Classifications

• • 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
• • 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
  • A61K8/046—Aerosols; Foams
• • 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
  • A61K8/81—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
  • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; 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
  • A61K8/81—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
  • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; 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
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
  • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate

Definitions

• the present invention relates to cosmetic and pharmaceutical compositions comprising copolymers which comprise copolymerized ethyl methacrylate and at least one monoethylenically unsaturated carboxylic acid, the copolymers themselves and their Verwen ⁇ tion.
• Polymers with film-forming properties have found many applications in the field of pharmacy and cosmetics.
• pharmacies they serve, for example, as a coating agent or binder for solid dosage forms.
• cosmetics polymers with film-forming properties u. a. used for strengthening, structural improvement and shaping of the hair. They serve, for example, as conditioners to improve the dry and wet combability, the feeling of touch, the gloss and the appearance and also to give the hair antistatic properties.
• the provision of products with a complex property profile is often difficult.
• EP-A-379 082 describes hair setting agents which contain as film formers copolymers with a K value of from 10 to 50, which are composed of 75 to 99% by weight of t-butyl acrylate and / or t-butyl methacrylate, 1 to 25% by weight of acrylic acid and / or methacrylic acid and 0 to 10% by weight of another free-radically copolymerizable monomer.
• the carboxyl groups of the copolymers are partially or completely neutralized by amines.
• DE-A-43 14 305 describes hair-setting compositions which contain as film formers copolymers of the type mentioned in EP-A-379 082 which are composed of 30 to 72% by weight of t-butyl acrylate and / or t-butyl methacrylate, 10 to 28 wt .-% of acrylic acid and / or methacrylic acid and 0 to 60 wt .-% of a radically copolymerizable monomer or a free-radically copolymerizable monomeric mixture, wherein at least one of these monomers provides a homopolymer having a glass transition temperature below 30 0 C.
• No. 3,577,517 describes hair lacquers and aerosol formulations which comprise neutralized solution polymers of from 5 to 40% by weight of a (meth) acrylic acid ester with C 8 -C 18 aliphatic alcohols, from 6 to 35% by weight of (meth) acrylic acid and 25 to 89 wt .-% ei ⁇ nes further vinyl monomer, a water-soluble organic solvent and propellant.
• neutralized solution polymers of from 5 to 40% by weight of a (meth) acrylic acid ester with C 8 -C 18 aliphatic alcohols, from 6 to 35% by weight of (meth) acrylic acid and 25 to 89 wt .-% ei ⁇ nes further vinyl monomer, a water-soluble organic solvent and propellant.
• US 5,589,157 and EP-A 590 604 describe aqueous acrylic polymer compositions containing copolymers consisting of 35 to 74 wt .-% of an alkyl acrylate, 25 to 65 wt .-% of an alkyl methacrylate and 1 to 15 wt .-% of a (Meth) acrylic acid or salts thereof and their use in hair cosmetic preparations.
• JP 3056409 describes hairspray preparations containing an anionic resin which is composed of 30 to 70% by weight of C 1 -C 7 -alkyl or alkenyl (meth) acrylate, 10 to 50% by weight of C 9 -C 24 Alkyl or alkenyl (meth) acrylate and 10 to 40% by weight of a polymerizable carboxyl group-containing compound.
• No. 3,405,084 describes terpolymer resins consisting of 25 to 75% by weight of vinylpyrrolidone, 20 to 70% by weight of (meth) acrylate and 3 to 25% by weight of olefinically unsaturated carboxylic acid for use in hair cosmetic preparations, in particular as hair sprays ,
• EP-A 331 994 describes hair setting preparations comprising copolymers of a) 40-60% by weight of Ca-C 1-4 -alkyl methacrylates, b) 20 to 40% by weight of C 4 -C 10 -N-alkyl-substituted acrylamides and c ) 10 to 25% by weight of (meth) acrylic acid.
• Copolymers of a) isobutyl methacrylate, b) N-tert-octylacrylamide and c) acrylic acid are preferably used.
• EP-A 985 401 describes hairstyling preparations comprising a resin consisting of 5-95% C 1 -C 10 alkyl (meth) acrylate, 2-16% hydroxyalkyl (meth) acrylate, 0-50% C 3 -C 8 monoethylenically unsaturated monocarboxylic acids and 2-10% monoethylenically unsaturated dicarboxylic acids.
• GB 1410012 describes aerosol hair spray preparations which contain methacrylic acid C r C 3 -alkyl (meth) acrylate copolymers, in particular methyl acrylate copolymers or methacrylic acid-methyl acrylate-methyl methacrylate terpolymers.
• EP-A 62 002 describes hair cosmetic preparations containing terpolymers which are obtained by copolymerizing a) 40 to 60% by weight of an N-alkylacrylamide or N-alkylmethacrylamide having from 1 to 4 carbon atoms with b) 35 to 50% by weight. % of a CrCzrHydroxyalkylester or preferably C 1 -C 4 alkyl esters of acrylic or methacrylic acid and c) 3 to 11 wt .-% of an ⁇ , ß-unsaturated monocarboxylic acid or dicarboxylic acid are prepared.
