation Polyquaternium according to INCI, in particular copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat TM FC, Luviquat TM HM, Luviquat TM MS, Luviquat TM Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat TM PQ 11), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat TM Hold); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7).
  • Protein hydrolyzates can also be used, and conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
  • silicone compounds for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyether siloxanes or silicone resins.
  • Other suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicone (CTFA).
  • the graft polymers according to the invention can be prepared analogously to the following examples.
  • Example 2 Hydrolysis of Example 1
  • Example 1 500 g of the solution obtained in Example 1 are heated to 80 ° C. with 100 g of distilled water and 1 g of sodium pyrosulfite. After adding 33 g of 25% sodium hydroxide solution, the mixture is stirred at 80 ° C. for 3 hours. After cooling, the pH is adjusted to 8 with 15 g of 38% hydrochloric acid.
  • Example 6 was carried out analogously to Example 5, instead of PEG-PPG block copolymer 72 g of alkylpolyethylene glycol with an average molecular weight of 3500 (Pluriol A 2000, BASF Aktiengesellschaft) were used.
  • Example 7 was carried out analogously to Example 5, instead of PEG-PPG block copolymer, 103 g of polyethylene glycol with an average molecular weight of 20,000 were used.
  • Example 8
  • Example 8 was carried out analogously to Example 5, instead of PEG-PPG block copolymer, 137 g of polyethylene glycol with an average molecular weight of 35,000 were used.
  • Example 9 was carried out analogously to Example 5, instead of PEG-PPG block copolymer, 103 g of polyethylene glycol with an average molecular weight of 20,000 were used.
  • Example 10 was carried out analogously to Example 5, instead of PEG-PPG block copolymer 202 g of dimethicone copolyol (Belsil DMC 6031 TM, from Wacker Chemie GmbH) were used.
  • Example 11 was carried out analogously to Example 5, instead of PEG-PPG block copolymer, 137 g of ethoxylated polyethyleneimine (prepared from 12.5% polyethyleneimine with an average molecular weight of 1400 and 87.5% ethylene oxide) were used.
  • Example 1 Formulation of aerosol hair foam:
  • Example 3 Aerosol hair foam: INCI 4.00% copolymer from Example 3 0.20% Cremophor A 25 Ceteareth-25 1.00% Luviquat Mono CP hydroxyethyl cetyldimonium phosphate
  • Example 6 Pump spray: INCI 4.00% copolymer from Example 3
  • Example of use 12 shower gel
  • a shower gel formulation was prepared according to the following recipe
  • Plantacare 2000 decyl glucoside 5.0
  • Citric acid (pH 6-7) q.s.
  • phase a was stirred into b), homogenized and cold-stirred and then adjusted to pH 6 with 10% aqueous NaOH solution.
  • Example of use 14 O / W cream for moisturizing the skin
  • Example of use 20 Body Care Cream
  • the formulation had a pH of 6.8.
  • the viscosity (Brookfield
  • phase A and phase B separately to 80 ° C. Then mix phase B in phase A with a stirrer. Allow everything to cool to 40 ° C and add phase C and phase D. Homogenize repeatedly.
  • phase A with butylene glycol add to phase B and mix well.
  • Warm phase AB to 75 ° C.
  • Powder phase C feedstocks add to phase AB and homogenize well.
  • Mix feed materials from phase D heat to 80 ° C and add to phase ABC. Mix for a while until everything is homogeneous. Transfer everything to a vessel with a propeller mixer.
  • Mix feed materials from phase E add to phase ABCD and mix well.
  • Premix phase B Mix phase B into phase A with a propeller mixer, allowing the thickener to swell.
  • Moisten phase C with phase D add everything in phase AB and mix well.
  • phase A feedstocks Use a propeller mixer to mix the phase A feedstocks in the order given. Then add phase B to phase A. Stir slowly until everything is homogeneous. Homogenize phase C well until the pigments are well distributed. Add phase C and phase D to phase AB and mix well.
  • Example of use 25 Waterproof mascara
  • phase A Mix the components of phase A. Allow phase B to swell and stir into phase A with homogenization. Neutralize with phase C and homogenize again.
  • phase A Warm phase A to at least 90 ° C and stir until dissolved.
  • Dissolve phase B at 50 ° C and stir into phase A.
  • Compensate for the loss of ethanol at approx. 35 ° C.
  • Example of use 32 Facial toner for dry and sensitive skin
  • Example of use 33 Facial washing paste with peeling effect
  • Example of use 35 Facial cleansing milk type O / W
  • Example of use 37 Peeling cream, type O W phase A
  • Example of use 38 shaving foam
  • Bottling 90 parts of active substance and 10 parts of propane / butane mixture 25:75.
  • Preparation Mix the components of phase A. Stir phase B into phase A while homogenizing, briefly post-homogenize. Neutralize with phase C and homogenize again.
  • Example of use 40 Body care cream phase A
  • Example of use 32 Skin care cream, type O / W
  • Phase A 8.00 Cetearyl Alcohol 2.00 Ceteareth-6 2.00 Ceteareth-25 10.00 Mineral Oil 5.00 Cetearyl Octanoate 5.00 Dimethicone Phase B
  • Example of use 45 lip care cream
  • Phase C 4.00 mica, titanium dioxide
  • phase A components Weigh in and dissolve phase A components. Set pH to 6-7. Add phase B and warm to 50 ° C. Allow to cool to room temperature while stirring.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Veterinary Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Birds (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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  • Cosmetics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

