Classifications

• • 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
  • 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
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—Emulsions
• • 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
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
  • A61K8/06—Emulsions
  • A61K8/066—Multiple emulsions, e.g. water-in-oil-in-water
• • 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
  • A61K8/8141—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; 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
  • A61K8/90—Block copolymers
• • 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
  • A61Q15/00—Anti-perspirants or body deodorants
• • 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
• • 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
  • A61Q19/004—Aftersun 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
  • A61Q19/06—Preparations for care of the skin for countering cellulitis
• • 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
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/04—Polymerisation in solution
  • C08F2/10—Aqueous solvent
• • 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

Definitions

• the present invention relates to the use of optionally present in the form of an aqueous dispersion, polymers of ethylenically unsaturated anionic monomers for modifying the rheology of aqueous, alcoholic or aqueous / alcoholic cosmetic or dermatological compositions.
• Polymers are widely used in cosmetics. Their task in hair cosmetics is to influence the properties of the hair, in particular to give the hair firming, to improve combability and to convey a pleasant feel.
• 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. 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.
• Difficulties are often caused by the combination of different properties, such as strong firmness, pleasant feel of the hair and simultaneous thickening effect of the polymers in the hair cosmetic preparations.
• Thickeners are widely used in the pharmaceutical and cosmetic arts to increase the viscosity of aqueous formulations.
• Examples of commonly used thickening agents are fatty acid polyethylene glycol monoesters, fatty acid polyethylene glycol diesters, fatty acid alkanolamides, ethoxylated fatty alcohols, ethoxylated glycerol fatty acid esters, cellulose ethers, sodium alginate, polyacrylic acids and neutral salts.
• Carboxyl group-containing polymers are known as thickeners. These include homo- and copolymers of monoethylenically unsaturated carboxylic acids such as acrylic acid. methacrylic acid, maleic acid, maleic anhydride and itaconic acid. These polymers are often crosslinked at least to a small extent. Such polymers are described, for example, in US 2,798,053, US 3,915,921, US 3,940,351, US 4,062,817, US 4,066,583, US 4,267,103, US 5,349,030 and US 5,373,044. Common disadvantages of these polymers when used as thickeners are their pH dependence and hydrolytic instability. Furthermore, large amounts of the polymers are often needed to achieve the desired thickening effect and the stability of the preparations in the presence of electrolytes is low.
• Naturally occurring materials such as casein, alginates, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and carbomethoxycellulose are also used as thickeners. These have u.a. the disadvantage of susceptibility to microbiological factors and consequently the addition of biocides.
• aqueous dispersions of water-soluble, anionic polymers are known, which are obtainable by free-radical polymerization of ethylenically unsaturated anionic monomers in aqueous medium in the presence of at least one stabilizer, wherein as a stabilizer at least one water-soluble polymer from the groups
• nonionic monoethylenically unsaturated monomers (b1) nonionic monoethylenically unsaturated monomers, (b2) cationic monoethylenically unsaturated monomers and, if appropriate, (b3) anionic monoethylenically unsaturated monomers, the proportion of copolymerized cationic monomers being greater than that of the anionic monomers
• Monomers as a stabilizer.
• Cosmetic gel preparations cosmetic cleansing agents such as, for example, shampoos or skin cosmetic preparations are not described.
• An object of the present invention was to find rheology-modifying, in particular thickening polymers which are well suited for cosmetic applications and have good performance properties, in particular in the field of skin and hair cosmetics.
• this also includes clarity in gel applications, (co) emulsifying and stabilizing action for water-insoluble and / or difficult-to-stabilize components such as silicones and enzymes, hydrolysis- and / or oxidation-sensitive Substances, compatibility with cosmetically customary polymers such as, for example, cationic polymers, good incorporation into cosmetic preparations, compatibility with high surfactant contents, for example in cosmetic cleansing agents such as shampoos.
• Cosmetic preparations are generally aqueous, alcoholic or mixed aqueous-alcoholic nature. It is therefore very particularly desirable to provide thickeners which make it possible to adjust the rheology of both alcohol-based and water-based preparations over a broad pH range.
• the object is achieved by the use of, optionally present in the form of an aqueous dispersion, polymers of ethylenically unsaturated anionic monomers obtainable by free radical polymerization of the monomers in aqueous medium, wherein the polymerization is carried out in the presence of at least one polymer selected from the group a) and at least one polymer selected from the group b), wherein group a) consists of a1) graft polymers of vinyl acetate and / or vinyl propionate on (i) polyethylene glycols or (ii) on one or both sides with alkyl, carboxyl or A) polyalkylene glycols, a3) polyalkylene glycols terminated on one or both sides with alkyl, carboxyl or amino groups, a4) copolymers of alkylpolyalkylene glycol (meth) acrylates and (meth) acrylic acid, and wherein group b ) consists of b1) at least partially h b) water -
• the W / W emulsion polymers of ethylenically unsaturated anionic monomers which are suitable for the use according to the invention and are optionally in the form of an aqueous dispersion are sometimes referred to below as "emulsion polymers of the invention” or "W / W polymers” or "W / W emulsion polymers”
• the polymers of groups a) and b) are also referred to below as “stabilizers”. It is preferred that the W / W emulsion polymers and the polymers a) and polymers b), also referred to as stabilizers, are water-soluble. Water-soluble polymers are understood to mean polymers which are clearly soluble at 20 ° C.
• ethylenically unsaturated anionic monomers include monoethylenically unsaturated C 3 -C 5 -carboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid, itaconic acid and / or the alkali metal or ammonium salts of these acids into consideration.
• monoethylenically unsaturated anionic monomers include monoethylenically unsaturated C 3 -C 5 -carboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid, itaconic acid and /
• Preferred anionic monomers include acrylic acid, methacrylic acid, maleic acid and acrylamido-2-methylpropanesulfonic acid. Particularly preferred are aqueous dispersions of polymers based on acrylic acid.
• the anionic monomers can be polymerized either alone to form homopolymers or else mixed with one another to give copolymers. Examples of these are the homopolymers of acrylic acid or copolymers of acrylic acid with methacrylic acid and / or maleic acid.
• the polymerization of the anionic monomers can also be carried out in the presence of other ethylenically unsaturated monomers.
• These monomers may be nonionic or may carry a cationic charge.
• examples of such monomers are acrylamide, methacrylamide, (meth) acrylic esters of monohydric C r C 22 -alcohols, C 3 -C 22 -alkyl vinyl ethers, C 6 -C 6 -olefins, polyisobutene derivatives, vinyl acetate, vinyl propionate, dialkylaminoethyl ( meth) acrylates, dialkylaminopropyl (meth) acrylates, diallyldimethylammonium chloride, N-vinylformamide, vinylimidazole and quaternized vinylimidazole and partially or completely neutralized or quaternized dialkylamininoalkyl (meth) acrylamides.
• hydrophobic monomers such as (meth) Acrylklareestern of monohydric alcohols having 4 to 22 carbon atoms, C 3 -C 22 -Alkylvinylethem, C 6 -C 6 - olefins or polyisobutene is possible tolerance to salts (salt stability) to increase the thickened with the W / W emulsion polymers cosmetic or dermatological preparations.
• Basic monomers such as dialkylaminoalkyl (meth) acrylates, for example dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate, can be used in the polymerization both in the form of the free bases and in partially or completely neutralized form or quaternized in, for example, C 1 to C 1 alkyl halides.
• the comonomers are used in the preparation of the anionic polymers, for example in amounts such that the resulting polymers are water-soluble and have an anionic charge.
• the amount of nonionic and / or cationic comonomers is, for example, from 0 to 99, preferably from 5 to 75,% by weight.
• Examples of preferred copolymers are copolymers of from 25 to 90% by weight of acrylic acid and from 75 to 10% by weight of acrylamide. Particular preference is given to homopolymers of acrylic acid which are obtainable by free-radical polymerization of acrylic acid in the absence of other monomers, and also copolymers of acrylic acid and / or methacrylic acid which are prepared by copolymerizing acrylic acid and / or methacrylic acid in the presence of pentaerythritol triallyl ether, N, N'-divinylethyleneurea, methylenebisacrylamide, esters of dihydric alcohols with 2 to 8 C-atoms and C 3 - to C 5 carboxylic acids, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane lolpropantrimethylacrylat, pentaerythritol triacrylate, pentaerythritol tetraacrylate, Triallylmethy- lammoniumch
• the polymerization can therefore be carried out in the presence of at least one crosslinker.
• W / W polymers having a higher molecular weight are then obtained than when the anionic monomers are polymerized in the absence of a crosslinker.
• Incorporation of a crosslinker in the polymers also results in reduced solubility of the polymers in water.
• the polymers become water-insoluble, but are swellable in water. There are fluid transitions between complete solubility of the polymers in water and swelling of the polymers in water.
• Crosslinked polymers have a high water absorption capacity due to their swelling capacity in water.
• Crosslinkers which can be used are all compounds which have at least two ethylenically unsaturated double bonds in the molecule. Such compounds are used, for example, in the preparation of crosslinked polyacrylic acids such as superabsorbent polymers, cf. EP-A 858478, page 4, line 30 to page 5, line 43.
• crosslinking agents are triallylamine, pentaerythritol triallether, methylenebisacrylamide, N, N'-divinylethyleneurea, allyl ethers containing at least two allyl groups or vinyl ethers of polyhydric alcohols having at least two vinyl groups, for example Sorbitol, 1, 2-ethanediol, 1, 4-butanediol, trimethylolpropane, glycerol, diethylene glycol and of sugars such as sucrose, glucose, mannose, fully esterified with acrylic or methacrylic dihydric alcohols having 2 to 4 carbon atoms such as ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol dimethacrylate , Butanediol diacrylate, diacrylates or dimethacrylates of polyethylene glycols having molecular weights of from 300 to 600, ethoxylated trimethylolpropane triacrylates or ethoxy
• crosslinking agents are used in the preparation of the anionic dispersions, the amounts of crosslinker used in each case are, for example, 0.0005 to 5.0, preferably 0.001 to 1.0,% by weight, based on the total during the polymerization used monomers.
• Crosslinkers preferably used are pentaerythritol triallyl ether, N, N'-divinylethyleneurea, allyl ethers containing at least two allyl groups of sugars such as sucrose, glucose or mannose and triallylamine and / or ethoxylated trimethylolpropane triacrylate and mixtures of these compounds.
• the polymerization can additionally be carried out in the presence of at least one chain transfer agent.
• chain transfer agents are compounds which contain sulfur in bonded form, such as dodecyl mercaptan, thiodiglycol, ethylthioethanol, di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, diisopropyl disulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, 3 Mercaptopropane-1,2-diol, 1,4-mercaptobutanol, thioglycolic acid, 3-mercaptopropionic acid, mercaptobemic acid, thioacetic acid and thiourea, aldehydes, organic acids such as formic acid, sodium formate or ammonium formate, alcohols such as, in particular, isopro panol and also phosphorus compounds, eg sodium.
• chain transfer agents are compounds which contain sulfur in bonded form, such as dodecyl mercaptan, thio
• the chain transfer agents are preferably used together with at least one crosslinker in the polymerization. By varying the amount and the ratio of chain transfer agent and crosslinker, it is possible to control the rheology of the resulting polymers.
• Chain transfer agents and / or crosslinkers may be initially charged in the polymerization, for example, in the aqueous polymerization medium or dosed together or separately from the monomers, depending on the progress of the polymerization, to the polymerization batch.
• the polymerization usually uses initiators which form radicals under the reaction conditions.
• Suitable polymerization initiators are, for example, peroxides, hydroperoxides, hydrogen peroxide, sodium or potassium persulfate, redox catalysts and azo compounds such as 2,2-azobis (N, N-dimethyleneisobutyricin) dihydrochloride, 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile ), 2,2-azobis (2,4-dimethylvaleronitrile) and 2,2-azobis (2-amidinopropane) dihydrochloride).
• the initiators are used in the amounts customary in the polymerization.
• Azo starters are preferably used as polymerization initiators.
• the aqueous dispersions of the preferably water-soluble anionic W / W emulsion polymers have a polymer concentration of anionic polymers of, for example, 1 to 70% by weight, usually 5 to 50, preferably 10 to 25 and particularly preferably 15 to 20% by weight. According to the invention, they contain at least two different groups of the above mentioned polymers (a) and (b) for stabilizing the anionic polymers formed in the polymerization.
• the amount of stabilizers (a) and (b) in the aqueous dispersion is, for example, from 1 to 40% by weight, usually from 5 to 30% by weight and preferably from 10 to 25% by weight.
• the aqueous dispersions have, for example at a pH of 2.5, viscosities in the range of 200 to 100,000 mPas, preferably 200 to 20,000 mPas, preferably 200 to 10,000 mPas (measured in a Brookfield viscometer at 20 ° C, Spindle 6, 100 rpm).
• Unmated anionic polymers which are suitable for use according to the invention regularly have molecular weights M w in the range from 10,000 to 15 million, preferably from 50,000 to 10 million g / mol.
• the molecular weights are determined, for example, by conventional methods known to the expert, such as SEC (size exclusion chromatography) against a polyacrylic acid standard or with FFF (field-flow fractionation).
• SEC size exclusion chromatography
• FFF field-flow fractionation
• the stabilizers of group (a) include a1) graft polymers of vinyl acetate and / or vinyl propionate on (i) polyethylene glycols or (ii) on one or both sides with alkyl, carboxyl or amino end-capped polyethylene glycols or polypropylene glycols, copolymers from alkylpolyalkylene glycol (meth) acrylates and (meth) acrylic acid and, in addition, polyalkylene glycols and polyalkylene glycols which are end-capped on one or both sides with alkyl, carboxyl or amino groups.
• Polyalkylene glycols are described, for example, in WO 03/046024, page 4, line 37 to page 8, line 9.
• the polyalkylene glycols described therein can either be used directly as a stabilizer of group (a) or modified to grafted onto 100 parts by weight of the polyalkylene glycols, for example 10 to 1000, preferably 30 to 300 parts by weight of vinyl acetate and / or vinyl propionate.
• Polyethylene glycol having a molecular weight M N of 1000 to 100 000 is preferably used as the grafting base, and vinyl acetate is grafted thereon.
• Suitable stabilizers of group (a) are a2) copolymers of alkylpolyalkylene glycol acrylates or alkylpolyalkylene glycol methacrylates and acrylic acid and / or methacrylic acid. They are prepared by first esterifying addition products of ethylene oxide and / or propylene oxide onto, for example, C 1 - to C 8 -alcohols with acrylic acid and / or methacrylic acid and then copolymerizing these esters with acrylic acid and / or methacrylic acid.
• the commonly used Copolymers contain, for example, 5 to 60, preferably 10 to 35 wt .-% of copolymerized units of alkylpolyalkylene glycol (meth) acrylates and 95 to 40, preferably 90 to 65 wt .-% of copolymerized units of (meth) acrylic acid. They usually have molar masses M w of 2,000 to 50,000, preferably 5,000 to 20,000. These copolymers can be used in the form of the free acid groups or else in completely or partially neutralized form in the preparation of the dispersions. The carboxyl groups of the copolymers are preferably neutralized with sodium hydroxide or ammonia.
• Further suitable stabilizers (a) are the above-mentioned polyalkylene glycols (ae3) and the polyalkylene glycols a4) which are end-capped on one or both sides with alkyl, carboxyl or amino groups.
• the abovementioned polymers have, for example, molar masses M n of from 100 to 100,000, preferably from 300 to 80,000, particularly preferably from 600 to 50,000 and in particular from 1,000 to 50,000.
• polymers of group (a) are polyalkylene glycols having molecular weights M n of 100 to 100,000, one or both sides with alkyl, carboxyl or amino groups end-capped polyalkylene glycols having molecular weights M n of 100 to 100,000 used.
• polymers are described, for example, in WO 03/046024, page 4, line 37 to page 8, line 9, cited above.
• Preferred polyalkylene glycols are, for example, polyethylene glycol, polypropylene glycol and block copolymers of ethylene oxide and propylene oxide.
• the block copolymers may contain copolymerized ethylene oxide and propylene oxide in any desired amounts and in any order.
• the OH end groups of the polyalkylene glycols may optionally be end-capped on one or both sides with alkyl, carboxyl or amino groups, preferably a methyl group being considered as an end group.