• EP-A 100 890 discloses copolymers obtained by free-radical copolymerization of
• 25 0 C have a K value according to Fikentscher of 15 to 75.
• VOCs volatile organic compounds
• Requirements for hair setting resins are, for example, a strong consolidation at high humidity, elasticity, good washability from the hair, compatibility in the formulation, the lowest possible stickiness of the film formed and a pleasant handle of the treated hair.
• spray formulations in particular a homogeneous distribution of small droplets to form a fine spray pattern is desired. Difficulties often arise in the provision of products with a complex property profile.
• cosmetic preparations which are capable of forming substantially smooth, tack-free films which impart to the hair and the skin good sensory properties, such as a pleasant feel, and at the same time a good conditioning effect or strength Have ⁇ effect.
• the object of the present invention was to provide polymers for cosmetic preparations which can be formulated in solvents or solvent mixtures with an increased water content and whose formulations when sprayed as spray good sprayability and a fine, homogeneous spray pattern with good mechanical properties of the have formed films.
• the polymers are said to confer good firmness and longer hold on the hair, have good leachability and have to be optically clear VOC-55 aerosols (ie with a VOC content of at most 55% by weight). -%).
• compositions which can be derived from acrylic acid and methacrylic acid are sometimes abbreviated by insertion of the syllable "(meth)" into the compound derived from the acrylic acid.
• the invention relates to cosmetic preparations comprising at least one copolymer which is obtainable by free-radical polymerization of
• the invention preferably relates to cosmetic preparations comprising at least one copolymer which is obtainable by free-radical polymerization of
• the invention also relates to polymers obtainable by radical polymerization of a) from 16 to 40% by weight of at least one monoethylenic compound b) from 30 to 84% by weight of ethyl methacrylate, c) from 0 to 50% by weight of at least one further radically polymerizable monomer c) different from a) and b), the amounts of components a), b and c) add up to 100% by weight, with the proviso that if the free radical polymerization is a solution polymerization and a) consists exclusively of acrylic acid and methacrylic acid and at the same time c) is selected from the group of Esters of (meth) acrylic acid with aliphatic C 8 -C 18 -alcohols, c) then may not be selected from 5 to 40 wt .-% esters of (meth) acrylic acid with aliphatic C 8 -C 18 alcohols and with with the proviso that, when c) is selected from the group consisting of
• the object is further achieved by the provision of cosmetic preparations comprising at least one copolymer obtainable by free-radical polymerization of a) from 16 to 40% by weight of at least one monoethylenically unsaturated carboxylic acid, b) from 30 to 84% by weight % Of ethyl methacrylate, c) 0 to 50% by weight of at least one further radically polymerizable monomer c) which differs from a) and b), the amounts of components a), b) and c) being too 100 wt .-% add and wherein the polymerization is an emulsion polymerization.
• the invention accordingly also provides polymers obtainable by free-radical polymerization of a) from 16 to 40% by weight of at least one monoethylenically unsaturated carboxylic acid, b) from 30 to 84% by weight of ethyl methacrylate, c) from 0 to 50% by weight At least one further, of a) and b) different radically polymerizable Mo ⁇ nomeren c), wherein the amounts of the compo nents a), b) and c) add up to 100 wt .-% and wherein the polymerization is an emulsion polymerization ,
• the invention further provides polymers obtainable by free-radical polymerization of a) from 5 to 40% by weight, preferably from 10 to 35% by weight, more preferably from 12 to 30% by weight, of at least one monoethylenically unsaturated carboxylic acid, b) 30 to 95 wt .-%, preferably 40 to 80 wt .-%, particularly preferably 45 to 75 wt .-% ethyl methacrylate, c) 0 to 50 wt .-% of at least one further, of a) and b) free-radically polymerizable monomers c), the amounts of a), b) and c) adding up to 100% by weight, with the proviso that when the free-radical polymerization is a solution polymerization and a) exclusively from Acrylic acid and methacrylic acid and at the same time c) is selected from the group of the esters of (meth) acrylic acid with ⁇ -aliphatic C 8 -C 8 -alcohol
• the monomers a) include monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 25, preferably 3 to 6, carbon atoms, which can also be used in the form of their salts or anhydrides. Examples thereof are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid.
• the monomers a) furthermore include the half-esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, eg.
• the monomers a) also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts.
• the monomers a) can be used as such or as mixtures with one another. The stated proportions by weight are all based on the sheu ⁇ reform.
• monomer a) is selected from the group consisting of 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, particularly preferably Acrylic acid, methacrylic acid and mixtures thereof and in particular methacrylic acid.
• a) consists of a1) methacrylic acid and optionally a2) other monoethylenically unsaturated monocarboxylic acids other than methacrylic acid.