Polymères greffés obtenus par polymérisation greffante radicalaire (a) d'au moins un monomère contenant du N-vinyle, (b) éventuellement d'un ou de plusieurs autres monomères copolymérisables sur un support de greffage polymère (c) qui contient au moins un composé du groupe (c1) et au moins un composé du groupe (c2), le groupe (c1) étant constitué par des composés contenant du polyéther et le groupe (c2) étant constitué par des polymères contenant au moins 5 % en poids d'unités vinylpyrrolidone, et (d) éventuellement d'au moins un réticulant. La présente invention concerne également l'utilisation desdits polymères dans des préparations cosmétiques.
EP04717606A 2003-03-14 2004-03-05 Polymeres greffes et leur utilisation dans des preparations cosmetiques Ceased EP1606328A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE2003111616 DE10311616A1 (de) 2003-03-14 2003-03-14 Pfropfpolymerisate und ihre Verwendung
DE10311616 2003-03-14
PCT/EP2004/002243 WO2004081067A1 (fr) 2003-03-14 2004-03-05 Polymeres greffes et leur utilisation dans des preparations cosmetiques

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EP1606328A1 true EP1606328A1 (fr) 2005-12-21

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Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8084513B2 (en) * 2003-12-30 2011-12-27 Beisang Arthur A Implant filling material and method
US7521404B2 (en) * 2004-12-16 2009-04-21 Georgia-Pacific Consumer Products Lp Antimicrobial liquid hand soap composition with tactile signal comprising a phospholipid surfactant
US7803746B2 (en) * 2004-12-16 2010-09-28 Georgia-Pacific Consumer Products Lp Antimicrobial foam hand soap comprising inulin or an inulin surfactant
FR2926981B1 (fr) * 2008-01-31 2013-03-15 Oreal Composition cosmetique comprenant un copolumere vinylformamide/vinylformamine et un polymere cationique
DE102010002180A1 (de) * 2010-02-22 2011-08-25 Evonik Goldschmidt GmbH, 45127 Stickstoffhaltige silizium-organische Pfropfmischpolymere
EP2571493A1 (fr) * 2010-05-21 2013-03-27 Basf Se Préparations de substances bioactives à base de copolymères amphiphiles présentant une surface augmentée
US20110288181A1 (en) * 2010-05-21 2011-11-24 Basf Se Preparations of biologically active substances with enlarged surface based on amphiphilic copolymers
EP2532691A1 (fr) 2011-06-07 2012-12-12 Basf Se Epaississant associatif à base de méthacrylate
US9095730B2 (en) 2011-06-07 2015-08-04 Basf Se Associative thickeners based on methacrylate
PL2788466T3 (pl) * 2011-12-09 2016-09-30 Zastosowanie kompozycji do maszynowego czyszczenia naczyń kuchennych
US8840731B2 (en) 2011-12-09 2014-09-23 Basf Se Preparations, their production and use
JP6365225B2 (ja) * 2014-10-21 2018-08-01 日油株式会社 枠練り固形石けん
CN105441049B (zh) * 2015-12-02 2018-07-10 四川安东油气工程技术服务有限公司 油气井压裂用可溶性暂堵材料、暂堵剂、压裂液及其制备方法
WO2017117480A1 (fr) * 2015-12-31 2017-07-06 Colgate-Palmolive Company Compositions de nettoyage
US20190175486A1 (en) * 2017-12-07 2019-06-13 Johnson & Johnson Consumer Inc. Oral Care Compositions
FR3075631B1 (fr) * 2017-12-21 2020-04-03 Lvmh Recherche Composition de mascara contenant un ester de tetrahydroxypropylethylene diamine
WO2022020332A1 (fr) 2020-07-21 2022-01-27 Chembeau LLC Formulations cosmétiques à base de diester et leurs utilisations
CN113698549B (zh) * 2021-09-03 2024-05-14 上海昶法新材料有限公司 超支化聚合物及其制备方法、应用、洗涤产品

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
LU72593A1 (fr) * 1975-05-28 1977-02-10
US4713236A (en) * 1981-12-07 1987-12-15 Morton Thiokol, Inc. Polymeric amine conditioning additives for hair care products
DE4127733A1 (de) * 1991-08-22 1993-02-25 Basf Ag Pfropfpolymerisate aus saccharidstrukturen enthaltenden naturstoffen oder deren derivaten und ethylenisch ungesaettigten verbindungen und ihre verwendung
US5270379A (en) * 1992-08-31 1993-12-14 Air Products And Chemcials, Inc. Amine functional polymers as thickening agents
DE4409903A1 (de) * 1994-03-23 1995-09-28 Basf Ag N-Vinyleinheiten enthaltende Pfropfpolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19515943A1 (de) * 1995-05-02 1996-11-07 Basf Ag Pfropfpolymerisate aus Alkylenoxideinheiten enthaltenden Polymerisaten und ethylenisch ungesättigten Verbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE19640363A1 (de) * 1996-09-30 1998-04-02 Basf Ag Verwendung wasserlöslicher Copolymere als Wirkstoffe in kosmetischen Formulierungen
DE19651243A1 (de) * 1996-12-10 1998-06-18 Basf Ag Amphiphile Pfropfpolymerisate auf Basis von N-Vinylcarbonsäureamid-Einheiten enthaltenden Pfropfgrundlagen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10041220A1 (de) * 2000-08-22 2002-03-07 Basf Ag Hautkosmetische Formulierungen
DE10041211A1 (de) * 2000-08-22 2002-03-07 Basf Ag Verwendung hydrophiler Pfropfcopolymere mit N-Vinylamin-und /oder offenkettigen n-Vinylamdeinheiten in kosmetischen Formulierungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004081067A1 *

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CN1751075A (zh) 2006-03-22
JP2006520413A (ja) 2006-09-07
US20060228317A1 (en) 2006-10-12
WO2004081067A1 (fr) 2004-09-23

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