• Particularly preferably used stabilizers of group (a) are copolymers of ethylene oxide and propylene oxide. Particular preference is given to block copolymers of ethylene oxide and propylene oxide having a molecular weight M n of from 500 to 20 000 g / mol and a content of ethylene oxide units of from 10 to 80 mol%. Particularly preferably used stabilizers of group (a) are block copolymers of the general formula (EO) x (PO) y (EO) z .
• the OH end groups of these polyalkylene glycols may optionally be end-capped on one or both sides with alkyl, carboxyl or amino groups, with the end group preferably being a methyl group.
• the molar mass of preferred polyalkylene glycols is in the range from 300 to 20,000, preferably from 900 to 9000 g / mol, with a proportion of ethylene oxide in the range from 10 to 90% by weight.
• Such polyalkylene glycols are commercially available for example as Pluronic ® brands.
• Pluronic ® PE grades are non-ionic, non-ionic surfactants made by copolymerizing propylene oxide and ethylene oxide. As the following general formula (I) shows, it is at the Pluronic ® PE brands block polymers in which polypropylene glycol is the central part of the molecule:
• the Pluronic PE types such as Pluronic ® PE 3100 Pluronic ® PE 4300, Pluronic ® PE 6100, Pluronic ® PE 6120, Pluronic ® PE 6200 Pluronic ® PE 6400 Pluronic ® PE 7400 Pluronic ® PE 8100 are particularly preferred , Pluronic ® PE 9200, Pluronic ® PE 9400, PE 10100 Pluronic ®, Pluronic ® PE 10300 Pluronic ® PE 10400, Pluronic ® PE 10500, Pluronic ® PE 10500 solution Pluronic ® PE 3500th
• mixtures of the abovementioned polyalkylene glycols are used as polymers a).
• Preferred mixtures are, for example, mixtures of different Pluronic brands, the mixing weight ratio being in the range from 5: 1 to 1: 5, preferably in the range from 2: 1 to 1: 2, in particular in the range from 1.3: 1 to 1: 1, 3 is located.
• Particularly suitable for the preparation of W / W emulsion polymers for use in the invention are the mixtures of Pluronic ® PE 4300 and Pluronic ® PE 6200 comprise or consist thereof.
• the polymers of group (a) are used, for example, in amounts of 1 to 39.5% by weight, preferably 5 to 30% by weight and more preferably 10 to 25% by weight, based on the total dispersion, in the preparation the dispersions used.
• Suitable polymers of group b) are selected from b1) at least partially hydrolyzed copolymers of vinyl alkyl ethers and maleic anhydride, which may at least partially be in salt form, b2) water-soluble starch from the group of cationically modified starch, anionically modified starch, degraded starch and maltodextrin, b3) anionic copolymers selected from the group consisting of
• Suitable polymers of group (b) are: b1) at least partially hydrolyzed copolymers of vinyl alkyl ethers and maleic anhydride, which may be present at least partly in the form of the alkali metal or ammonium salts.
• the alkyl group of the vinyl alkyl ethers preferably has 1 to 4 carbon atoms.
• the copolymers are obtainable by copolymerizing the vinyl alkyl ethers with maleic anhydride followed by partial or complete hydrolysis of the anhydride groups to carboxyl groups and optionally partial or complete neutralization of the carboxyl groups to form the salts.
• Particularly important Preferred polymers of group (b) are at least partially or fully hydrolyzed copolymers of vinyl methyl ether and maleic anhydride, which are present at least partially in the form of their alkali metal or ammonium salts.
• Preferred starches are water-soluble starches, in particular water-soluble potato starches.
• Examples of cationically modified potato starches are the commercial products Amylofax ® 15 and Perlbond ® 970.
• C * Pur® 1906 is an example of an enzymatically degraded potato starch and maltodextrin C 01915 for a hydrolytically degraded potato starch.
• maltodextrin is preferably used.
• anionic copolymers selected from the group of b3-1) homo- and copolymers comprising or consisting of anionic monomers, b3-2) copolymers of anionic and cationic and optionally neutral monomers, wherein the proportion of copolymerized anionic monomers is greater than that of the cationic monomers and b3-3) copolymers of at least one anionic monomer and at least one monomer from the group of esters of anionic monomers with monohydric alcohols, styrene, N-vinylpryrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylformamide, acrylamide , Methacrylamide, vinyl acetate and vinyl propionate.
• the polymers of group (b3-1) are, for example, at least one homopolymer of an ethylenically unsaturated C 3 - to C 5 -carboxylic acid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid, the partially or completely with alkali metal and / or Ammonium bases neutralized SaI ze and / or at least one copolymer of these monomers.
• ethylenically unsaturated carboxylic acids which are used for the preparation of the aqueous dispersions have already been mentioned. Accordingly, these anionic monomers can likewise be used for the preparation of the polymers (b) of the stabilizer mixtures.
• Acrylic acid, methacrylic acid, acrylamidomethylpropanesulfonic acid and / or the mixtures in any ratios are preferably suitable for this purpose.
• copolymers of methacrylic acid and acrylamidomethylpropanesulfonic acid wherein in a preferred embodiment, the molar ratio of Methacrylic acid to acrylamidomethylpropanesulfonic acid used in the preparation of the copolymers in the range from 9: 1 to 1: 9, preferably from 9: 1 to 6: 4.
• suitable polymers of group (b3-2) of the stabilizer mixture are copolymers of (i) at least one ethylenically unsaturated C 3 - to C 5 -carboxylic acid, vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, vinylphosphonic acid and / or their alkali metal and / or ammonium salts,
• At least one cationic monomer from the group of partially or completely neutralized dialkylaminoalkyl (meth) acrylates, partially or completely quaternized dialkylaminoalkyl (meth) acrylates, dialkylaminoalkyl (meth) acrylamides in quaternized or neutralized form, dialkyldiallylamonium halides and quaternized n Vinylimidazole and optionally
• anionic monomers (i) have already been mentioned above.
• Examples of cationic monomers (ii) are dialkylaminoalkyl (meth) acrylates, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate and diethylaminopropyl methacrylate, dialkyldialylammonium halides such as dimethyldiallylammonium chloride and diethyldiallylammonium chloride, N-vinylimidazole, quaternized N Vinylimidazole and dialkylaminoalkyl acrylamides such as dimethylaminoethylacrylamide or dimethylaminoethylmethacrylamide.
• dialkylaminoalkyl (meth) acrylates
• Basic monomers such as dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate can be used both in the form of the free bases and in partially or completely neutralized form with acids such as hydrochloric acid, sulfuric acid, formic acid and p-toluenesulfonic acid.
• the basic monomers can also be partially or completely quaternized by reaction with d- to Ci ⁇ -alkyl halides and / or Cr to C-alkyl or d- to C ⁇ -Alkylar ⁇ lhalogeniden and used in this form in the polymerization.
• dimethylaminoethyl (meth) acrylates completely quaternized with methyl chloride such as dimethylaminoethyl acrylate methochloride or dimethylaminoethyl methacrylate methochloride.
• the polymers of group (b) can also contain vinylamine units as cationogenic groups. Such polymers are obtainable, for example, by optionally adding N-vinylformamide together with at least one anionic water-soluble mono- polymerized and the polymers then hydrolyzed with partial elimination of formyl groups to polymers containing vinylamine units.
• neutral monomers (iii) for example, the esters of anionic monomers, in particular C 3 - to C 5 -carboxylic acids, and monohydric alcohols having 1 to 20 carbon atoms, in particular methyl acrylate, methyl methacrylate, ethyl acrylate, n-, sec-.
• Copolymers of group (b3-3) are also copolymers of (i) at least one anionic monomer and
• the polymers (b3) may contain the monomers in question in any ratios in copolymerized form, with only the amphoteric copolymers being constructed so that they always carry an anionic charge.
• the average molecular weight M w of the polymers of group (b) of the stabilizer mixture is, for example, up to 1.5 million, usually up to 1.2 million, and is preferably in the range of 1000 to 1 million, usually 1500 to 100,000 and especially 2000 to 70 000 (determined by the method of light scattering).
• water-soluble, nonionic monomers (b1) are acrylamide, methacrylamide, N-vinylformamide, N-vinylpyrrolidone and N-vinylcaprolactam.
• all nonionic, monoethylenically unsaturated monomers which have a water solubility of at least 100 g / l at a temperature of 20 ° C. are suitable as monomers of group (b1).
• monomers (b1) which are miscible with water in any ratio and form clear aqueous solutions, such as acrylamide or N-vinylformamide.
• Water-soluble, cationic, monoethylenically unsaturated monomers are, for example, dialkylaminoalkyl (meth) acrlylates, such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate and diethylaminopropyl methacrylate, dialkyldiallyammonium halides, such as dimethyldiallylammonium chloride and diethyldiallylammonium chloride.
• dialkylaminoalkyl (meth) acrlylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl
• Basic monomers such as dimethylaminoethyl acrylate or dimethylaminoethyl methacrylate can be used both in the form of the free bases and in partially or completely neutralized form with acids such as hydrochloric acid, sulfuric acid, formic acid and p-toluenesulfonic acid.
• the basic monomers can also be partially or 8 -alkylaryl by reacting with d- to C-alkyl halides and / or d- to C 8 alkyl d- to Ci temiert square completely and used in this form in the polymerization.
• dimethylaminoethyl (meth) acrylates quaternized completely with methyl chloride such as dimethylaminoethyl acrylate methochloride or dimethylaminoethyl methacrylate methochloride.
• the polymers of group (b4) may also contain vinylamine units as a cationic group. Such polymers can be obtained, for example, by polymerizing N-vinylformamide, if appropriate together with at least one anionic, water-soluble monomer, and then hydrolyzing the polymers with partial removal of formyl groups to polymers containing vinylamine units.
• the polymers of group (b4) may optionally contain at least one anionic monoethylenically unsaturated monomer (b4-3) in copolymerized form.
• anionic monomers which form water-soluble polymers such as acrylic acid, methacrylic acid, vinylsulfonic acid, vinylphosphonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and the alkali metal and ammonium salts of these acids.
• copolymers of group (b4) are copolymers of (b4-1) acrylamide, methacrylamide, N-vinylformamide, N-vinylpyrrolidone and / or N-vinylcaprolactam,
• dialkylaminoalkyl acrylate dialkylaminoalkyl methacrylate, partially or completely neutralized dialkylaminoalkyl (meth) acrylates, quaternized dialkylaminoalkyl (meth) acrylates, dialkyldiallylammonium halides, N-vinylimidazole and quaternized N-vinylimidazole, and optionally
• the polymers (b4-3) acrylic acid, methacrylic acid, vinylsulfonic acid, vinylphosphonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and the alkali metal and ammonium salts of these acids.
• the polymers (b4) contain, for example
• (b4-1) 2 to 90, preferably 20 to 80 and particularly preferably 35 to 70 mol% of at least one nonionic monomer
• (b4-2) 2 to 90, preferably 20 to 80 and particularly preferably 35 to 70 mol% of at least one cationic monomer and
• (b4-3) 0 to 48.9 mol%, preferably 0 to 30 and particularly preferably 0 to 10 mol% of at least one anionic monomer in copolymerized form, wherein the proportion of the cationic monomer units is greater than that of the anionic monomer units.
• polymers (b4) are copolymers of acrylamide and dimethylaminoethyl acrylate methochloride, copolymers of acrylamide and dimethylaminoethyl methacrylate methacrylate, copolymers of acrylamide and dimethylaminopropyl acrylate methochloride, copolymers of methacrylamide and dimethylaminoethyl methacrylmetochloride, copolymers of acrylamide, dimethylaminoethyl acrylate methacrylate and acrylic acid, Copolymers of acrylamide, Dimethylami- noethylmethacrylatmethochlorid and methacrylic acid and copolymers of acrylamide, Dimethylaminoethylacrylatmethochlorid and acrylic acid.
• the polymers (b) can also be characterized by means of the K value. They have, for example, a K value of from 15 to 200, preferably from 30 to 150 and particularly preferably from 45 to 110 (determined by H. Fikentscher, Cellulose-Chemie, Volume 13, 58-64 and 71-74 (1932) in FIG wt .-% aqueous saline at 25 ° C, a polymer concentration of 0.1 wt .-% and a pH of 7).
• the aqueous dispersions used according to the invention contain the polymers of group (b), for example, in amounts of 0.5 to 15, preferably 1 to 10% by weight.
• the ratio of the polymers of group (a) to polymers of group (b) is in the dispersions used according to the invention, for example 1: 5 to 5: 1 and is preferably in the range of 1: 2 to 2: 1.
• the aqueous dispersions of the anionic polymers preferably contain a combination as stabilizer
• (b1) at least one at least partially hydrolyzed copolymer of vinyl alkyl ether, preferably vinyl methyl ether and maleic anhydride, which may be present at least partially in salt form.
• the following combination of polymers is used: (a) copolymers of alkylpolyalkylene glycol acrylates or alkylpolyalkylene glycol methacrylates and acrylic acid and / or methacrylic acid and
• (b1) at least one hydrolyzed copolymer of vinyl methyl ether and maleic anhydride in the form of the free carboxyl groups and at least partially in the form of the salts formed with sodium hydroxide solution, potassium hydroxide solution or ammonia.
• stabilizers for the preparation of the aqueous dispersions of anionic polymers are, for example, mixtures of
• the aqueous dispersions of the anionic polymers preferably contain as stabilizer a combination of (a) at least one block copolymer of ethylene oxide and propylene oxide and
• (b3) at least one copolymer of methacrylic acid and acrylamidomethylpropanesulfonic acid, copolymer of methyl acrylate, acrylamidomethylpropanesulfonic acid and quaternized vinylimidazole with a total of anionic La fertil, copolymer of acrylamidomethylpropanesulfonic acid, acrylic acid, methyl acrylate and styrene, polyacrylic acid, polymethacrylic acid and polyacrylamido methylpropanesulfonic acid.
• the aqueous dispersions of the anionic polymers preferably contain as stabilizer a combination of
• the copolymer (b4) may optionally contain up to 5 mol% of acrylic acid in a polymerized form.
• the weight ratio of the components (a) and (b) in the stabilizer mixtures can be varied within a wide range. For example, it can be 50: 1 to 1:10. It is preferable to choose a ratio of (a) :( b) of at least 1.5: 1, in particular from 7: 1 to 10: 1.
• the particle sizes of the anionic W / W polymers in the stable aqueous dispersions are in the range from 0.1 to 200 .mu.m, preferably 0.5 to 70 .mu.m.
• the particle size can be z. For example, be determined by optical microscopy, light scattering or freezing Bruk electron microscopy.
• the aqueous dispersions are prepared, for example, at pH values of 0.5 to 9, preferably 1 to 5. At pH values below 9, dispersions containing about 5 to 35% by weight of anionic polymers have a relatively low viscosity. If they are diluted to a content of anionic polymers less than 4 wt .-%, the viscosity of the mixture increases sharply.
• anionic W / W emulsion polymers which are optionally present in the form of an aqueous dispersion are used as thickeners for cosmetic preparations.
• W / W emulsion polymers can be dried in a simple manner to redispersible polymer powders.
• Rheology modifiers and in particular thickeners based on conventional homo lyacrylates are usually obtained in solid form, preferably as a powder, because of the preparation process (preferably the precipitation polymerization).
• the problem then frequently arises of having to transfer the solids back into a liquid medium. This is often done by gradual wetting of the polymer particles with solvent, preferably with water at a pH of less than 7, often less than 4, and strong and / or prolonged stirring.
• the conventional Thickener first dissolved in an acidic medium and added the other ingredients.
• the incorporation of homopolyacrylate-based thickeners of the prior art in basic media is not possible.
• the medium thickened after addition of the thickener immediately and the powdery thickener does not form or hardly soluble particles and the setting of a defined viscosity is not possible in this way.
• Suitable neutralizing agents are the cosmetically or dermatologically acceptable and customary neutralizing agents.
• alkali metal bases such as sodium hydroxide solution, potassium hydroxide solution, soda, sodium bicarbonate, potassium carbonate or potassium bicarbonate and alkaline earth metal bases such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate and ammonia or amines can be used.
• Suitable amines are, for. B.
• CrC 6 alkylamines preferably n-propylamine and n-butylamine, dialkylamines, preferably diethylpropylamine and dipropylmethylamine, tri alkylamines, preferably triethylamine and triisopropylamine, Ci-C 6 -alkyldiethyanolamine, preferably methyl or ethyldiethanolamine and di-Ci-Ce -Alkylethanolamine.