• a) consists of a1) methacrylic acid and optionally a2), where a2) is selected from the group consisting of acrylic acid, ethacrylic acid, .alpha.-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, Citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.
• a) consists of a1) acrylic acid and optionally a2), where a2) is selected from the group consisting of methacrylic acid, ethacrylic acid, .alpha.-chloroacrylic acid, crotonic acid, maleic acid, maleic acid, Acid anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.
• component a) contains no monoethylenically unsaturated dicarboxylic acids.
• component a) comprises a mixture of methacrylic acid and itaconic acid or component a) consists of a mixture of methacrylic acid and itaconic acid.
• component a) comprises a mixture of methacrylic acid and acrylic acid or component a) consists of a mixture of methacrylic acid and acrylic acid.
• component a) is a mixture of methacrylic acid and further monoethylenically unsaturated carboxylic acids, it is advantageous if the weight ratio of methacrylic acid to further acids is greater than 1, preferably greater than 2, more preferably at least 3 and in particular at least 4.
• the amount of a) is at least 16, preferably at least 18, more preferably at least 20 and at most 40, preferably at most 38, more preferably at most 35 and most preferably at most 30 wt .-%.
• the polymers according to the invention consist exclusively of ethyl methacrylate and component a).
• esters of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids are esters of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids
• Suitable monomers c) are, for example, selected from C 1 -C 8 -alkyl acrylates and
• Suitable monomers c) are the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids other than ethyl methacrylate, such as, for example, methyl (meth) acrylate, ethyl acrylate, methyl methacrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-propylethacrylate, ethylethacrylate, i-propylethacrylate, n-butyl (meth) acrylate, n-butylethacrylate, tert-butyl (meth) acrylate, tert-butylethacrylate, i-butyl (meth) acrylate, i-butyl ethacrylate, sec-butyl (meth) acrylate, butlyethacrylate, 2-pentyl (meth) acrylate,
• Preferred monomers c) are the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids other than ethyl methacrylate with C 1 -C 4 -alkanols.
• Suitable monomers c) are furthermore esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with polyhydric alcohols, such as, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2- Hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate, 3 Hydroxy-2-ethylhexyl methacrylate and mixtures thereof.
• polyhydric alcohols such as, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy
• a) is composed exclusively of acrylic acid and methacrylic acid, and is selected at a time component c) from the group of esters of (meth) acrylic acid with aliphatic C 8 -C 8 alcohols, then c) will not be chosen from 5 to 40 wt .-% Esters of (meth) acrylic acid with aliphatic C 8 -C 18 -alcohols.
• Suitable monomers c) are also vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl ester of the Versatie Textre (VeoVa ® monomers), 4-tert-butylbenzoate and their mixtures.
• Suitable monomers c) are furthermore ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
• N-vinylamides of saturated C 1 -C 8 monocarboxylic acids Suitable monomers c) are N-vinylamides of saturated C r C 8 mono-carboxylic acids such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N- methylacetamide, N-vinyl-N-ethylacetamide , N-vinylpropionamide, N-vinyl-N-methyl-propionamide, N-vinylbutyramide and mixtures thereof.
• Suitable monomers c) are also NC r C 18 -alkylacrylamides and N-Ci-Ci 8 -alkyl methacrylamides.
• Suitable monomers c) are, in particular, primary amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives which, in addition to the carbonyl carbon atom of the amide group, have at most 8 further carbon atoms, for example acrylic acid amide , Methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) methacrylamide, N- (sec-butyl) methacrylamide, N- (tert Butyl) methacrylamide, N- (n-pentyl) (meth) acrylamide, N- (n-hexyl) (meth) acrylamide, N- (n-heptyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (tert
• c) comprises methacrylamide and / or N- (tert-butyl) acrylamide or consists of one of these components or of a mixture of methacrylamide and N- (tert-butyl) acrylamide.
• Suitable monomers c) are also amides of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols having a primary or secondary amino group, such as 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, 2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide, 2-hydroxypropylmethacrylamide , 3-hydroxypropylacrylamide, 3-hydroxypropylmethacrylamide, 3-hydroxybutylacrylamide, 3-hydroxybutylmethacrylamide, 4-hydroxybutylacrylamide, 4-hydroxybutylmethacrylamide, 6-hydroxyhexylacrylamide, 6-hydroxyhexylmethacrylamide, 3-hydroxy-2-ethylhexylacrylamide, 3-hydroxy-2-ethylhexylmethacrylamide and mixtures thereof.
• amino alcohols having a primary or secondary amino group such as 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, 2-hydroxyethylethacryl
• the copolymers of the invention may additionally contain at least one compound having a free-radically polymerizable, .alpha.,. Beta.-ethylenically unsaturated double bond and at least one cationogenic and / or cationic group per molecule.
• the cationogenic or cationic groups of component c) are preferably nitrogen-containing groups, such as primary, secondary and tertiary amino groups, and quaternary ammonium groups.
• the nitrogen-containing groups are tertiary amino groups.
• the compounds c) are preferably used in an uncharged form for the polymerization. However, use in charged form is also suitable.
• Charged cationic groups can be z. B. from the amine nitrogens by protonation, z. B. with monohydric or polyhydric carboxylic acids such as lactic acid or tartaric acid, or mineral acids such as Phos ⁇ phosphoric acid, sulfuric acid and hydrochloric acid.
• Component c) can be selected from esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, which may be mono- or dialkylated on the amine nitrogen, amides of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines, which at least one primary or secondary amino group, N, N-diallylamine, N, N-diallyl-N-alkylamines and their derivatives, vinyl- and aliyl-substituted nitrogen heterocycles, vinyl- and allyl-substituted heteroaromatic compounds and mixtures thereof.
• esters As the acid component of these esters are z. Acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. Preference is given to using acrylic acid, methacrylic acid and mixtures thereof.
• Examples of such compounds c) are N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, N- (n-propyl) aminoethyl (meth) acrylate, N- (n-butyl) aminoethyl (meth) acrylate, N N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth ) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate.
• N- (tert-butyl) aminoethyl acrylate and N- (tert-butyl) aminoethyl methacrylate are used.
• Suitable monomers c) are furthermore the amides of the abovementioned ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group. Preference is given to diamines which have a tertiary and a primary or secondary amino group.
• These cationogenic monomers c) can also be present in quaternized form.
• the quaternization is carried out in the case of the abovementioned monomers, if appropriate using methyl chloride, methyl sulfate or diethyl sulfate.
• Suitable monomers c) are also NN-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts.
• Alkyl is preferably C r C 24 -alkyl.
• cationogenic monomers c) can also be present in quaternized form.
• the quaternization is carried out with conventional quaternizing agents such as methyl chloride, methyl sulfate or diethyl sulfate.
• Suitable monomers c) are also vinyl- and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinylimidazole derivatives, eg. N-vinyl-2-methylimidazole, vinyl- and allyl-substituted heteroaromatic compounds such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.
• N-vinylimidazole N-vinylimidazole derivatives, eg. N-vinyl-2-methylimidazole
• vinyl- and allyl-substituted heteroaromatic compounds such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.
• Suitable monomers c) are also N-vinylimidazoles of the general formula (I) in which R 1 to R 3 are hydrogen, C 1-4 -alkyl or phenyl
• component c) is selected from N- (tert-butylamino) ethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- [3- (dimethylamino) propyl] (meth) acrylamide , Vinylimidazole and mixtures thereof.
• cationogenic monomers c) can also be present in quaternized form.
• the quaternization is carried out with conventional quaternizing agents such as methyl chloride, methyl sulfate or diethyl sulfate.
• Suitable components c) are also polyether acrylates.
• polyether acrylates are generally understood to mean esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with polyetherols.
• Suitable polyetherols are linear or branched, terminal hydroxyl-containing substances containing ether bonds. In general, they have a molecular weight in the range of about 150 to 20,000.
• Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers.
• Suitable alkylene oxides for the preparation of alkylene oxide copolymers are e.g.
• the alkylene oxide copolymers may randomly distribute the alkylene oxide units or contain them in copolymerized form in the form of blocks. Preferred are ethylene oxide / propylene oxide copolymers.
• Component c) are polyether acrylates of the general formula V
• k and I independently of one another represent an integer from 0 to 1000, the sum of k and I being at least 5,
• R 4 is hydrogen, C 1 -C 30 -alkyl or C 5 -C 8 -cycloalkyl
• R 5 is hydrogen or C 8 alkyl R C
• Y 2 is O or NR 6 , where R 6 is hydrogen, C 1 -C 10 -alkyl or C 5 -C 8 -cycloalkyl,
• k is an integer from 1 to 500, in particular 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 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 the formula V is O or NH.
• Suitable polyether acrylates c) 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 epi-chlorohydrin 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 c) can be used alone or in mixtures for the preparation of the polymers used according to the invention.
• Suitable components c) are also allyl alcohol propoxylates or allyl alcohol ethoxylates.
• Suitable monomers c) are also N-vinyllactams are unsubstituted N-vinyllactams and N-vinyllactam derivatives, the z.
• N-vinylpyrrolidone N-vinylpiperidone, N-vinylcaprolactam
• N-vinyl-5-methyl-2-pyrrolidone N-vinyl-5-ethyl-2-pyrrolidone
• N-vinyl-6-methyl-2-piperidone N-vinyl-6-ethyl-2-piperidone
• N-vinyl-7-methyl-2-caprolactam N-vinyl-7-ethyl-2-caprolactam etc.
• the copolymers according to the invention preferably comprise less than 10% by weight, preferably less than 5% by weight, particularly preferably less than 3% by weight, of copolymerized N-vinyllactams. With very particular preference the copolymers according to the invention contain less than 1% by weight and in particular no N-vinyllactams.