• 2-amino-2-methyl-1-propanol (AMP), 2-amino-2-ethyl-propane-1, 3, have especially for use in cosmetic preparations, in particular in skin and hair treatment agents, for the neutralization of polymers containing acid groups -diol, Diethy- laminopropylamine, triisopropanolamine and triethanolamine proven.
• the neutralization of the polymers containing acid groups can also be carried out with the aid of mixtures of several bases, for.
• the extent of the thickening effect can be determined by the choice of the appropriate neutralizing agent. For example, using AMP results in a higher viscosity than when using NaOH.
• the degree of neutralization may be 5 to 95%, preferably 30 to 95%, or more than 99% depending on the purpose of use. Furthermore, the neutralizing agent can also be added in more than equivalent amount.
• the use of the W / W emulsion polymers gives rise to numerous new possibilities for producing thickened cosmetic preparations.
• the W / W emulsion polymers can be added to the preparation to be thickened at any pH.
• the W / W emulsion polymers and their dispersions can be in both acidic and are also dissolved in the basic medium, advantageously with the application of only low shear forces.
• the W / W emulsion polymers and their dispersions can be incorporated into alkaline preparations.
• Homopolyacrylate thickeners of the prior art can, if at all, be incorporated into alkaline preparations only to a very small extent and using high shear forces or long stirring times.
• W / W emulsion polymers can be added at any stage of the preparation of the cosmetic preparations.
• the W / W emulsion polymers can be added only at the end of the preparation of the preparations. This in turn means that the other ingredients can be incorporated into the low-viscosity preparation and for this no high shear forces are necessary. The incorporation of solid, mechanically unstable ingredients is thus facilitated.
• the polymers and dispersions suitable for the use according to the invention furthermore have the advantage that, owing to their low viscosity, they are easy to handle and dose and dissolve rapidly in the medium to be thickened. This in turn results in shorter process times.
• the W / W emulsion polymer dispersion can either be incorporated directly into a cosmetic preparation, for example a hair setting preparation, preparations for skin or hair cleansing or a shampoo, or a conventional drying of the dispersion known to the person skilled in the art, e.g. Spray drying or freeze drying, so that the W / W emulsion polymer can be used as a powder and processed.
• a cosmetic preparation for example a hair setting preparation, preparations for skin or hair cleansing or a shampoo
• a conventional drying of the dispersion known to the person skilled in the art e.g. Spray drying or freeze drying, so that the W / W emulsion polymer can be used as a powder and processed.
• emulsion polymers described above are outstandingly suitable for use according to the invention, in particular as thickeners in cosmetic preparations.
• Such cosmetic preparations are, for example, aqueous, aqueous-alcoholic or alcoholic solutions, O / W, W / O, W / O / W and PIT emulsions, hydrodispersion formulations, solid-stabilized formulations, stick formulations.
• Important preparation types are creams, foams, sprays (pump spray or aerosol), gels, gel sprays, lotions, oils, oil gels or mousses, which are accordingly formulated with customary further excipients.
• Preferred cosmetic compositions for the purposes of the present invention are shampoos, gels, gel creams, hydroformulations, stick formulations, cosmetic oils and oil gels, mascara, self-tanner, facial care, personal care products, after-sun preparations, hair shaping compositions, hair setting agents, hair conditioners and decorative cosmetics.
• Cosmetic and dermatological formulations containing W / W emulsion polymers become rheologically modified systems as soon as mono- or polyolic components or water are present.
• This allows the preparation of preparations in the form of transparent gels, water-free, hydrophilic gels with stabilized water-sensitive agents, the stabilization of oxidation-sensitive substances, the production of low-dryness or drip-free hair dyes, the production of disinfectant gels, the construction of preservative-free gel systems or the preparation gels with a high concentration of highly polar solvents such as glycerine.
• the cosmetic compositions contain preferably in addition to thickening W / W polymers nor in such formulations usual, cosmetically acceptable additives such as emulsifiers and co-emulsifiers, solvents, surfactants, oil, preservatives, perfume oils, cosmetic care and active ingredients such as AHA acids, fruit acids, Ceramides, phytantriol, collagen, vitamins and provitamins, for example vitamins A, E and C, retinol, bisabolol, panthenol, natural and synthetic sunscreens, natural products, opacifiers, solubilizers, repellents, bleaches, colorants, tints, tanning agents (eg dihydroxyacetone), mic pigments such as titanium oxide or zinc oxide, superfatting agents, pearlescent waxes, bodying agents, thickeners, solubilizers, complexing agents, fats, waxes, silicone compounds, hydrotropes, dyes, stabilizers, pH regulators, reflectors, proteins and protein hydrolysates (eg wheat, almond or
• compositions of the invention in such a liquid form that cloths of various materials and embossing can be soaked with them.
• the person skilled in the art knows how to prepare such impregnated wipes.
• UV light stabilizers may also be present in the cosmetic compositions.
• Another object of the invention are cosmetic compositions containing the optionally present in the form of an aqueous dispersion W / W emulsion polymers.
• Particularly preferred cosmetic agents are shampoos and gels.
• the W / W emulsion polymers described above, if present in the form of an aqueous dispersion, are suitable for the production of hair cosmetic preparations such as hair treatments, hair lotions, hair rinses, hair emulsions, top fluids, permeasuring agents, hot oil treatment preparations, conditioners Depending on the application, the hair cosmetic preparations can be applied as a spray, foam, gel, gel spray or mousse.
• the W / W emulsion polymers are outstandingly suitable for the thickening of hydrogen peroxide-containing oxidation hair dyes and thus for the production of viscous, low-drip or even drip-free hair dyes.
• the W / W emulsion polymers can be used, in particular, in nonaqueous, alcoholic media for stabilizing substances susceptible to oxidation and / or hydrolysis, for example vitamin C.
• the W / W emulsion polymers are advantageously used to formulate subtilisin, lecithin and coenzyme Q10.
• compositions are aqueous, alcoholic or aqueous / alcoholic compositions containing the at least one W / W 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.%, Based on the composition.
• aqueous compositions is meant 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 comprising at least one W / W polymer and preferably at least 50% by weight of water and preferably at most 40% by weight of alcohol.
• Another embodiment of the invention is alcoholic compositions comprising at least one W / W polymer and at most 10, preferably at most 5, more preferably at most 2 and in particular at most 1 wt.% Water.
• Such low-water or nearly anhydrous preparations can be thickened by the W / W polymers.
• the W / W 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 W / W polymers which are suitable for the uses according to the invention are particularly 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.
• Polyols which are suitable according to the invention can advantageously be chosen from the group of the at least bifunctional alcohols. Particularly advantageous are the polyols selected from the following group:
• Ethylene glycol polyethylene glycols having molecular weights of up to about 2,000, propylene glycol-1,2, polypropylene glycols-1,2 with molecular weights of up to about 2,000, propylene glycol-1,3, polypropylene.
• ethylene glycol-1, 3 having molecular weights of up to about 2,000, butylene glycol-1,2, polybutylene glycol-1,2, having molecular weights of up to about 2,000, butylene glycol-1,3, polybutylene glycols-1,3, having molar masses of up to approx 2,000, butylene glycol-1,4, polybutylene glycol-1,4, having molecular weights up to about 2,000, butylene glycol-2,3, polybutylene glycol-2,3 having molecular weights up to about 2,000, glycerol, diglycerol, triglycerol, tetraglycerol and pentaglycerol in which the ON-goglycerols are composed of glycerol units condensed via one or more ether bridges, for example as follows:
• the alcohol is or comprises ethanol, glycerol and / or isopropanol, particularly preferably glycerol and / or ethanol.
• the W / W polymers act as thickeners both in alcoholic and essentially anhydrous, as well as in aqueous and substantially alcohol-free and aqueous / alcoholic compositions.
• the compositions according to the invention contain a) 0.05-20% by weight W / W emulsion polymer b) 20-99.95% by weight water and / or alcohol c) 0-79.5 parts by weight % further constituents
• Further constituents are understood to mean the additives customary in cosmetics, for example propellants, defoamers, surface-active compounds, ie surfactants, emulsifiers, foaming agents and solubilizers.
• the surface-active compounds used can be anionic, cationic, amphoteric or neutral.
• typical ingredients may also be, for example, preservatives, perfume oils, opacifiers, active ingredients, UV filters, care agents such as panthenol, collagen, vitamins, protein hydrolysates, alpha- and beta-hydroxycarboxylic acids, protein hydrolysates, stabilizers, pH regulators, dyes, viscosity regulators, Gel formers, dyes, salts, humectants, moisturizers and other common additives.
• care agents such as panthenol, collagen, vitamins, protein hydrolysates, alpha- and beta-hydroxycarboxylic acids, protein hydrolysates, stabilizers, pH regulators, dyes, viscosity regulators, Gel formers, dyes, salts, humectants, moisturizers and other common additives.
• the W / W polymers can be used in combination with the known styling and conditioner polymers.
• Suitable conventional hair cosmetic polymers are, for example, anionic polymers.
• anionic polymers are homo- and copolymers of acrylic acid and methacrylic acid or their salts, copolymers of acrylic acid and acrylamide and their salts; Sodium salts of polyhydroxycarboxylic acids, water-soluble or water--dispersible polyesters, polyurethanes (PUR Luviset ®) and polyureas.
• Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, Methac- rylklare (eg Luvimer 100P ®), copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold ® 8, strong), copolymers of vinyl acetate, crotonic acid and, where In addition, further Vinylestem (eg Luviset ® brands), maleic anhydride copolymers, optionally reacted with alcohols, anionic polysiloxanes, for example carboxy-functional, copolymers of vinylpyrrolidone, t-butyl acrylate, methacrylic acid (eg Luviskol ® VBM).
• anionic polymers acrylates having an acid number greater than or equal to 120 and copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid are very particularly preferred.
• Suitable hair cosmetic polymers are cationic polymers having the INCI name Polyquaternium, eg copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ® FC, Luviquat ® HM, Luviquat ® MS, Luviquat ® Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat ® PQ 11), copolymers of N-vinyl caprolactam, N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat Hold ®); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7).
• Polyquaternium eg copolymers of vinylpyrrolidone / N-vinylimida
• hair cosmetic polymers which are also suitable are neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinylpropionate, polysiloxanes, polyvinylcaprolactam and copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and salts thereof , Cellulose derivatives, polyaspartic acid salts and derivatives.
• the preparations may additionally contain conditioning substances based on silicone compounds.
• Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyaralkylalkylsiloxanes, polyethersiloxanes, silicone resins or dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).
• CTFA dimethicone copolyol
• the W / W emulsion polymers are suitable, for example, for producing hairstyling preparations, in particular clear, transparent gels and gel sprays.
• these preparations comprise a) 0.1-10% by weight W / W emulsion polymer b) 20-99.9% by weight water and / or alcohol c) 0-70% by weight of a blowing agent d) 0-20% by weight of further constituents
• Blowing agents are the blowing agents commonly used for hairsprays or aerosol foams. Preference is given to mixtures of propane / butane, pentane, dimethyl ether, 1,1-difluoroethane (HFC-152a), carbon dioxide, nitrogen or compressed air.
• a preferred formulation for aerosol hair foams according to the invention contains a) 0.1-10% by weight W / W emulsion polymer b) 55-94.8% by weight water and / or alcohol c) 5-20% by weight of a blowing agent d) 0.1-5 wt .-% of an emulsifier e) 0-10 wt .-% further constituents
• emulsifiers all emulsifiers commonly used in hair foams can be used. Suitable emulsifiers may be nonionic, cationic or anionic.
• 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 W / W emulsion polymers can be used as the only gelling agent in the cosmetic preparations due to their thickening effect. In addition, they are also suitable for use in combination with other gelling agents.
• a preparation suitable for clear styling gels according to the invention can be composed, for example, as follows: a) 0.1-10% by weight of W / W emulsion polymer b) 60-99.85% by weight of water and / or alcohol c) 0-10% by weight of a further gelling agent d) 0-20 wt .-% further constituents
• Other gel formers which can be used are all gel formers customary in cosmetics.
• polyacrylic acid for example carbomer (INCI)
• cellulose derivatives for example hydroxypropylcellulose, hydroxyethylcellulose, cationically modified celluloses
• polysaccharides for example xanthum gum
• caprylic / capric triglycerides sodium acrylate copolymer
• polyquaternium-32 and) paraffin liquidum (INCI)
• Sodium Acrylate Copolymer and) Paraffin Liquidum (and) PPG-1 Trideceth-6, Acrylamidopropyl Trimonium Chloride / Acrylamide Copolymer, Steareth-1 O Allyl Ether Acrylate Copolymer
• Polyquaternium-37 and) Paraffinum Liquidum (and) PPG-1 Tri deceth-6, Polyquaternium 37 (and) Propylene Glycols Dicaprate Dicaprylate (and) PPG-1 Trideceth-6, Polyquaternium-7, Polyquaternium-44.
• An embodiment of the invention are cosmetic preparations, in particular hair gels on an alcoholic, substantially anhydrous basis with a content of W / W emulsion polymers, at least 30 wt.% DC 4 -alcohols and optionally an alcohol-soluble, film-forming and hair-setting polymer.
• Gels based on dC 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 W / W emulsion polymer is used preferably 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 alcoholic, substantially anhydrous basis are monohydric or polyhydric alcohols which are liquid at room temperature (20 ° C.) and have 1 to 4 C atoms. These are in particular the customarily used for cosmetic purposes lower alcohols such. For example, ethanol, isopropanol, glycerol, ethylene glycol or propylene glycol. Particular preference is given to monohydric alcohols having 2 to 4 C atoms, in particular ethanol and isopropanol.
• the hair gel is preferably substantially anhydrous, but it may to improve the solubility of other ingredients contain small amounts of water, 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 W / W emulsion polymers can advantageously also be used in shampoo formulations.
• Preferred shampoo formulations contain a) 0.05-10 wt% W / W emulsion polymer b) 25-94.95 wt% water c) 5-50 wt% surfactants d) 0-5 wt% of a conditioning agent e) 0-5% by weight of a setting agent f) 0-10% by weight Further cosmetic constituents
• Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoxy 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. Sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
• 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, for example, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or -propionates, alkylamphodiacetates or -dipropionates.
• alkylbetaines alkylamidopropylbetaines
• alkylsulfobetaines alkylglycinates
• alkylcarboxyglycinates alkylamphoacetates or -propionates
• alkylamphodiacetates or -dipropionates 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, 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.
• Conventional conditioning agents in combination with the emulsion polymers according to the invention can be used in the shampoo formulations to achieve certain effects.
• These include for example cationic polymers with the loading drawing Polyquaternium INCI, in particular copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ® FC, Luviquat ® HM, Luviquat ® MS, Luviquat Care ®), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, square temdeck with diethyl sulfate (Luviquat ® PQ 11), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat Hold ®); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7
• 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).
• Skin cosmetic compositions according to the invention in particular those for the care of the skin, can be present and used in various forms. So they can z.
• Emulsifier-free formulations such as hydrodispersions, hydrogels or a Pickering emulsion are advantageous embodiments.
• the consistency of the formulations can range from pasty formulations via flowable formulations to low-viscosity, sprayable products. Accordingly, creams, lotions or sprays can be formulated.
• the cosmetic compositions of the invention are applied to the skin in a sufficient amount in the usual manner for cosmetics and dermatological agents.
• the salt content of the skin surface is sufficient to lower the viscosity of the preparations according to the invention in such a way that a simple distribution and incorporation of the preparations is made possible.
• the skin cosmetic preparations according to the invention are in particular as W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-wrinkle creams, facial expressions creams, moisturizing creams, bleach creams, vitamin creams, skin lotions, body lotions and moisturizing lotions.
• skin cosmetic preparations are toners, face masks, deodorants and other cosmetic lotions and preparations for decorative cosmetics, such as concealers, theatrical paint, mascara, eye shadows, lipsticks, kohl pencils, eyeliner, make-up, foundation, rouge, powder and eyebrow pencils.
• compositions according to the invention can be used in nasal strips for pore cleansing, in anti-acne agents, repellents, shaving agents, hair-removing agents, personal care products, foot care agents and in baby care.
• the skin-cosmetic preparations according to the invention contain, in addition to the W / W emulsion polymer and suitable carriers, other active ingredients and / or adjuvants customary in cosmetics, as described above and below.