• monomer c) is selected from the group consisting of N-vinylpyrrolidone, N-vinylcaprolactam and mixtures thereof
• the amount of c) is less than 10, preferably less than 5,% by weight, especially preferably less than 3 and in particular less than 1 wt .-%.
• the at least one monomer c) is selected from the group consisting of C 1 -C 4 -alkyl acrylates, C 1 -C 4 -alkyl methacrylates, acrylamide, methacrylamide, N-C 1 -C 6 -alkyl acrylamides and N-C 1 -C 18 - Alkyl methacrylamides, with n-butyl acrylate, tert-butyl acrylate, hydroxyethyl methacrylate, ethyl acrylate and mixtures thereof are particularly preferred.
• the abovementioned monomers c) can each be used individually or in the form of any desired mixtures.
• a preferred cosmetic formulation comprises a copolymer obtainable by free radical polymerization of
• a particularly preferred cosmetic formulation comprises a copolymer obtainable by radical polymerization of a) from 20 to 35% by weight of a monoethylenically unsaturated carboxylic acid, b) from 45 to 80% by weight of ethyl methacrylate, c) from 0 to 50% by weight of monomer c), the amounts of components a), b) and c) add to 100 wt .-%.
• the monomers c) are used in amounts of from 0 to 50% by weight, preferably in amounts of from 0 to 30, more preferably in amounts of from 0 to 20% by weight, most preferably in amounts of from 0 to 15% by weight. -% and in particular in amounts of less than 10 wt .-% used.
• the copolymers according to the invention may contain at least one crosslinker, ie. H. in copolymerized form contain a compound having two or more than two ethylenically unsaturated, non-conjugated double bonds.
• Crosslinkers are preferably used in an amount of 0.01 to 7 wt .-%, particularly preferably 0.1 to 5 wt .-%, based on the total weight of the monomers used for the polymerization.
• Suitable crosslinkers are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols.
• the OH groups of the underlying alcohols can be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.
• Examples of the underlying alcohols are dihydric alcohols such as 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1, 4-butanediol , But-2-ene-1, 4-diol, 1,2-pentanediol, 1,5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1 , 12-dodecanediol, neopentyl glycol, 3-methylpentane-1, 5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanedio
• the homopolymers of ethylene oxide or propylene oxide also block copolymers of ethylene oxide or propylene oxide or copolymers containing incorporated incorporated ethylene oxide and propylene oxide groups.
• underlying alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, triethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose.
• the polyhydric alcohols are also used after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates.
• the polyhydric alcohols can also be first converted by reaction with epichlorohydrin in the corresponding glycidyl ether.
• crosslinkers are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C 3 -C 6 -carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
• examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamyl alcohol Citronellol,
• Crotyl alcohol or cis-9-octadecen-1-ol it is also possible to esterify the monohydric, unsaturated alcohols with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
• polybasic carboxylic acids for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
• crosslinkers are esters of unsaturated carboxylic acids with the above-described polyhydric alcohols, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
• crosslinking agents are straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated in aliphatic hydrocarbons, eg. B. divinylbenzene, divinyltoluene, 1, 7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights of 200 to 20,000.
• crosslinking agents are the acrylic acid amides, methacrylic acid amides and N-allylamines of at least divalent amines.
• amines are 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine.
• amides of allylamine and unsaturated Carbonkla ren such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least bivalent carboxylic acids, as described above.
• triallylamine and Triallylmonoalkylammoniumsalze, z As triallylmethylammonium chloride or methyl sulfate, suitable as a crosslinker.
• N-vinyl compounds of urea derivatives at least bivalent amides, cyanurates or urethanes, for example of urea, ethylene urea, propylene urea or tartaramide, for. N, N'-divinylethyleneurea or N, N'-divinylpropyleneurea.
• Further suitable crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane.
• Crosslinkers used with particular preference are, for example, methylenebisacrylamide, triallylamine and triallylalkylammonium salts, divinylimidazole, pentaerythritol triallyl ether, N, N'-divinylethyleneurea, reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic acid esters and acrylic esters of polyalkylene oxides or polyhydric alcohols which react with ethylene oxide and / or Propylene oxide and / or epichlorohydrin have been implemented.
• Very particularly preferred crosslinkers are pentaerythritol triallyl ether, Methylenbis ⁇ , N, N J divinylethyleneurea, triallylamine and salts and Triallylmonoalkylammonium- acrylate of glycol, butanediol, trimethylolpropane or glycerol or of acrylate with ethylene oxide and / or epichlorohydrin unreacted glycol, Bu ⁇ tandiol, Trimethylolpropane or glycerin.
• copolymers are prepared by customary methods known to the person skilled in the art, e.g. by solution, precipitation, suspension or emulsion polymerization.
• the preparation is preferably by solution or emulsion polymerization.
• Preferred solvents for the solution polymerization are aqueous solvents such as water and mixtures of water with water-miscible solvents, for example alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-butyl Hexanol and cyclohexanol and glycols such as ethylene glycol, propylene glycol and butylene glycol and the methyl or ethyl ethers of dihydric alcohols, diethylene glycol, triethylene glycol, polyethylene glycols with number average molecular weights up to about 3000, glycerol and dioxane.
• alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-butyl Hexanol
• water desalted water is preferably used.
• the copolymers are particularly preferably prepared in a known manner by free-radically initiated aqueous emulsion polymerization of the monomers a), b) and optionally c).
• the free-radically initiated aqueous emulsion polymerization is usually carried out by dispersing the monomers, generally with co-use of dispersants, in aqueous medium and polymerizing them by means of at least one free radical polymerization initiator.
• Suitable free-radical polymerization initiators for the inventive radical aqueous emulsion polymerization are all those which are capable of initiating a free-radical aqueous emulsion polymerization.
• inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric acid, such as, for example, their mono- and di-sodium, potassium or ammonium salts or organic peroxides, can be used as peroxides.
• alkyl hydroperoxides for example tert-butyl, p-menthyl or cumyl hydroperoxide, tert-butyl perpivalate and dialkyl or diaryl peroxides, such as di-tert-butyl or di-cumyl peroxide, 2,5-dimethyl-2, 5-di (t) butyl peroxy (hexane) or dibenzoyl peroxide are used.
• the azo compounds are essentially 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (amidinopropyl) dihydrochloride (AIBA, corresponding to V-50 TM from Wako Chemicals ), 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2-amidinopropane) salts, 4,4'-azobis (4-cyanovaleric acid) or 2- (carbamoylazo) isobutyronitrile ,
• Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides.
• Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium bisulfite, alkali metal metisulfites, for example potassium and / or sodium metabisulfite.
• alkali metal salts especially potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrogensulfides, for example potassium and / or sodium hydrogensulfide, salts of polyvalent metals, such as iron (II ) sulfate, iron (II) ammonium sulfate, iron (II) phosphate, endiols, such as dihydroxymaleic acid, benzoin and / or ascorbic acid, and reducing saccharides, such as sorbose, glucose, fructose and / or dihydroxyacetone ,
• the initiators are usually used in amounts of up to 10, preferably 0.02 to 5 wt .-%, based on the monomers to be polymerized.
• the emulsion polymerization is usually carried out in the presence of surfactants and / or
• Protective colloids performed.
• at least one dispersing assistant is used which can hold both the monomer droplets and polymer particles dispersed in the aqueous phase and thus ensures the stability of the aqueous polymer dispersion produced.
• both the protective colloids commonly used for carrying out free-radical aqueous emulsion polymerizations and emulsifiers are suitable.
• Suitable protective colloids are, for example, polyvinyl alcohols, cellulose derivatives or vinylpyrrolidone-containing copolymers. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, pages 411 to 420, Georg Thieme Verlag, Stuttgart, 1961.
• mixtures of emulsifiers and / or protective colloids can be used.
• the dispersants used are preferably exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1000. They may be anionic, cationic or nonionic in nature.
• anionic emulsifiers are compatible with each other and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually incompatible with one another.
• emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 to C 12 ), ethoxylated fatty alcohols (EO degree: 3 to 50; Alkyl: 8 to C 36) and alkali metal and ammonium salts (of alkyl sulfates alkyl radical C: ethoxylated C 12 to C 18) and C 8 to C 12), ethoxylated sulfuric acid monoesters of alkanols (EO units: 4 to 30, alkyl radical alkylphenols (EO units: 3 to 50, alkyl radical: C 4 to C I2), of alkylsulfonic acids (alkyl radical: C 12 to C 8) and of alkylarylsulfonic acids (alkyl radical: C 9 to C 18). Further suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Mac
• R 9 and R 10 are C 4 - to C 24 -alkyl and one of R 9 or R 10 may also be hydrogen, and A and B may be alkali metal ions and / or ammonium ions proved.
• R 9 and R 10 are preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or H atoms, where R 9 and R 10 are not both simultaneously H and Atoms are.
• a and B are preferably sodium, potassium or ammonium ions, with sodium ions being particularly preferred.
• Particularly advantageous are compounds II in which A and B are sodium ions, R 9 is a branched alkyl radical having 12 C atoms and R 10 is an H atom or R 9 .
• Industrial mixtures are used which have a share of 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ® 2A1 (trademark of Dow Chemical Company).
• the compounds II are well known, for example from US-A 4,269,749, and commercially available.
• Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl 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, as well as ammonium and triethanolamine salts.
• alkali and alkaline earth metal salts e.g. Sodium, potassium, magnesium, calcium, as well as ammonium and triethanolamine salts.
• alkyl ether sulfates, alkyl ether phosphates, alkyl glycol alkoxylates and diglycol alkoxylates 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 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 Alkylene oxide is about 6 to 60 moles per mole of alcohol.