• These preferably include emulsifiers, preservatives, perfume oils, cosmetic active substances such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, natural and synthetic light stabilizers, bleaching agents, colorants, tinting agents, suntanning agents, collagen, protein hydrolysates, stabilizers, pH-stabilizers. Value regulators, dyes, salts, thickeners, gelling agents, bodying agents, silicones, humectants, conditioners, moisturizers and other conventional additives. Other polymers can also be added to the compositions if special properties are to be set. To set certain properties such. B.
• the compositions may additionally contain conditioning substances based on silicone compounds.
• Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
• oils oils, fats and waxes
• the skin and hair cosmetic compositions preferably also contain oils, fats or waxes.
• Components of the oil and / or fat phase of the cosmetic compositions are advantageously selected from the group of lecithins and fatty acid triglycerides, namely the triglycerol esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 8 to 24, in particular 12 to 18 C -atoms.
• the fatty acid triglycerides may be advantageously selected from the group of synthetic, semi-synthetic and natural oils, such as e.g.
• polar oil components can be selected from the group of esters of saturated and / or unsaturated, branched and / or unbranched alkanecarboxylic acids having a chain length of 3 to 30 carbon atoms and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms and from the group of esters of aromatic carboxylic acids and saturated and / or unsaturated, branched and / or unbranched alcohols having a chain length of 3 to 30 carbon atoms.
• ester oils can then be advantageously selected from the group isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, 2 Octyl dodecyl palmitate, oleyl oleate, oleylureacate, erucyl oleate, erucyl erucate dicaprylyl carbonate (Cetiol CC) and cocoglycerides (Myrito 331), butylene glycol dicaprylate / dicaprate and dibuty
• one or more oil components can advantageously be selected from the group of branched and unbranched hydrocarbons and waxes, the silane konöle, the dialkyl ethers, the group of saturated or unsaturated, branched or unbranched alcohols.
• any mixtures of such oil and wax components are also advantageous to use in the context of the present invention. It may also be advantageous to use waxes, for example cetyl palmitate, as the sole lipid component of the oil phase.
• the olefin component is advantageously selected from the group consisting of 2-ethylhexyl isostearate, octyldodecanol, isotridecyl isononanoate, isoeicosane, 2-ethylhexyl cocoate, C12-15-alkyl benzoate, caprylic capric acid triglyceride, dicaprylyl ether.
• oil phase can advantageously be selected from the group of Guerbet alcohols.
• Guerbet alcohols are formed according to the reaction equation
• Guerbet alcohols are fluid even at low temperatures and cause virtually no skin irritation.
• They can be used as greasing, overfatting and also moisturizing ingredients in cosmetic compositions.
• the use of Guerbet alcohols in cosmetics is known per se.
• Such spe- cies are usually characterized by the structure
• R 1 and R 2 are generally unbranched alkyl radicals.
• the Guerbet alcohol or alcohols are selected from among
• Ri propyl, butyl, pentyl, hexyl, heptyl or octyl and
• R 2 hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl or tetradecyl.
• preferred Guerbet alcohols are (commercially available, for example as lsofol ® 12 (Condea)) 2-butyloctanol and 2-hexyl decanol (for example commercially available as iso- fol ® 16 (Condea)).
• Guerbet alcohols according to the invention are also advantageously usable according to the invention, for example mixtures of 2-butyloctanol and
• Hexyldecanol (commercially available, for example, as Isofol 14 (Condea)).
• polydecenes are the preferred substances.
• the oil component may further contain cyclic or linear content
• Silicone oils or consist entirely of such oils, although it is preferred to use an additional content of other oil phase components except the silicone oil or silicone oils.
• Low molecular weight silicones or silicone oils are generally defined by the following general formula
• silicon atoms can be substituted with identical or different alkyl radicals and / or aryl radicals, which are here generalized by the radicals Ri to R 4 .
• the number of different radicals is not necessarily limited to 4, n may assume values of 3/2 to 20. Broken values for n take into account that odd numbers of siloxyl groups may be present in the cycle.
• phenyltrimethicone is chosen as the silicone oil.
• silicone oils for example dimethicone, hexamethylcyclotrisiloxane, phenyldimethicone, cyclomethicone (eg decamethylcyclopentasiloxane), hexamethylcyclotrisiloxane, polydimethylsiloxane, poly (methylphenylsiloxane), cetyldimethicone, behenoxydimethicone, are to be used advantageously in the context of the present invention. Also advantageous are mixtures of cyclomethicone and Isotridecylisononanoat, and those of cyclomethicone and 2-Ethylhexylisostearat.
• silicone oils of similar constitution as the compounds described above, whose organic side chains are derivatized, for example polyethoxylated and / or polypropoxylated.
• these include, for example, polysiloxane-polyalkyl-polyether copolymers such as e.g. Cetyl dimethicone copolyol.
• cyclomethicone octamethylcyclotetrasiloxane
• Advantageously used fat and / or wax components can be selected from the group of vegetable waxes, animal waxes, mineral waxes and petrochemical waxes.
• Advantageous are, for example, candelilla wax, carnauba wax, Japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugarcane wax, berry wax, ouricury wax, montan wax, jojoba wax, shea butter, beeswax, shellac wax, spermaceti, lanolin (wool wax), crepe fat, ceresin, ozokerite (Earthwax), paraffin waxes and microwaxes.
• Further advantageous fat and / or wax components are chemically modified
• Waxes and synthetic waxes such as Syncrowax ® (glyceryl tribehenate), and Syncrowax ® AW 1 C (C 8-36 fatty acid) as well as Montanesterwachse, sasol waxes, hydrogenated jojoba e.g., synthetic or modified beeswaxes (. B. dimethicone Copolyol beeswax and / or C 3O-5 o-alkyl beeswax), cetyl ricinol leate such as Tegosoft ® CR, polyalkylene waxes, polyethylene glycol waxes, but also chemically modified fats such.
• Syncrowax ® glycol waxes
• Syncrowax ® AW 1 C C 8-36 fatty acid
• Montanesterwachse sasol waxes
• hydrogenated jojoba e.g., synthetic or modified beeswaxes (. B. dimethicon
• Hydrogenated vegetable oils for example hydrogenated castor oil and / or hydrogenated coconut fat glycerides
• triglycerides such as hydrogenated soy glyceride, trihydroxystearin, fatty acids, fatty acid esters and glycol kolester such as C 2 o- 4 o-alkyl stearate, C 2 o- 4 o-Alkylhydroxystearoylstearat and / or glycol montanate.
• Other advantageous compounds are certain organosilicon compounds which have similar physical properties to the abovementioned fatty and / or wax components, for example stearoxytrimethylsilane.
• the fat and / or wax components can be used both individually and as a mixture in the compositions.
• the oil phase is selected from the group 2-ethylhexyl advantageous Octyldo- decanol, isotridecyl isononanoate, butylene glycol dicaprylate / dicaprate, 2-ethylhexyl cocoate, C 2- i 5 alkyl benzoate, caprylic-capric acid triglyceride, dicaprylyl ether.
• Particularly advantageous are mixtures of octyldodecanol, caprylic-capric acid triglyceride, dicaprylyl ether, dicaprylyl carbonate, cocoglycerides, or mixtures of C 2 i 5 alkyl benzoate and 2-ethylhexyl isostearate, mixtures of C 2 i 5 alkyl benzoate and butylene glycol dicaprylate / dicaprate and Mixtures of Ci 2- i 5 -Alkylbenzoat, 2-Ethylhexylisostearat and Isotridecylisononanoat.
• hydrocarbons paraffin oil, cycloparaffin, squalane, squalene, hydrogenated polyisobutene or polydecene are to be used advantageously in the context of the present invention.
• the oil component can also be selected advantageously from the group of phospholipids.
• the phospholipids are phosphoric acid esters of acylated glycerols.
• the lecithins which are distinguished by the general structure
• R 1 and R are typically unbranched aliphatic radicals having 15 or 17 carbon atoms and up to represent to 4 cis-double bonds.
• advantageous paraffin oil according to the invention Mercury Weissoel Pharma 40 from Merkur Vaseline, Shell Ondina ® 917, Shell Ondina ® 927, Shell Oil 4222, Shell Ondina 933 ® from Shell & DEA OiI, pioneer ® 6301 S, pioneer ® 2071 (Han sen & Rosenthal) are used.
• Suitable cosmetically acceptable oil and fat components are described in Karl-Heinz Schrader, Kunststoffn und Japaneseuren der Kosmetika, 2nd edition, Verlag Wegig, Heidelberg, pp. 319-355, to which reference is hereby made in its entirety.
• the cosmetic compositions further contain conditioning agents.
• Suitable conditioning agents are, for example, those compounds which are described in the International Cosmetic Ingredient Dictionary and Handbook (Volume 4, editors: RC Pepe, JA Wenninger, GN McEwen, The Cosmetic, Toiletry, and Fragrance Association, 9th edition, 2002) Section 4 under the headings "Hair Conditioning Agents”, “Humectants”, “Skin Conditioning Agents”, “Skin Conditioning Agents Emollient”, “Skin Conditioning Agents Humectant”, “Skin Conditioning Agents - Miscellaneous”, “ Skin-Conditioning Agents-Occlusive "and” Skin Protectants "and all the compounds listed in EP-A 934 956 (p.11-13) under” water-soluble conditioning agent "and” oil-soluble conditioning agent " Advantageous conditioning agents are, for example, the compounds designated as polyquaternium according to INCI (in particular Polyquaternium-1 to Polyquaternium-56.) Suitable conditioning agents include, for example, polymers quaternary ammonium compounds, cationic cellulose derivatives, chitosan derivatives
• Conditioning agents which are advantageous according to the invention can also be chosen from the compounds shown in Table 1 below.
• guar hydroxypropylammonium eg Jaguar Excel ®, Jaguar C 162 ® (Rhodia), CAS 65497-29-2, CAS 39421-75-5.
• non-ionic poly N-vinylpyrrolidone / polyvinyl acetate copolymers eg Lu viskol ® VA 64 (BASF)
• anionic acrylate copolymers eg Luviflex soft ® (BASF)
• amphoteric amide / acrylate / methacrylate copolymers for example, Amphomer ® (National Starlings)
• Other possible conditioning agents are quaternized silicones.
• the cosmetic compositions according to the invention may contain, in addition to the W / W emulsion polymers, further thickening agents.
• suitable thickening agents are crosslinked polyacrylic acids and their derivatives, polysaccharides such as xanthan gum, guar-guar, agar-agar, alginates or tyloses, cellulose derivatives, eg. As carboxymethylcellulose or hydroxycarboxymethylcellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinylpyrrolidone.
• Suitable thickeners are also polyacrylates such as Carbopol ® (Noveon), Ultrez ® (Noveon), Luvigel EM ® (BASF), Capigel ® 98 (Seppic), Synthalens ® (Sigma), the Aculyn ® -. Trademarks of Rohm and Haas as Aculyn ® 22 (copolymer of acrylates and methacrylic acid with stearyl (20 EO units)) and Aculyn ® 28 (copolymer of acrylates and methacrylic acid with behenyl (25 EO units)).
• thickeners are, for example, Aerosil types (hydrophilic silicas), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with restricted hornolene distribution or alkyl oligoglucosides and electrolytes such as sodium chloride and ammonium chloride.
• Particularly preferred thickening agents for the preparation of gels are ® Ultrez 21, Aculyn ® 28, Luvigel EM ® and Capigel ® 98.
• in highly concentrated compositions may also contain substances are added, the viscosity of the wrestlers the Formulmaschinever- such to regulate the consistency. As propylene glycol or glycerol. These substances have little influence on the product properties.
• the cosmetic preparations contain no further thickening agents apart from the W / W emulsion polymers.
• aqueous cosmetic compositions according to the invention may also contain preservatives.
• Compositions with high water contents must be reliably protected against microbial contamination.
• the most important preservatives used for this purpose are urea condensates, p-hydroxybenzoic acid esters, the combination of phenoxyethanol with methyldibromoglutaronitrile and acid preservation with benzoic acid, salicylic acid and sorbic acid.
• compositions with high levels of surfactants or polyols and low water contents can also be formulated preservative-free.
• compositions of the invention may contain one or more preservatives.
• preservatives for the purposes of the present inven- tion, for example, formaldehyde donors (such as, for example, DMDM hydantoin, which is commercially available for example under the trade name Glydant ® (Lonza)), iodopropyl butylcarbamates (for example Glycacil-L ®, Glycacil-S ® (Lonza ), deca- ben ® LMB (Jan Dekker)), parabens (p-hydroxybenzoic acid alkyl ester such as methyl, ethyl, propyl and / or butyl paraben), Dehydroacetic Acid (Euxyl® K 702 (Schül- ke & Mayr), phenoxyethanol, Ethanol, benzoic acid
• so-called preservatives such as octoxyglycerol, glycine, soy,
• Preservatives or preservatives which are common in cosmetics are also advantageous, such as dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile), phenoxyethanol, 3-iodo-2-propynyl butyl carbamate, 2-bromo-2-nitropropane-1,3-diol, imidazolidinyl urea, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-chloroacetamide, benzalkonium chloride, benzyl alcohol, salicylic acid and salicylates.
• dibromodicyanobutane (2-bromo-2-bromomethylglutarodinitrile)
• phenoxyethanol 3-iodo-2-propynyl butyl carbamate
• 2-bromo-2-nitropropane-1,3-diol imidazolidinyl urea
• iodopropyl butylcarbamates parabens (methyl, ethyl, propyl and / or butylparaben) and / or phenoxyethanol are used as preservatives.
• preservatives are often unnecessary. Accordingly, preferred alcohol or water / alcohol based cosmetic formulations containing a W / W emulsion polymer as thickener do not require preservatives.
• the W / W emulsion polymers are outstandingly suitable for the preparation of alcohol-based disinfecting gels (ethanol, isopropanol, polyethylene glycols which are liquid under normal conditions, such as, for example, PEG-8).
• the end products may contain iron (ions) in trace amounts.
• complexing agents such as salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodisuccinic acid or phosphates are added.
• UV sunscreen such as. As benzophenone derivatives are incorporated. Suitable for this purpose are all cosmetically acceptable UV light protection filters.
• UV protection filters which may be present in the compositions according to the invention include, for example:
• compositions according to the invention are light stabilizers which are mentioned in EP-A 1 084 696 in paragraphs [0036] to [0053], to which reference is made in full at this point.
• Suitable for use according to the invention are all UV photoprotective filters, which are mentioned in Appendix 7 (to ⁇ 3b) of the German Cosmetics Regulation under "Ultraviolet filters for cosmetic products”.
• UV screening filters that can be used in the compositions of the invention is not exhaustive.
• antioxidants are selected from the group consisting of amino acids (eg glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (eg urocaninic acid) and their derivatives.
• amino acids eg glycine, histidine, tyrosine, tryptophan
• imidazoles eg urocaninic acid
• peptides such as DL-carnosine, D-camosine, L-camosine and their derivatives (eg anserine), carotenoids, carotenes (eg ⁇ -carotene, ß-carotene, ⁇ -lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and their derivatives (eg dihydrolipoic acid), aurothioglucose, propylthiouracil and other thiols (eg thiorexdoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, ⁇ -linoleyl, cholesteryl and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate
• Citric acid lactic acid, malic acid
• humic acid bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (eg ⁇ -linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, furfurylidene sorbitol and its derivatives
• Derivatives ubiquinone and ubiquinol and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (eg vitamin E acetate), vitamin A and derivatives (vitamin A palmitate ) and coniferyl benzoate of benzoin, rutinic acid and derivatives thereof, ⁇ -glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, buty
• the amount of the aforementioned antioxidants (one or more compounds) in the compositions is preferably from 0.001 to 30% by weight, more preferably from 0.05 to 20% by weight, especially from 0.1 to 10% by weight, based on the Total weight of the composition.
• vitamin E and / or its derivatives are the antioxidant (s), it is advantageous to provide them in concentrations of from 0.001 to 10% by weight, based on the total weight of the composition.
• vitamin A or vitamin A derivatives, or carotenes or derivatives thereof are the antioxidant or antioxidants, it is advantageous to provide them in concentrations of from 0.001 to 10% by weight, based on the total weight of the composition.
• buffer Buffers ensure the pH stability of aqueous compositions of the invention. Citrate, lactate and phosphate buffers are preferably used.
• Solubilizers can be used to bring nourishing oils or perfume oils clearly into solution and to keep them clear even in the cold.
• the most common solubilizers are ethoxylated nonionic surfactants, eg. B. hydrogenated and ethoxylated castor oils.