• Suitable surfactants are, for example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium laurylsuccinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.
• the amount of dispersant used is 0.1 to 5 wt .-%, preferably 1 to 3 wt .-%, each based on the total amount of the monomers to be radically polymerized. It is often favorable if a partial or total amount of the dispersing assistant is supplied to the fluid reaction medium before the initiation of the free-radical polymerization. In addition, a partial or total amount of the dispersing assistant may advantageously also be added to the reaction medium together with the monomers to be polymerized, in particular in the form of an aqueous monomer emulsion during the polymerization. Preference is given to a combination of ionic and nonionic dispersion auxiliaries.
• the regulators used are preferably alkanethiols. Mixtures of several controllers can also be used.
• alkanethiols linear and branched alkanethiols with a carbon chain length of C io to C are used 22nd Particular preference is given to linear alkanethiols, furthermore preference is given to alkanethiols having a chain length of from C 12 to C 22 , in particular from C 12 to C 18 .
• alkanethiols which may be mentioned are n-decanethiol, n-dodecanethiol, tert-dodecanethiol, n-tetradecanethiol, n-pentadecanethiol, n-hexadecanethiol, n-heptanecanethiol, n-octadecanethiol, n-nonadecanethiol, n-eicosanthiol, n- Docosanthiol. Particularly preferred are linear, even alkane thiols. The alkanethiols can also be used in mixtures.
• the alkanethiols are usually used in amounts of 0.1 to 5 wt .-%, in particular 0.25 to 2 wt .-% based on the monomers to be polymerized. Usually the alkanethiols are added to the polymerization together with the monomers. Particularly preferred for use as a regulator is n-dodecanethiol.
• alkanethiols with a C chain length of C 14 to C 22 are used, the hydrogen peroxide treatment can be omitted. In a further embodiment of the invention, however, a hydrogen peroxide treatment can also be used in the use of alkanethiols having a chain length of C 4 to C 22 .
• the K value of the polymers according to the invention is in the range from 20 to 70, particularly preferably in the range from 20 to 55 and very particularly preferably in the range from 25 to 45.
• the respectively desired K value can be selected the polymerization conditions, for example, the Polymerisa ⁇ tion temperature and the initiator concentration set.
• regulators are used to set the K value, in particular when the emulsion and suspension polymerization are used.
• the K value can be adjusted by selecting the type and / or the amount of the regulator. In a preferred embodiment, lower K values are set by larger amounts of regulator based on the total amount of monomer.
• the emulsion polymerization is usually carried out with exclusion of oxygen, spielnem under nitrogen or argon atmosphere, at temperatures ranging from 20 to 200 0 C.
• polymerization temperatures are in the range of 50 to 130, especially 70 to 95 ° C.
• the polymerisation mixture does not boil, especially at relatively high temperatures in order to avoid coagulum formation.
• This can be avoided, for example, by carrying out the polymerization reaction at an inert gas pressure which is higher than the vapor pressure of the polymerization mixture, for example 1, 2 bar, 1, 5 bar, 2 bar, 3 bar, 5 bar, 10 bar or even higher (absolute values in each case).
• the polymerization can be carried out batchwise, semicontinuously or continuously. Often, the polymerization or the monomer and the regulator dosage semikontinu ⁇ ierlich after the feed process.
• the amounts of monomers and dispersants are conveniently chosen so as to contain a 30 to 80 wt .-% dispersion of the copolymers.
• at least some of the monomers, initiators and, if appropriate, regulators are metered uniformly into the reaction vessel during the polymerization (feed run).
• the monomers and the initiator can also be initially charged in the reactor and polymerized, it being necessary to cool.
• the polymerization is carried out using a seed latex.
• the seed latex is usually prepared from the polymers to be polymerized in the first polymerization. Subsequently, the remaining portion of the monomer mixture is added, preferably by the feed process.
• the polymerization reaction is advantageously carried out to a monomer conversion> 95 wt .-%, preferably> 98 wt .-% or> 99 wt .-%.
• aqueous polymer dispersions obtainable according to the invention can be converted in a simple manner into redispersible polymer powders.
• the resulting dispersion may either be incorporated directly into the aqueous, aqueous-alcoholic or alcoholic hair cosmetic preparation or the dispersion may be dried, e.g. Spray drying, fluidized spray drying, drum drying or Ge freeze drying, so that the polymer can be used as a powder and processed.
• the spray drying is used.
• the resulting polymer dry powders can advantageously be converted again into an aqueous solution or dispersion by dissolving or redispersing in water.
• Powdery copolymers have the advantage of a better shelf life, a ein ⁇ easier transport and usually show a lower propensity for microbial attack. These include, in general, anionic, cationic, amphoteric and neutral polymers.
• aqueous polymer dispersion obtained before or after the postpolymerization step to an inert gas and / or water vapor stripping which is likewise known to the person skilled in the art.