• antimicrobial agents can also be used. These generally include all suitable preservatives having specific activity against gram-positive bacteria, e.g. Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether), chlorhexidine (1,1'-hexamethylenebis [5- (4-chlorophenyl) biguanide), and TTC (3,4,4'-trichlorocarbanilide). Quaternary ammonium compounds are also suitable in principle. Also numerous fragrances have antimicrobial properties. Also, a large number of essential oils or their characteristic ingredients such. Clove oil (eugenol), mint oil
• the antibacterial substances are usually used in concentrations of about 0.1 to 0.3 wt .-%. dispersants
• insoluble active ingredients such as anti-dandruff agents or silicone oils
• dispersants and thickeners such as, for example, dispersants.
• dispersants for example, magnesium-aluminum silicates, bentonites, fatty acyl derivatives, polyvinylpyrrolidone or hydrocolloids, for.
• xanthan gum or carbomers use.
• compositions according to the invention optionally contain, in addition to the abovementioned substances, the further additives customary in cosmetics, for example perfumes, dyes, antimicrobial substances, lipid-replenishing agents, complexing and sequestering agents, pearlescing agents, plant extracts, vitamins, active substances, bactericides, pigments which have a coloring effect, softening, moisturizing and / or moisturizing substances, or other conventional constituents of a cosmetic or dermatological formulation such as alcohols, polyols, polymers, organic pH-adjusting acids, foam stabilizers, electrolytes, organic solvents or silicone derivatives.
• Ethoxylated glycerol fatty acid esters for example perfumes, dyes, antimicrobial substances, lipid-replenishing agents, complexing and sequestering agents, pearlescing agents, plant extracts, vitamins, active substances, bactericides, pigments which have a coloring effect, softening, moisturizing and / or moisturizing substances, or other conventional constituents of
• the cosmetic compositions according to the invention optionally contain ethoxylated oils selected from the group of ethoxylated glycerol fatty acid esters, more preferably PEG-10 olive oil glycerides, PEG-11 avocado oil glycerides, PEG-11 cocoa butter glycerides, PEG-13 sunflower oil glycerides, PEG-15 glyceryl isosteate, PEG-9 Coconut fatty acid glycerides, PEG-54 hydrogenated castor oil, PEG-7 hydrogenated castor oil, PEG-60 hydrogenated castor oil, jojoba oil ethoxylate (PEG-26 jojoba fatty acids, PEG-26 jojoba alcohol), glycereth-5 cocoate, PEG-9 coconut fatty acid glycerides, PEG 7 Glyceryl cocoate, PEG-45 palm oil glycerides, PEG-35 castor oil, Olive oil PEG-7 ester, PEG-6 caprylic acid / capric acid glyceride,
• Preferred ethoxylated oils are PEG-7 glyceryl cocoate, PEG-9 coconut glycerides, PEG-40 hydrogenated castor oil, PEG-200 hydrogenated glyceryl palmitate.
• Ethoxylated glycerol fatty acid esters are used in aqueous cleaning formulations for various purposes.
• Low ethoxylated glycerol fatty acid esters (3-12 ethylene oxide units) are usually used as a moisturizer to improve the skin feel after drying, glycerol fatty acid esters with a degree of ethoxylation of about 30-50 serve as solubilizers for non-polar substances such as perfume oils.
• Highly ethoxylated glycerol fatty acid esters are used as thickeners. All these substances have in common that they produce on the skin when used in dilution with water, a special skin feel.
• the active ingredients can be advantageously selected from the group consisting of acetylsalicylic acid, atropine, azulene, hydrocortisone and its derivatives, for.
• B. hydrocortisone 17-valerate vitamins of the B and D series, in particular vitamin B 1 , vitamin B 12 , vitamin D, vitamin A or its derivatives such as retinyl palmitate, vitamin E or its derivatives such as tocopheryl acetates, Vitamin C and its derivatives such as ascorbyl glucoside but also niacinamide, Panthenol, bisabolol, polydocanol, unsaturated fatty acids such as the essential fatty acids (commonly referred to as vitamin F), in particular ⁇ -linolenic acid, oleic acid, eicosapentaenoic acid, docosahexaenoic acid and its derivatives, chloramphenicol, caffeine, prostaglandins, th
• antidandruff active ingredients eg, selenium disulfide, zinc pyrithione, piroctone, olamine, climbazole, octopirox, polydocanol and their combinatines
• complexing agents such as those from ⁇ -oryzanol and calcium salts such as calcium panthotenate, calcium chloride, calcium acetate.
• the active ingredients from the group of emollients advantageous, for example PurCellin, Eucerit ® and Neocerit® ®.
• the active ingredient (s) are furthermore advantageously selected from the group of NO synthase inhibitors, in particular when the compositions according to the invention are used for the treatment and prophylaxis of the symptoms of intrinsic and / or extrinsic skin aging and for the treatment and prophylaxis of the harmful effects of ultraviolet radiation on the skin and the Hair should serve.
• Preferred NO synthase inhibitor is nitroarginine.
• the active ingredient (s) are selected from the group comprising catechins and bile acid esters of catechins and aqueous or organic extracts from plants or plant parts which have a content of catechins or bile acid esters of catechins, such as the leaves of the plant family Theaceae, in particular of the species Camellia sinensis (green tea). Particularly advantageous are their typical ingredients (eg polyphenols or catechins, caffeine, vitamins, sugars, minerals, amino acids, lipids).
• Catechins represent a group of compounds which are to be regarded as hydrogenated flavones or anthocyanidins and derivatives of "catechol” (catechol, 3,3 ', 4', 5J-flavanpentaol, 2- (3,4-dihydroxyphenyl) -chroman-3
• epicatec chin ⁇ R.SRJ-S.S ' ⁇ '. ⁇ y-flavanpentaol
• herbal extracts containing catechins especially extracts of green tea, such as. B. extracts from leaves of the plants of the species Camellia spec, especially the teas Camellia sinenis, C. assamica, C. taliensis and C. inawadiensis and crosses of these with, for example, Camellia japonica.
• active substances are polyphenols or catechins from the group (-) - catechin, (+) - catechin, (-) - catechin gallate, (-) - gallocatechin gallate, (+) - epicatechin, (-) - epicatechin, (-) Epicatechin gallate, (-) - epigallocatechin, (-) - epigallocatechin gallate.
• flavone and its derivatives are advantageous active ingredients in the sense of the present invention and are characterized by the following basic structure (substitution positions indicated):
• flavones usually occur in glycosidated form.
• the flavonoids are preferably selected from the group of substances of the general formula
• Z 1 to Z 7 independently of one another, are selected from the group consisting of H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups may be branched and unbranched and have 1 to 18 C atoms, and where GIy is selected from the group of mono- and Oligoglycosidreste.
• the flavonoids can also be chosen advantageously from the group of substances of the general formula
• Z 1 to Z 6 are independently selected from the group consisting of H, OH, alkoxy and hydroxyalkoxy, where the alkoxy or hydroxyalkoxy groups can be branched and unbranched and have 1 to 18 C atoms, and wherein GIy is selected from the group of mono- and oligoglycoside radicals.
• such structures can be selected from the group of substances of the general formula
• Gly 2 and Gly 3 independently represent monoglycoside or Oligoglycosidreste.
• GIy 2 or GIy 3 can also individually or together represent hydrogen atom saturation.
• Glyi, Gly 2 and Gly 3 are preferably selected independently of one another from the group of the hexosyl radicals, in particular the rhamnosyl radicals and glucosyl radicals.
• hexosyl radicals for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be advantageous to use. It may also be advantageous according to the invention to use pentosyl radicals.
• Z 1 to Z 5 are independently selected from the group H, OH, methoxy, ethoxy and 2-hydroxyethoxy, and the flavone glycosides correspond to the general structural formula
• the flavone glycosides are selected from the group represented by the following structure.
• Glyi, Gly 2 and Gly 3 independently of one another are monoglycoside radicals or oligoglycoside radicals.
• GIy 2 or GIy 3 can also individually or jointly represent saturations by hydrogen atoms.
• Glyi, Gly 2 and Gly 3 are preferably selected independently of one another from the group of the hexosyl radicals, in particular the rhamnosyl radicals and glucosyl radicals.
• hexosyl radicals for example allosyl, altrosyl, galactosyl, gulosyl, idosyl, mannosyl and talosyl, may also be advantageous to use. It may also be advantageous according to the invention to use pentosyl radicals.
• the flavone glycoside (s) from the group ⁇ -glucosylrutin, ⁇ -glucosylmyricetin, ⁇ -glucosylisoquercitrin, ⁇ -glucosylisoquercetin and ⁇ -glucosylquercitrin.
• beneficial agents are sericoside, pyridoxol, vitamin K, biotin and flavorings.
• the active ingredients can also be chosen very advantageously from the group of hydrophilic active ingredients, in particular from the following group: ⁇ -hydroxy acids such as lactic acid or salicylic acid or salts thereof, such as. Na lactate, Ca lactate, TEA lactate, urea, allantoin, serine, sorbitol, glycerin, milk proteins, panthenol, chitosan.
• ⁇ -hydroxy acids such as lactic acid or salicylic acid or salts thereof, such as. Na lactate, Ca lactate, TEA lactate, urea, allantoin, serine, sorbitol, glycerin, milk proteins, panthenol, chitosan.
• compositions according to the invention should, of course, not be limiting.
• active substances can be used individually or in any desired combinations with one another.
• the amount of such active ingredients (one or more compounds) in the compositions according to the invention is preferably 0.001 to 30 wt .-%, particularly preferably 0.05 to 20 wt .-%, in particular 1 to 10 wt .-%, based on the Total weight of the composition.
• Suitable pearlescent waxes are, for example: alkylene glycol esters, special ethylene glycol disterate; Fatty acid alkanolamides, especially coconut fatty acid diethanoamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polybasic, optionally hydroxysubstituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms Atonnen, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and D isearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring-opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms and / or polyols
• compositions of the invention may further contain glitter and / or other effect substances (e.g., color streaks).
• the cosmetic compositions according to the invention are present in the form of emulsions in a preferred embodiment of the invention.
• the preparation of such emulsions is carried out by known methods.
• the emulsions may also contain fatty alcohols, fatty acid esters and in particular fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
• the selection of the emulsion type-specific additives and the preparation of suitable emulsions is described for example in Schrader, bases and formulations of cosmetics, Hüthig book Verlag, Heidelberg, 2nd edition, 1989, third part, which is hereby incorporated by reference.
• a suitable emulsion e.g. for a skin cream, generally contains an aqueous phase which is emulsified by means of a suitable emulsifier system in an oil or fat phase.
• the proportion of the emulsifier system in this type of emulsion is preferably about 4 to 35% by weight, based on the total weight of the emulsion.
• the proportion of the fatty phase is about 20 to 60 wt .-%.
• the proportion of the aqueous phase is preferably about 20 and 70%, in each case based on the total weight of the emulsion.
• suitable emulsifiers are nonionic surfactants from at least one of the following groups:
• alkyl mono- and oligoglycosides having 8 to 22 carbon atoms in the alkyl group and their ethoxylated analogs
• oils for example castor oil and / or hydrogenated castor oil
• polystyrene resin e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate. Also suitable are mixtures of compounds from several of these classes of substances;
• polyglucosides e.g., cellulose
• the addition products of ethylene oxide and / or of propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or to castor oil are known, commercially available products. These are homolog mixtures, whose average degree of alkoxylation corresponds to the ratio of the molar amounts of ethylene oxide and / or propylene oxide and substrate with which the addition reaction is carried out.
• C 2 to C 8 fatty acid monoesters and diesters of addition products of ethylene oxide onto glycerol are known from DE-PS 2024051 as refatting agents for cosmetic composi- tions known.
• C 8 to C 8 alkyl mono- and oligoglycosides their preparation and their use are known from the prior art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 C atoms. With respect to the glycoside ester, both monoglycosides in which a cyclic sugar residue is glycosidically linked to the fatty alcohol and oligomeric glycosides having a degree of oligomerization of preferably about 8 are suitable. The degree of oligomerization is a statistical mean, which is based on a homolog distribution typical for such technical products.
• zwitterionic surfactants can be used as emulsifiers.
• Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one carboxylate and / or one sulfonate group in the molecule.
• Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N, N-dimethylammonium glycinates, for example the Kokosalkyldimethylammoniumglyci- nat, N-acylaminopropyl-N, N-dimethylammoniumglycinate, for example, the Kokosa- cylaminopropyldimethylammoniumglycinat, and 2-alkyl-3-carboxylmethyl -3- hydroxyethylimidazolines having in each case 8 to 18 carbon atoms in the alkyl or acyl group and Kokosacylaminoethylhydroxyethylcarboxy methylglycinat.
• betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example the Kokosalkyldimethylammoniumglyci- nat, N-acylaminopropy
• fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.
• ampholytic surfactants are surface-active compounds which, apart from a C 8 to C 8 alkyl or acyl group in the molecule at least one free amino group and at least one -COOH and / or -SO 3 H
• ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C Atoms in the alkyl group.
• Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C 2 to C 8 acyl sarcosine.
• quaternary emulsifiers are also suitable, with those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
• the cosmetic compositions of the invention may contain perfume oils.
• perfume oils for example, mixtures of natural and synthetic fragrances may be mentioned. Natural fragrances are extracts of flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (aniseed, coriander, caraway, juniper), fruit peel (bergamot, Lemon, orange), roots (mace, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), tern and grasses (tarragon, lemongrass, sage, thyme), needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Furthermore, animal raw materials come into question, such as civet and Castore
• Fragrance compounds of the ester type are known e.g. Benzylacetate, phenoxyethylisobutyrate, 4-tert-butylcyclohexylacetate, linalylacetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
• the ethers include, for example, benzyl ethyl ethers, to the
• Aldehydes e.g. the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonate, to the ketones e.g. the ionones, cc-lsomethylionen and Methylcedrylketon, to the alcohols anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terioneol, the hydrocarbons include mainly the terpenes and balsams.
• fragrance oils are useful as perfume oils, e.g. Sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden flower oil, juniper berry oil, vetiver oil, oliban oil,
• Galbanum oil, labolanum oil and lavandin oil Preferably, bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, ⁇ -hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene ® Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclovertal, lavandin oil, muscatel sage oil, geranium oil bourbon, cyclohexyl salicylate, Vertofix ® Coeur, Iso-e-Super ®, Fixolide ® NP, Evemyl, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl
• the cosmetic compositions of the invention further contain pigments.
• the pigments are present in undissolved form in the product composition and may be present in an amount of from 0.01 to 25% by weight, particularly preferably from 5 to 15% by weight.
• 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 inorganic pigments may be of natural origin, for example produced from chalk, ocher, umber, green earth, calcined terpene. ra di Siena or graphite.
• the pigments may be white pigments such as titanium dioxide or zinc oxide, black pigments such as iron oxide black, colored pigments such as ultramarine or iron oxide red, luster pigments, metal effect pigments, pearlescent pigments and fluorescence or phosphorescent pigments, preferably at least one pigment is colored, non-white pigment.
• Suitable are metal oxides, hydroxides and oxide hydrates, mixed phase pigments, sulfur-containing silicates, metal sulfides, complex metal cyanides, metal sulfates, chromates and molybdates 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 (Cl 77742), ultramarines (sodium aluminum sulfosilicates, Cl 77007, Pigment Blue 29 ), Chromium oxide hydrate (C177289), iron blue (Ferric Ferro-Cyanide, CI7751 0), Carmine (Cochineal).
• pearlescent and color pigments based on mica or mica which are coated with a metal oxide or a metal oxychloride, such as titanium dioxide or bismuth chloride, and optionally other coloring substances, such as iron oxides, iron blue, ultramarines, carmines, etc., and the color can be modified by varying Layer thickness can be determined.
• a metal oxide or a metal oxychloride such as titanium dioxide or bismuth chloride
• other coloring substances such as iron oxides, iron blue, ultramarines, carmines, etc.
• Such pigments are sold, for example under the trade names Rona ®, Colorona ®, Dichrona and Timiron ® ® (Merck).
• Organic pigments include, for example, the natural pigments sepia, cambogia, bone charcoal, Kasseler brown, indigo, chlorophyll and other plant pigments.
• Synthetic organic pigments include azo pigments, anthraquinoids, indigoids, dioxazine, quinacridone, phthalocyanine, isoindolinone, perylene and perinone, metal complex, alkali blue and diketopyrrolopyrrole pigments.
• the composition according to the invention contains from 0.01 to 10, particularly preferably from 0.05 to 5,% by weight of at least one particulate substance.
• Suitable substances are e.g. Substances which are solid at room temperature (25 ° C) and in the form of particles. Suitable examples are silica, silicates, aluminates, clays, mica, salts, in particular inorganic metal salts, metal oxides, e.g. Titanium dioxide, minerals and polymer particles.
• the particles are present in the agent undissolved, preferably stably dispersed form and can be deposited in solid form after application to the application surface and evaporation of the solvent.
• Preferred particulates are silica (silica gel, silica) and metal salts, especially inorganic metal salts, with silica being particularly preferred.
• Metal salts are, for example, alkali or alkaline earth halides such as sodium chloride or potassium chloride; Alkali or alkaline earth sulfates such as sodium sulfate or magnesium sulfate.
• the cosmetic compositions of the invention may further contain additional polymers.
• Suitable polymers are, for example, cationic polymers with the name Polyquater- nium according to INCI, for example, copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ® FC, Luviquat ® HM, Luviquat ® MS, Luviquat ® Care, Luviquat ® Ultra Care), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized (11 Luviquat ® PQ) with diethyl sulfate, a copolymer of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat Hold ®); cationic cellulose derivatives (polyquaternium-4 and -10), acrylamidocopolymers (polyquaternium-7) and chitosan.
• Suitable cationic (quaternized) polymers are also Merquat ® (polymer based on dimethyldiallylammonium chloride), Gafquat ® (quaternary polymers which are formed by reaction of polyvinylpyrrolidone with quaternary ammonium compounds), Polymer JR (hydroxyethylcellulose with cationic groups) and cationic polymers based on plants, For example, guar polymers, such as the Jaguar ® brands Fa. Rhodia.
• polystyrene resin examples include polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinylpropionate and / or stearyl (meth) acrylate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their Salts, cellulose derivatives, polyaspartic acid salts and derivatives.
• Luviflex® ® Swing partially hydrolyzed copolymer of polyvinyl acetate and Polyethylengly- kol, Messrs. BASF
• Kollicoat ® IR examples include a Luviflex® ® Swing (partially hydrolyzed copolymer of polyvinyl acetate and Polyethylengly- kol, Messrs. BASF) or Kollicoat ® IR.
• Suitable polymers are also those described in WO 03/092640, in particular those described as Examples 1 to 50 (Table 1, page 40 et seq.) And Examples 51 to 65 (Table 2, page 43) described (meth) Acryl Acidmidcopolymere, to the this site is fully incorporated by reference.
• Suitable polymers are also nonionic, water-soluble or wasserdispergierba- re polymers or oligomers, such as polyvinylcaprolactam, including Luviskol Plus ® (BASF), or polyvinyl pyrrolidone and their copolymers, in particular vinyl esters such as vinyl acetate, for example, Luviskol ® VA 37 (BASF); Polyamides, for example based on itaconic acid and aliphatic diamines, as described, for example, in DE-A-43 33 238.
• polyvinylcaprolactam including Luviskol Plus ® (BASF)
• BASF Luviskol Plus ®
• polyvinyl pyrrolidone and their copolymers in particular vinyl esters such as vinyl acetate, for example, Luviskol ® VA 37 (BASF);
• Polyamides for example based on itaconic acid and aliphatic diamines, as described, for example, in DE-A-43 33 238.
• Suitable polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer ® (National Starch) Octylacryla- mid / methyl methacrylate / tert-Butylaminoethylmethacryla ⁇ -hydroxypropylmethacrylat- 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 those available under the name Amersette® ® (AMERCHOL) methacroylethylbetaine / methacrylate copolymers, methacrylate and copolymers of hydroxyethyl methacrylate, methyl, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon ®).
• Suitable polymers are also nonionic, siloxane-containing, water soluble or dispersible polymers, for example, polyether siloxanes, such as Tegopren ® (Fa. Goldschmidt) or Belsil ® (Fa. Wacker). Also suitable are biopolymers, ie polymers which are obtained from naturally renewable raw materials and are composed of natural monomer building blocks, for example cellulose derivatives, chitin, chitosan, DNA, hyaluronic acid and RNA derivatives.
• polyether siloxanes such as Tegopren ® (Fa. Goldschmidt) or Belsil ® (Fa. Wacker).
• biopolymers ie polymers which are obtained from naturally renewable raw materials and are composed of natural monomer building blocks, for example cellulose derivatives, chitin, chitosan, DNA, hyaluronic acid and RNA derivatives.
• compositions according to the invention comprise at least one further water-soluble polymer, in particular chitosans (poly (D-glucosamine)) of different molecular weight and / or chitosan derivatives.
• chitosans poly (D-glucosamine)
• suitable polymers for the compositions according to the invention are copolymers containing carboxylic acid groups. These are polyelectrolytes with a larger number of anionically dissociable groups in the main chain and / or a side chain. They are capable of forming polyelectrolyte complexes (symplexes) with the copolymers A).
• the polyelectrolyte complexes used in the agents according to the invention have an excess of anionogenic / anionic groups.
• the polyelectrolyte complexes also comprise at least one acid group-containing polymer.
• the polyelectrolyte complexes preferably comprise copolymer (e) A) and acid group-containing polymers in a weight ratio of from about 50: 1 to 1:20, particularly preferably from 20: 1 to 1: 5.
• Suitable carboxylic acid group-containing polymers are obtainable, for example, by free-radical polymerization of ⁇ , ⁇ -ethylenically unsaturated monomers.
• monomers m1) are used which contain at least one radically polymerizable, ⁇ , ⁇ -ethylenically unsaturated double bond and at least one anionogenic and / or anionic group per molecule.
• Suitable polymers containing carboxylic acid groups are also polyurethanes containing carboxylic acid groups.
• the monomers are selected from monoethylenically unsaturated carboxylic acids, sulfonic acids, phosphonic acids and mixtures thereof.
• the monomers m1) include monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms, which can also be used in the form of their salts or anhydrides. Examples of these are acrylic, methacrylic, ethacrylic, ⁇ -chloroacrylic, crotonic, maleic, maleic, itaconic, citraconic, mesaconic, glutaconic, aconitic and fumaric acid.
• the monomers also include the half-esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, for example of maleic acid, such as monomethyl maleate.
• the monomers also include monoethylenically unsaturated sulfonic acids and phosphonic acids, for example vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, Vinylphosphonic acid and allylphosphonic acid.
• monoethylenically unsaturated sulfonic acids and phosphonic acids for example vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfoprop
• the monomers also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts, and also the salts with the abovementioned amines.
• the monomers can be used as such or as mixtures with one another. The stated proportions by weight are all based on the acid form.
• the monomer m1) is selected from acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof, more preferably acrylic acid, methacrylic acid and mixtures thereof.
• the abovementioned monomers m1) can each be used individually or in the form of any desired mixtures.
• the comonomers used for the preparation of the carboxylic acid group-containing polymers are the compounds a) to d) previously mentioned as components of the copolymer A), with the proviso that the molar proportion of anionogenic and anionic groups which contains the polymer containing carboxylic acid groups in a larger proportion increases is the mole fraction of cationogenic and cationic groups.
• the carboxylic acid group-containing polymers comprise at least one monomer in copolymerized form, which is selected from the abovementioned crosslinkers.
• the polymers containing carboxylic acid groups preferably contain in copolymerized form at least one monomer m2) which is selected from compounds of the general formula (VI)
• R 1 is hydrogen or C 8 alkyl R C
• Y 1 is O, NH or NR 3 , and
• R 2 and R 3 independently of one another are C 1 -C 30 -alkyl or C 5 -C 8 -cycloalkyl, where the alkyl groups are substituted by up to four nonadjacent heteroatoms or heteroatom-containing groups selected from O, S and NH can be interrupted.
• R 1 in the formula VI is preferably hydrogen or C 1 -C 4 -alkyl, in particular
• R 2 in the formula VI is preferably C 1 -C 8 -alkyl, preferably methyl, ethyl, n-butyl, isobutyl, tert-butyl or a group of the formula
• R 3 is alkyl, then preferably C r C 4 alkyl, such as
• Suitable monomers m2) are methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl ethacrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, n-octyl (meth) acrylate, 1, 1,3,3 Tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate , Pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth)
• Suitable monomers m2) are furthermore acrylic acid amide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide, N- (tert Butyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide piperidinyl (meth) acrylamide and morpholinyl (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide, N- (n-undecy
• polymers containing carboxylic acid groups preferably contain, in copolymerized form, at least one monomer m3) which is selected from compounds of the general formula VII
• the sequence of the alkylene oxide units is arbitrary, k and I independently of one another are an integer from 0 to 1000, the sum of k and I being at least 5,
• R 4 represents hydrogen, Ci-C 30 alkyl or C 5 -C 8 -cycloalkyl
• R 5 is hydrogen or C 8 alkyl C r
• Y 2 is O or NR 6 wherein R 6 is hydrogen, C C 30 alkyl or C 5 -C 8 - cycloalkyl.
• k is preferably an integer from 1 to 500, in particular from 3 to 250.
• I is an integer from 0 to 100.
• R 5 is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular for hydrogen, methyl or ethyl.
• R 4 is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl, decyl, lauryl, palmityl or stearyl ,
• Y 2 in formula VII is O or NH.
• Suitable polyether acrylates VII) are, for example, the polycondensation products of the abovementioned ⁇ , ⁇ -ethylenically unsaturated mono- and / or dicarboxylic acids and their acid chlorides, amides and anhydrides with polyetherols.
• Suitable polyetherols can easily be prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule, such as water or a short-chain alcohol R 4 -OH.
• the alkylene oxides can be used individually, alternately in succession or as a mixture.
• the polyether acrylates VII) can be used alone or in Mixtures for the preparation of the polymers used in the invention can be used.
• Suitable polyether acrylates II) are also urethane (meth) acrylates with alkylene oxide groups. Such compounds are described in DE 198 38 851 (component e2)), to which reference is made in its entirety.
• anionic polymers which are preferred as carboxylic acid-containing polymers are, for example, homo- and copolymers of acrylic acid and methacrylic acid and salts thereof. These also include crosslinked polymers of acrylic acid, such as those available under the INCI name Carbomer. Such crosslinked homopolymers of acrylic acid are available commercially for example under the name Carbopol ® by the company Noveon. Also hydrophobically modified crosslinked polyacrylate polymers such as Carbopol ® Ultrez 21 are preferably from Noveon.
• suitable 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.
• Particularly suitable polymers are copolymers of (meth) acrylic acid and polyether acrylates, the polyether chain being terminated by a C 8 -C 30 -alkyl radical.
• These include, for example, acrylate / beheneth-25-methacrylate copolymers, which are available under the name Aculyn ® from Rohm and Haas.
• Particularly suitable polymers are also copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (for example, Luvimer ® 100P, Luvimer ® Pro55), copolymers of ethyl acrylate and methacrylic acid (eg Luviu- mer MAE ®), copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold ® 8, Ultrahold ® strand), copolymers of vinyl acetate, crotonic acid and optionally further Vinylester (eg Luviset ® brands), maleic anhydride copolymers, optionally reacted with alcohol, anionic polysiloxanes, for example carboxy, t- butyl acrylate, methacrylic acid (for example, Luviskol ® VBM ), Copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, such as C 4 -C 30 alky
• anionic polymers are also vinyl acetate / crotonic acid copolymers, as are, for example, under the names Resyn ® (National Starch) and Gafset ® (GAF), and vinyl pyrrolidone / vinyl acrylate copolymers, obtainable for example under the trade name Luviflex ® (BASF) ,
• Other suitable polymers are the commercially available under the name Luviflex 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 / butylaminoethyl methacrylate copolymer ) Aquaflex ® FX 64 (ISP; isobutylene Ien / ethylmaleimide / 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, polyester-1), and ® Diaformer Z-400 (Clariant; methacryloyleth
• Suitable carboxylic acid group-containing polymers are the terpolymers described in US No. 3,405,084 of vinylpyrrolidone, Ci-Ci o alkyl, cycloalkyl and ryl A- (meth) acrylates and acrylic acid.
• Suitable polymers containing carboxylic acid groups are furthermore the terpolymers of vinylpyrrolidone, tert-butyl (meth) acrylate and (meth) acrylic acid described in EP-AO 257 444 and EP-AO 480 280.
• Suitable polymers containing carboxylic acid groups are furthermore the copolymers described in DE-A-42 23 066, which comprise at least one (meth) acrylic ester, (meth) acrylic acid and also N-vinylpyrrolidone and / or N-vinylcaprolactam in copolymerized form.
• the disclosure of these documents is hereby fully incorporated by reference.
• the preparation of the abovementioned carboxylic acid group-containing polymers is carried out by known processes, for example the solution, precipitation, suspension or emulsion polymerization, as described above for the copolymers A).
• 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, the carboxylic acid and / or sulfonic acid groups exhibit. 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.
• the acid groups of the carboxylic acid group-containing polymers may be partially or completely neutralized. Then at least a part of the acid groups is present in deprotonated form, the counterions are preferably selected from alkali metal ions, such as Na + , K + , ammonium ions and their organic derivatives, etc.
• Propellant gases Propellant gases
• compositions according to the invention are to be provided as an aerosol spray, then blowing agents are necessary.
• Suitable propellants are the customary propellants, such as n-propane, isopropane, n-butane, isobutane, 2,2-dimethylbutane, n-pentane, isopentane, dimethyl ether, difluoroethane, fluorotrichloromethane, dichlorodifluoromethane or dichlorotetrafluoroethane, HFC 152 A or mixtures thereof.
• hydrocarbons in particular propane, n-butane, n-pentane and mixtures thereof, as well as dimethyl ether and difluoroethane are used.
• one or more of said chlorinated hydrocarbons are used in propellant mixtures, but only in small amounts, for example up to 20 wt .-%, based on the propellant mixture.
• the hair cosmetic preparations according to the invention are also suitable for pump spray formulations without the addition of propellants or else for aerosol sprays with customary compressed gases such as nitrogen, compressed air or carbon dioxide as propellant.
• compositions of the invention may also contain surfactants.
• surfactants anionic, cationic, nonionic and / or amphoteric surfactants can be used.
• acylamino acids and their salts such as
• Sarcosinates for example myristoyl sarcosine, TEA-lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate,
• Sulfonic acids and their salts such as acyl isethionates, for example sodium or ammonium cocoyl isethionate Sulfosuccinates, for example dioctyl sodium sulphosuccinate, disodium laureth sulphosuccinate, disodium lauryl sulphosuccinate and disodium undecylenamido MEA sulphosuccinate, disodium PEG-5 lauryl citrate sulphosuccinate and derivatives, and sulfuric acid esters such as alkyl ether sulphate, for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulphate, sodium myreth sulfate and sodium C 12 - 13 pareth,
• alkyl ether sulphate for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulphate, sodium myreth sulfate and sodium C 12 - 13 pareth
• Alkyl sulfates for example sodium, ammonium and TEA lauryl sulfate. Further advantageous anionic surfactants are
• Taurates for example sodium lauroyl taurate and sodium methyl cocoyl taurate, ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate, sodium PEG-7 olive oil carboxylate
• Phosphoric acid esters and salts such as, for example, DEA-oleth-10-phosphate and dilaureth-4-phosphate,
• alkylsulfonates for example sodium, sodium C 12 - 14 olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate,
• Acylglutamates such as di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate,
• Acyl peptides for example palmitoyl-hydrolyzed milk protein, sodium cocoyl-hydrolyzed soy protein and sodium / potassium cocoyl-hydrolyzed collagen, and also carboxylic acids and derivatives, for example lauric acid, aluminum stearate, magnesium alkoxide and zinc undecylenate, ester carboxylic acids, for example calcium stearoyl lactylate, laureth-6-citrate and sodium PEG-4 lauramide carboxylate
• Advantageous cationic surfactants for the purposes of the present invention are quaternary surfactants. Quaternary surfactants contain at least one N atom covalently linked to 4 alkyl or aryl groups. For example, alkylbetaine, alkylamidopropylbetaine and alkylamidopropylhydroxysultaine are advantageous. Further advantageous cationic surfactants for the purposes of the present invention are further
• amphoteric surfactants for the purposes of the present invention are acyl
• dialkylethylenediamines for example, sodium acylamphoacetate, disodium acylamphodipropionate, disodium alkylamphodiacetate, sodium acylamphohydroxypropylsulfonate, disodium acylamphodiacetate, sodium acylamphopropionate, and N-coconut fatty acid amidoethyl-N-hydroxyethylglycinate sodium salts.
• Further advantageous amphoteric surfactants are N-alkylamino acids, for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.
• compositions for the purposes of the present invention are alkanolamides, such as cocamide MEA / DEA / MIPA,
• ethers for example ethoxylated alcohols, ethoxylated lanolin, ethoxylated polysilane Loxane, propoxylated POE ethers, alkyl polyglycosides, such as lauryl glucoside, decyl glycoside and cocoglycoside, glycosides with an HLB value of at least 20 (for example, BEI sil ® SPG 128V (Wacker)).
• nonionic surfactants are alcohols and amine oxides, such as cocoamidopropylamine oxide.
• alkyl ether sulfates sodium alkyl ether sulfates based on di- or tri-ethoxylated lauryl and myristyl alcohol are particularly preferred. They clearly outperform the alkyl sulfates with regard to their resistance to water hardness, colourability, low solubility and, in particular, skin and mucous membrane compatibility. Lauryl ether sulfate has better foam properties than myristyl ether sulfate, but this is inferior in mildness. Medium and especially higher alkyl ether carboxylates are among the mildest surfactants ever but exhibit poor foam and viscosity performance. They are often used in combination with alkyl ether sulfates and amphoteric surfactants.
• Sulfosuccinic acid esters are mild and, because of their poor thickenability, preference is given to using surfactants which are preferred only in neutral or well-buffered products only together with other anionic and amphoteric surfactants and, owing to their low hydrolytic stability.
• Amidopropylbetains have excellent skin and eye mucous membrane compatibility. In combination with anionic surfactants, their mildness can be synergistically improved. Preferred is the use of cocamidopropyl betaine.
• Amphoacetate / Arnphodiacetate have as amphoteric surfactants a very good skin and mucous membrane compatibility and can have a conditioning effect or increase the care effect of additives. They are similar to the betaines used to optimize alkyl ether sulfate formulations. Most preferred are sodium cocoamphoacetate and disodium cocoamphodiacetate.
• Alkyl polyglycosides are mild, have good universal properties, but foam weakly. For this reason, they are preferably used in combination with anionic surfactants.
• polysorbate agents can advantageously be incorporated into the composition.
• advantageous polysorbates are the
• compositions according to the invention comprise copolymer a) and, in each case based on the composition, less than 1% by weight, preferably less than 0.1% by weight and in particular no oligomer b).
• compositions of the invention containing copolymer a) can be used advantageously for the removal of excess oil or lipid from the skin surface.
• these compositions contain, based on the composition, less than 1 wt .-%, preferably less than 0.1 wt .-% and in particular no oligomer b).
• compositions according to the invention can be present and used in various forms. So they can z.
• emulsion of the type oil-in-water (O / W) or a multiple emulsion for example, the type of water-in-oil-in-water (W / O / W).
• Emulsifier-free formulations such as hydrodispersions, hydrogels or a Pickering emulsion are advantageous embodiments.
• the consistency of the formulations can range from pasty formulations via flowable formulations to low-viscosity, sprayable products. Accordingly, creams, lotions or sprays can be formulated.
• the cosmetic compositions of the invention are applied to the skin in a sufficient amount in the usual manner for cosmetics and dermatological agents. Not only does the application achieve uniform skin coloration, it also makes it possible to dye different colored skin areas naturally or through pathological changes.
• Glycerol aldehyde, hydroxymethylglyoxal, ⁇ -dialdehyde, erythrulose, 5-hydroxy-1,4-naphthoquinone (Jug ion) and the 2-hydroxy-1,4-naphthoquinone occurring in the henna leaves are advantageously used according to the invention as bristles.
• DHA 1, 3-dihydroxyacetone
• 6-aldo-D-fructose and ninhydrin can also be used as self-tanning agents according to the invention.
• a self-tanner in the context of the invention are also substances to understand that cause a deviating from Braunton skin color.
• these compositions comprise a plurality of self-tanning substances in a concentration of from 0.1 to 10% by weight and more preferably from 0.5 to 6% by weight, based in each case on the total weight of the composition.
• these compositions contain them as a self-tanning substance 1, 3-dihydroxyacetone. More preferably, these compositions contain organic and / or inorganic sunscreen filters. The compositions may also contain inorganic and / or organic and / or modified inorganic pigments.
• compositions according to the invention are mentioned above and in DE 103 21 147, [0024] to [0132].
• An object of the invention is also the cosmetic use of such compositions for coloring the skin of multicellular organisms, in particular the skin of humans and animals, in particular also for the color matching of differently pigmented skin sites.
• a further advantage of the compositions thickened by means of the W / W emulsion polymers is that O / W and W / O / W emulsions having a high content of humectants, such as, for example, glycerol, can be stably provided.
• W / W emulsion polymers for the rheology modification of cosmetic or dermatological preparations is that a thickening effect over a wide pH range of 4 to 11 and in particular from 6 to 10 is achieved.
• commercially available thickeners it is possible to achieve a continuous increase in viscosity, while commercial thickeners usually allow only a stepwise change in viscosity in relatively large increments. This makes it easier to adjust viscosities, as they are suitable for example for body milk or lotions.
• the K values of the polymers were determined according to H. Fikentscher, Cellulose-Chemie, Vol. 13, 58-64 and 71-74 (1932) in 3% strength by weight aqueous common salt solution at 25 ° C., a concentration of 0.1% by weight . -% certainly.
• the viscosity of the dispersions was measured in each case in a Brookfield viscometer with a spindle No. 4 at 20 rpm and a temperature of 20 ° C. Unless otherwise indicated, the percentages are by weight.
• the polymers of groups a) and b) used as stabilizers in the examples had the following composition:
• Stabilizer 1 graft polymer of vinyl acetate on polyethylene glycol of molecular weight M N 6000, polymer concentration 20%
• Stabilizer 2 Hydrolysed copolymer of vinyl methyl ether and maleic acid in the form of the free carboxyl groups, polymer concentration 35%
• Stabilizer 3 Copolymer of methyl polyethylene glycol methacrylate and methacrylic acid of molecular weight M w 1500, polymer concentration 40%
• Stabilizer 4 Polypropylene glycol having a molecular weight M N of 600
• Stabilizer 5 Polypropylene glycol having a molecular weight M N of 900
• Stabilizer 6 Polypropylene glycol terminated on one side with a methyl group and having a molecular weight M N of 1000
• Stabilizer 7 Block copolymer of polyalkylene glycols having a molecular weight
• Stabilizer 8 Maltodextrin (C-PUR01910, 100% strength)
• Stabilizer 9 Polypropylene glycol having a molecular weight M n of 2000 and end capped on one side with a methyl group
• Stabilizer 10 Copolymer of acrylamide and DMAEMA quaternized with a
• Stabilizer 12 Copolymer of methacrylic acid and acrylamidomethylpropanesulfonic acid with a molar ratio of 70:30
• Stabilizer 13 Copolymer of methacrylic acid and acrylamidomethylpropanesulfonic acid with a molar ratio of 60:40
• Stabilizer 14 Pluronic ® PE 4300: block copolymer of ethylene oxide and Propyleno- the general formula (I) (see above), wherein the mass of the
• Polypropylenglakolblocks is about 1100 g / mol and per molecule of
• Stabilizer 15 Pluronic ® PE 6200: block copolymer of ethylene oxide and Propyleno- the general formula (I) (see above), wherein the mass of the
• Polypropylene glycol block is about 1750 g / mol and per molecule of
• Block copolymer about 20 wt .-% polyethylene glycol are included.
• Stabilizer 16 copolymer of 50 mol% of acrylamide and 50 mol% of dimethylaminoethyl acrylate methochloride, K value 82.6;
• Stabilizer 17 Copolymer of 50 mol% of acrylamide and 45 mol% of dimethylaminoethyl acrylate methochloride, 5 mol% of acrylic acid, K value 45.1
• Stabilizer 18 copolymer of 60 mol% of acrylamide and 38 mol% of dimethylaminoethyl acrylate methochloride, 2 mol% of acrylic acid, K value 78.0;
• azo starter VA- 044® 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride
• azo starter V- 70® 2,2'-azobis (4-methoxy-2,4-bis) dimethylvaleronitrile
• azo starter V- 65® 2,2'-azobis (2 J 4-dimethylvaleronitrile)
• the reaction mixture was then treated with 0.05 g of azo initiator VA-044 ® lymerintestin 1 hour at 60 ° C nachpo-.
• An aqueous dispersion having a solids content of 33% was obtained. It had a pH of 4 and a viscosity of 5950 mPas.
• the polymer had a K value of 120.7.
• a 2% aqueous solution was prepared which had a viscosity of 2640 mPas at a pH of 7.
• the particle size distribution of the dispersed particles of the polymer dispersion was 3 to 8 ⁇ m.
• Azobis (4-methoxy-2,4-dimethylvaleronitrile) (azo starter V- 70® ) and polymerized the mixture at a temperature of 40 ° C for 5 hours.
• An aqueous dispersion having a viscosity of 2700 mPas was obtained. It had a pH of 4.
• a 2% aqueous solution was prepared. It had a viscosity of 39000 mPas at pH 7.
• the particle size distribution of the dispersed particles of the polymer dispersion was 5 to 60 ⁇ m.
• Example 2 was repeated with the exceptions that in the polymerization 12 g of stabilizer 4 51, 4 g of stabilizer 2 and 106.6 g of fully desalinated water submitted and waived the use of triallylamine. An aqueous solution was obtained
• Emulsion having a viscosity of 2240 mPas at pH 4.
• Example 5 was repeated with the exceptions that in the polymerization apparatus a mixture of 45 g of stabilizer 51, 4 g of stabilizer 2 and
• the particle size distribution of the dispersed particles of the polymer dispersion was 3 to 10 ⁇ m.
• Example 6 In the apparatus given in Example 1, 90.0 g of stabilizer i, 51.4 g of stabilizer 2 and 28.6 g of completely demineralized water were introduced and stirred while passing nitrogen at a speed of 300 rpm. To this solution was added dropwise within 5 to 10 minutes, a mixture of 30 g of acrylic acid and 0.22 g of pentaerythritol triallyl ether (70%) as a crosslinker and heated the mixture within 5 to 10 minutes at a temperature of 40 ° C. 0.03 g of azo starter V- 70® was then added and the mixture was polymerized at a temperature of 40 ° C. for 5 hours.
• a 2% aqueous solution was prepared. It had a viscosity of 29000 mPas at pH 7. The particle size distribution of the dispersed particles of the polymer dispersion was 5 to 30 ⁇ m.
• Example 9 In the apparatus given in Example 1, 90.0 g of stabilizer i, 45.7 g of stabilizer 2 and 34.3 g of fully deionized water were introduced and stirred while passing nitrogen at a speed of 300 rpm. To this solution was added dropwise within 5 to 10 minutes, a mixture of 30 g of acrylic acid and 0.09 g of triallylamine as a crosslinker and heated the mixture within 5 to 10 minutes at a temperature of 40 ° C. 0.03 g of azo starter V- 70® was then added and the mixture was polymerized at a temperature of 40 ° C. for 5 hours.
• azo initiator VA-044 ® For the postpolymerization was put 0.05 g of azo initiator VA-044 ® and to the dispersion was heated for one hour at a temperature of 50 ° C. An aqueous dispersion having a viscosity of 2300 mPas was obtained. By adding water and adjusting the pH to 7, a 2% aqueous solution was prepared which had a viscosity of 32,000 mPas.
• EXAMPLE 11 63.0 g of stabilizer 7 9.0 g of stabilizer 8 400 g of water and 45 g of acrylic acid were introduced into the apparatus indicated in Example 1 and stirred while passing nitrogen through at a speed of 100 rpm. To this solution, 0.45 g of sodium persulfate and 14.4 g of water were added and grafted at 25 ° C for 15 minutes. Then, 135 g of acrylic acid and 27 g of stabilizer 8 in 2 hours at 25 ° C closed. At the same time, 0.18 g of ascorbic acid were added in 7 hours. Subsequently, polymerization was continued for one hour. An aqueous dispersion having a viscosity of 800 mPas and a pH was obtained from 1, 5. By adding water and sodium hydroxide, a 2% dispersion having a pH of 7 was prepared. The viscosity of the dispersion was 5000 mPas.
• Example 12 In a 2-liter four-necked flask equipped with a Teflon stirrer and a device for working under nitrogen, 257.0 g of stabilizer 1, 449.0 g of stabilizer 2 and 102.5 g of deionized water were introduced while passing nitrogen through it and stirring while passing nitrogen at a speed of 200 rpm for 10 minutes. 60 g of acrylic acid were added dropwise to this solution over 10 minutes, the reaction mixture was heated to 60 ° C and a solution of 90 g of acrylic acid and 1, 5 g of ethoxylated trimethylene propane triacrylate was added over 3.5 hours.
• Example 12 257.0 g of stabilizer 1, 449.0 g of stabilizer 2 and 102.5 g of deionized water were introduced while passing nitrogen through it and stirred while passing nitrogen at a speed of 200 rpm for 10 minutes. 60 g of acrylic acid and 0.015 g of VA- 044® were added dropwise to this solution over 10 minutes, the reaction mixture was heated to 60 ° C and a solution of 90 g of acrylic acid and 1, 5 g of ethoxylated trimethylolpropane triacrylate was added over 3.5 hours.
• Example 12 257.0 g of stabilizer 1, 449.0 g of stabilizer 2 and 102.5 g of deionized water were introduced while passing nitrogen through it and stirred while passing nitrogen at a speed of 200 rpm for 10 minutes. 60 g of acrylic acid and 0.015 g of VA- 044® were added dropwise to this solution over 10 minutes, the reaction mixture was heated to 60 ° C and a solution of 75 g of acrylic acid, 15 g of methyl methacrylate and 1, 5 g of triallylamine was added over 3.5 hours , Simultaneously with the addition of the acrylic acid / Triallylamint solution began four-hour addition of a solution of 0.135 g of azo initiator VA-044 ® in 40 g water.
• Example 18 In a 250 ml four-necked flask equipped with a Teflon stirrer and an apparatus for working under nitrogen were added while passing nitrogen
• reaction mixture was then admixed with 0.3 g of azo starter VA- 044® in 20 g of water and polymerized at 40 ° C. for 1 hour. An aqueous dispersion having a solids content of 37.1% was obtained.
• Example 21 In a 250 ml four-necked flask equipped with a Teflon stirrer and a nitrogen working apparatus were passed while passing nitrogen
• Example 22 was repeated with the exceptions that in the polymerization reactor 359 g of fully desalinated water, 87.5 g of a block copolymer of ethylene oxide (EO) and propylene oxide (PO) with an EO content of 20% and a MoI mass of 1750 g / mol of the polypropylene glycol block, 87.5 g of a copolymer of 20.3 parts by weight of propylene oxide and 14.2 parts by weight of ethylene oxide, and 250 g of a 10% aqueous solution of a copolymer of 90 mol% methacrylic acid and 10 mol% of the Na salt submitted the acrylamidomethylpropanesulfonic. you received a white dispersion with a viscosity of 1 000 mPas. A 0.5% aqueous solution prepared therefrom had a viscosity of 30,000 mPas at a pH of 7.
• EO ethylene oxide
• PO propylene oxide
• Example 24 was repeated with the sole exception that instead of the copolymer of 90 mol% of methacrylic acid and 10 mol% of the sodium salt of acrylamidomethylpropanesulfonic acid, a copolymer of the composition 10 mol% methacrylic acid and 90 mol% of the Na salt of acrylamidomethylpropanesulfonic acid.
• An aqueous dispersion having a viscosity of 1500 mPas was obtained.
• An aqueous solution of the dispersion diluted to 0.5% had a viscosity of 25,000 mPas at a pH of 7.
• Example 24 was repeated with the sole exception that, instead of the copolymer of 90 mol% methacrylic acid and 10 mol% of the sodium salt of acrylamidomethylpropanesulfonic acid, a copolymer having a composition of 50 mol% methacrylic acid and 50 mol % of the sodium salt of acrylamidomethylpropanesulfonic acid.
• An aqueous dispersion having a viscosity of 1200 mPas was obtained.
• An aqueous solution of the dispersion diluted to 0.5% had a viscosity of 35,000 mPas at a pH of 7.
• Example 24 was repeated with the sole exception that, instead of the copolymer of 90 mol% of methacrylic acid and 10 mol% of the Na salt of acrylamidomethylpropanesulfonic acid, a copolymer of composition 80% by mol of methacrylic acid and 20% by mol is now used. of the Na salt of acrylamidomethylpropanesulfonic acid. An aqueous dispersion having a viscosity of 1,300 mPas was obtained. An aqueous solution of the dispersion diluted to 0.5% had a viscosity of 33,000 mPas at a pH of 7.
• Example 24 was repeated with the sole exception that, instead of the copolymer of 90 mol% of methacrylic acid and 10 mol% of the sodium salt of acrylamidomethylpropanesulfonic acid, a copolymer of composition 70% by mol of methacrylic acid and 30% by mol was used. Na salt of acrylamidomethylpropanesulfone acid used. An aqueous dispersion having a viscosity of 1100 mPas was obtained. An aqueous solution of the dispersion diluted to 0.5% had a viscosity of 29,000 mPas at a pH of 7.
• propylene oxide (PO) having an EO content of 20% and a molecular weight of 1750 g / mol of the polypropylene glycol block, 87.5 g of a copolymer of 20.3 parts by weight of propylene oxide and 14.2 parts by weight of ethylene oxide and 250 g of a 10% aqueous solution of a copolymer of 80 mol% of methacrylic acid and 20 mol% of the sodium salt of acrylamidomethylpropanesulfonic presented.
• PO propylene oxide
• propylene oxide (PO) having an EO content of 20% and a molecular weight of 1750 g / mol of the polypropylene glycol block, 87.5 g of a copolymer of 20.3 parts by weight of propylene oxide and 14.2 parts by weight of ethylene oxide and 250 g of a 10% aqueous solution of a copolymer of 80 mol% of methacrylic acid and 20 mol% of the Na salt of acrylamidomethylpropanesulfonic presented.
• PO propylene oxide
• Example 22 was repeated with the exceptions that a solution of 87.5 g of a block copolymer of ethylene oxide (EO) and propylene oxide (PO) having an EO content of 20% and a molecular weight of 1750 g / mol of the polypropylene glycol block, 87.5 g of a copolymer of 20.3 parts by weight of propylene oxide and 14.2 parts by weight of ethylene oxide, 53.4 g of a 45% aqueous polyacrylic acid of molecular weight M w 50 000 and 555.7 g completely desalinated water submitted. An aqueous dispersion having a viscosity of 2,000 mPas was obtained. A 0.5% aqueous solution of this dispersion had a viscosity of 26,000 mPas at pH 7.
• EO ethylene oxide
• PO propylene oxide
• Example 22 was repeated with the exceptions that a solution of 87.5 g of a block copolymer of ethylene oxide (EO) and propylene oxide (PO) having an EO content of 20% and a molecular weight of 1750 g / mol of the polypropylene glycol block, 87.5 g of a copolymer of 20.3 parts by weight of propylene oxide and 14.2 parts by weight of ethylene oxide, 120 g of a 20% aqueous solution of polyacrylamidomethyl-propanesulfonic acid and 555.7 g of completely demineralized water. An aqueous dispersion having a viscosity of 1,900 mPas was obtained. A 0.5% aqueous solution of this dispersion had a viscosity of 28,000 mPas at pH 7.
• EO ethylene oxide
• PO propylene oxide
• Example 33 Example 32 was repeated with the sole exception that in the template the poly-acrylamidomethylpropanesulfonic acid was replaced by the same amount of 20% aqueous polymethacrylic acid of molecular weight M w 40,000. An aqueous dispersion was obtained. persion with a viscosity of 1,900 mPas. A 0.5% aqueous solution of this dispersion had a viscosity of 36,000 mPas at pH 7.
• Example 34 Example 27 was repeated with the sole exception that instead of pentaerythritol triallyl ether, 1.75 g of a 10% strength aqueous solution of an ethoxylated trimethylolpropane triacrylate were used as crosslinking agent. An aqueous dispersion having a viscosity of 900 mPas was obtained. A 0.5% aqueous solution of this dispersion had a viscosity of 34,000 mPas at pH 7.
• Example 27 was repeated with the sole exception that instead of pentaerythritol triallyl ether, 4.35 g of a 10% strength aqueous solution of triallylamine were used as crosslinker. An aqueous dispersion having a viscosity of 1,000 mPas was obtained. A 0.5% aqueous solution of this dispersion had a viscosity of 38,000 mPas at pH 7
• Example 22 was repeated with the exceptions that a solution of 87.5 g of a block copolymer of ethylene oxide (EO) and propylene oxide (PO) with an EO content of 20% and a molecular weight of 1750 g / mol of the polypropylene was used as a template.
• EO ethylene oxide
• PO propylene oxide
• Glycol glycol 87.5 g of a copolymer of 20.3 parts by weight of propylene oxide and 14.2 parts by weight of ethylene oxide, 250 g of a 10% aqueous solution of a copolymer of 60 mol% of methacrylic acid, 20 mol% of the Na salt of acrylamidomethylpropanesulfonic acid and 20 mol% of a methyl chloride-quaternized vinylimidazole and 359 g of completely desalted water. This gave a dispersion having a viscosity of 2000 m Pas. A 0.5% aqueous solution of this dispersion had a viscosity of 20,000 mPas at pH 7.
• Example 22 was repeated with the exceptions that a solution of 87.5 g of a block copolymer of ethylene oxide (EO) and propylene oxide (PO) with an EO content of 20% and a molecular weight of 1750 g / mol of the polypropylene was used as a template.
• glycol block 87.5 g of a copolymer of 20.3 parts by weight of propylene oxide and 14.2 parts by weight of ethylene oxide, 250 g of a 10% aqueous solution of a copolymer of 20 mol% methyl acrylate, 69 mol% of the sodium salt of the acrylamic acid.
• Example 22 was repeated with the exceptions that a solution of 175 g of polyethylene glycol of molecular weight M w 1500, 250 g of a 10% aqueous solution of a copolymer of 80 mol% methacrylic acid and 20 mol% of Na salt of the Acrylamidomethylpropanesulfonic acid and 359 g of completely deionized water. This gave a dispersion having a viscosity of 2500 m Pas. A 0.5% aqueous solution of this dispersion had a viscosity of 34,000 mPas at pH 7.
• Example 39 In a glass reactor equipped with an anchor stirrer and a nitrogen working apparatus, 479.8 g of fully desalted water, 106.7 g of a block copolymer, were passed while passing nitrogen over with stirring at a rate of 200 rpm Ethylene oxide (EO) and propylene oxide (PO) with an EO content of 20% and a molecular weight of 1750 g / mol of the polypropylene glycol block, 53.3 g of a copolymer of 20.3 parts by weight of propylene oxide and 14.2 parts by weight of ethylene oxide and 110 g of a 20% aqueous solution of a copolymer of 59 parts by weight of acrylamidomethylpropanesulfonic acid, 20 parts by weight of methyl acrylate, 20 parts by weight of acrylic acid and 1 part by weight of styrene.
• EO Ethylene oxide
• PO propylene oxide
• a block copolymer of ethylene oxide (EO) and propylene oxide (PO) were mixed with a Content of EO of 40% and a molecular weight of 1750 g / mol of the polypropylene glycol block (Pluronic ⁇ PE 6400) and 89.41 g of stabilizer 16 submitted.
• EO ethylene oxide
• PO propylene oxide
• a 2% strength by weight aqueous solution based on polyacrylic acid had a viscosity of 550 mPas (spindle 4 20 rpm) after pH adjustment to 7 with triethanolamine.
• a 2% strength by weight aqueous solution based on polyacrylic acid had a viscosity of 600 mPas (spindle 4 20 rpm) after pH adjustment to 7 with triethanolamine,
• Example 42 In a 2 l glass reactor equipped with an anchor stirrer and an apparatus for working under nitrogen, 560.59 g. Were passed while passing nitrogen through it distilled water, 175 g of a block copolymer of ethylene oxide (EO) and product pylenoxid (PO) with an EO content of 40% and a molecular weight of 1750 g / mol of the polypropylene glycol block (Pluronic ® PE 6400) and 89,41g stabilizer 16 presented , Then, with stirring (200 rpm) at room temperature, 175 g of acrylic acid and 0.875 g of triallylamine were added dropwise within 10 minutes.
• EO ethylene oxide
• PO product pylenoxid
• a 1 wt .-% aqueous solution based on polyacrylic acid had after pH adjustment to 7 with triethanolamine a viscosity of 11500 mPa s (spindle 6 20 rpm).
• Example 44 In a 2 l glass reactor equipped with an anchor stirrer and a device for working under nitrogen, 560.59 g of distilled water, 175 g of a block copolymer of EO and PO with an EO content of 30% were passed through nitrogen. submitted and a molar mass of 1100 g / mol of the polypropylene glycol block (Pluronic ® PE 4300) and 89,41g stabilizer sixteenth Thereafter, with stirring (200 rpm) at room temperature, 173.55 g of acrylic acid and 1.75 g of triallylamine were added dropwise within 10 minutes.
• Pluronic ® PE 4300 polypropylene glycol block
• acrylic acid and 1.75 g of triallylamine were added dropwise within 10 minutes.
• a 1 wt .-% aqueous solution based on polyacrylic acid had after pH adjustment to 7 with triethanolamine a viscosity of 21000 mPa s (spindle 6, 20 rpm).
• the reaction mixture was heated to an internal temperature of 40 ° C and held at this temperature until the end of the polymerization.
• a milky white tixotropic dispersion was obtained.
• the dispersion has a particle size of 8 to 20 microns.
• a 1 wt .-% aqueous solution based on polyacrylic acid had after pH adjustment to 7 with triethanolamine a viscosity of 34000 mPas (spindle 6, 20 rpm).
• a 1 wt .-% aqueous solution based on polyacrylic acid had after pH adjustment to 7 with triethanolamine a viscosity of 13000 mPas (spindle 6, 20 rpm).
• Example 47 In a glass reactor equipped with an anchor stirrer and a device for working under nitrogen, 560.59 g of distilled water, 175 g of a block copolymer of EO and PO with an EO content of 30% and a flow rate were passed through nitrogen Molar mass of 1100 g / mol of the polypropylene glycol block (Pluronic ® PE 4300) and 89.41 g of stabilizer 16 submitted. Then, with stirring (200 rpm) at room temperature, 173.25 g of acrylic acid and 1.75 g of N 1 N'-divinylethylene-urea were added dropwise within 10 minutes.
• azo starter VA-044 was added for postpolymerization. This gave a milky white dispersion with a viscosity of 68,000 mPas (spindle 4, 2.5 rpm). The dispersion had a particle size of 6 to 30 microns.
• azo starter VA-044 After addition of 0.2 g of azo starter VA-044, the reaction mixture was heated to an internal temperature of 40 ° C and held at this temperature until the end of the polymerization. After the end of the actual polymerization, 0.4 g of azo starter VA-044 was added to the postpolymerization. This gave a milky white dispersion with a viscosity of 15400 mPas (spindle 4, 10 rpm). The dispersion had a particle size of 6 to 30 microns.
• isoalkane mixture whose 1 H-NMR spectrum in the range of a chemical shift ⁇ of 0.6 to 1, 0 ppm, based on tetramethylsilane, an area integral of 25 to 70%, based on the total integral area, having.
• isoalkane mixtures and the processes for their preparation are described in unpublished patent application DE 10 2005 022 021.5.
• the abovementioned isoalkane mixtures can advantageously also be used as mixtures with isohexadecane or as mixtures with paraffin liquid, in each case in a weight ratio of from 10: 1 to 1:10, instead of pure paraffin oil.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. It will receive a refreshing gel with good properties.
• Application example 2 Hair shampoo or shower gel
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case, a hair shampoo or shower gel with good properties is obtained.
• Water / oil cream emulsions were prepared according to the following recipe:
• Water ad 100 The example can be repeated with the polymers of Examples 1 to 50. In each case a skin cream with good properties is obtained.
• Citric acid (pH 6-7) q.s.
• Water ad 100 The example can be repeated with the polymers of the remaining Examples 1 to 50. It will receive a shower gel with good properties.
• Example 1 0.50% polymer of Example 1 neutralized with triethanolamine to pH 7.5
• the example can be repeated with the polymers of the remaining Examples 1 to 50. It will receive a refreshing gel with good properties.
• phase a) was stirred into b), homogenized and stirred cold and then adjusted to pH 6 with 10% aqueous NaOH solution.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case a moisturizing formulation with good properties is obtained.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case, an O / W creams for skin moisturizing with good properties is obtained.
• Sorbitan monooleate 1 0
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case, an O / W lotion with good properties is obtained.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case, a W / O creams with good properties are obtained.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case a hydrogel for skin care with good properties is obtained.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case, a hydrodispersion gel having good properties is obtained.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case, a sunscreen emulsion with good properties is obtained.
• Phase B 5.00 Propylene Glycol qs Preservative 1, 0 polymer from Example 1 66.30 dist.
• Water phase C 0.20 carbomer
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case, a facial cleansing milk with good properties is obtained.
• Oxynex ® 2004 propylene glycol, BHT, ascorbyl palmitate, glyceryl stearate, citric acid 0.1%
• the example can be repeated with the polymers of the remaining Examples 1 to 50. There will be a Body Care Cream with good properties.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. There will be a liquid makeup with good properties.
• Coat phase A with butylene glycol add to phase B and mix well.
• Heat phase AB to 75 ° C.
• Pulverize phase C feedstocks add to phase AB and homogenize well.
• Mix the starting materials of phase D, heat to 80 ° C and add to phase ABC. Mix for a while until everything is homogenous. Transfer everything to a vessel with a propeller mixer.
• Mix phase E starting materials add to phase ABCD and mix well.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. There will be an oil-free makeup with good properties.
• Premix Phase B Mix phase B into phase A with a propeller mixer, allowing the thickener to swell.
• Wet Phase C with Phase D add everything to Phases AB and mix well.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. It will receive an eyeliner with good properties.
• phase A Using a propeller mixer, mix the starting materials of phase A well in the order listed. Then add phase B to phase A. Stir slowly until everything is homogeneous. Homogenise Phase C well until the pigments are well dispersed. Add phase C and phase D to phase AB and mix well.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case, a shimmering gel with good properties is obtained.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case a waterproof mascara with good properties is obtained.
• BMBM Uvinul ® butyl Methoxydibenzoylmethane
• phase A Mix the components of phase A. Swell phase B and stir in phase A with homogenization. Neutralize with Phase C and homogenize again.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case a sunscreen gel with good properties is obtained.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case, a sunscreen lotion with good properties is obtained.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case a face mask with good properties is obtained.
• Preparation Heat phases A and B separately to approx. 80 ° C. Stir phase B into phase A and homogenize. Cool to about 40 ° C, add phase C and briefly homogenize again. Filling: 90% active ingredient and 10% propane / butane at 3.5 bar (20 ° C).
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case, a body lotion foam having good properties is obtained.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. In each case a tonic with good properties is obtained.
• Phase B qs perfume oil 7.00 Potassium Cocoyl Hydrolyzed Protein 4.00 Cocamidopropyl Betaine Phase C
• phase A swell. Clear phase B clearly. Stir phase B into phase A. Neutralize with Phase C. Then stir in phase D.
• the example can be repeated with the polymers of the remaining Examples 1 to 50.
• a face wash paste with good properties is obtained in each case.
• the example can be repeated with the polymers of the remaining Examples 1 to 50. It will receive a facial soap with good properties.

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• 2006
  • 2006-01-24 US US11/814,988 patent/US20080193405A1/en not_active Abandoned
  • 2006-01-24 CA CA002595692A patent/CA2595692A1/en not_active Abandoned
  • 2006-01-24 WO PCT/EP2006/050420 patent/WO2006079632A1/de active Application Filing
  • 2006-01-24 KR KR1020077019561A patent/KR20070099038A/ko not_active Application Discontinuation
  • 2006-01-24 JP JP2007552638A patent/JP2008528749A/ja not_active Withdrawn
  • 2006-01-24 BR BRPI0607038-8A patent/BRPI0607038A2/pt not_active IP Right Cessation
  • 2006-01-24 RU RU2007132228/15A patent/RU2007132228A/ru not_active Application Discontinuation
  • 2006-01-24 EP EP06707825A patent/EP1843742A1/de not_active Withdrawn

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