• This stripping process preferably takes place after the postpolymerization step.
• aqueous buffer solutions such as, for example, buffers based on alkali metal or ammonium carbonate or bicarbonate, are suitable.
• the neutralizing agents are preferably added as a dilute aqueous solution for polymer dispersion.
• the pH can also be adjusted by adding a buffer solution, with buffers based on alkali metal or ammonium carbonate or bicarbonate being preferred.
• the polymers present in the aqueous dispersion prior to or after the aftertreatment can be partly or completely neutralized.
• the polymers are for example at least 10, preferably at least 30, more preferably at least 40, more preferably at least 50, most preferably at least 70 and in particular at least 95% neutralized.
• the polymers are at least 99% neutralized. Most preferably, the neutralization is at least 100%. It is also advantageous if the neutralizing agent is added in more than equivalent amount, wherein the equivalent amount is understood to mean the amount needed to neutralize all neutralizable groups of the polymers.
• the neutralization can also be done with
• a mono-, di- or trialkanolamine having 2 to 5 carbon atoms in the alkanol radical which is optionally present in etherified form, for example mono-, di- and triethanolamine, mono-, di- and tri-n-propanolamine, mono-, di and triisopropanolamine, 2-amino-2-methylpropanol and di (2-methoxyethyl) amine, an alkanediolamine having 2 to 5 carbon atoms, for example 2-amino-2-methylpropane-1,3-diol and 2-amino-2 -ethylpropane-1,3-diol, or a primary, secondary or tertiary alkylamine having a total of 5 to 10 carbon atoms, for example N, N-diethylpropylamine or 3-diethylamino-1-propylamine.
• Suitable alkali metal hydroxides for neutralization are, in particular, sodium hydroxide or potassium hydroxide and also ammonium hydroxide.
• amino-containing silicone polymers are also suitable.
• Geeigne ⁇ te silicone polymers comprising amino groups for example, the silicone amino oxide block copolymers of WO 97/32917, the products Silsoft ® A-843 (di- methicone bisamino hydroxypropyl copolyol) and Silsoft ® A-858 (trimethylsilyl Amodi- methicone copolymer) (both company Witco).
• the neutralization polymers of EP-A 1035144 and in particular the silicone-containing neutralization polymers of claim 12 of EP-A 1035144 are also suitable.
• the invention relates to cosmetic and pharmaceutical preparations ent ⁇ holding the copolymers of the invention.
• copolymers described above contained in the preparations according to the invention are outstandingly suitable for the preparation of cosmetic and pharmaceutical preparations.
• shear means. They serve z.
• As a polymeric film former in preparations for personal care which includes the application in cosmetic preparations for keratinous Ober ⁇ surfaces such as skin, hair, nails and oral care preparations.
• copolymers according to the invention are suitable for the preparation of hair cosmetic compositions.
• copolymers according to the invention are also distinguished by good propellant gas compatibility, good solubility in water or aqueous / alcoholic solvent mixtures, the suitability for use in low-VOC formulations and good washability. In addition, they usually also have good conditioning properties, d. H. They improve treated hair in terms of its sensory properties such as grip, volume, handling, etc.
• Hairspray formulations based on the copolymers according to the invention are distinguished by good rheological properties such as flexural strength and elasticity and good sprayability. Furthermore, the films which can be prepared from the polymers according to the invention are not tacky.
• the cosmetic preparations according to the invention can be used as aqueous or aqueous-alcoholic solutions, O / W and W / O emulsions in the form of shampoos, creams, foams, sprays (pump spray or aerosol), gels, gel sprays, lotions or mousses be present and accordingly formulated with conventional further excipients.
• the polymers are preferably formulated in hair cosmetic preparations as sprays (pump spray or aerosol). Most preferably, they are provided as VOC-55 formulations.
• Cosmetically or pharmaceutically acceptable carrier B The preparations according to the invention additionally have at least one cosme ⁇ tically or pharmaceutically acceptable carrier B which is selected from
• Octyl salicylate Benzoates, such as C 10 -C 15 alkyl benzoates, benzyl benzoate; other cosmetic esters, such as fatty acid triglycerides, propylene glycol monolaurate, polyethylene glycol monolaurate, C 10 -C 15 -alkyl lactates, etc., and mixtures thereof.
• Suitable silicone oils B are z.
• linear polydimethylsiloxanes poly (methylphenylsiloxanes), cyclic siloxanes and mixtures thereof.
• the number-average molecular weight of the polydimethylsiloxanes and poly (methylphenylsiloxanes) is preferably in a range from about 1000 to 150 000 g / mol.
• Preferred cyclic siloxanes have 4- to 8-membered rings.
• Suitable cyclic siloxanes are, for. B. under the term cyclomethicone commercially available.
• Preferred oil or fat components B) are selected from paraffin and paraffin oils; Petroleum jelly; natural fats and oils such as castor oil, soybean oil, peanut oil, olive oil, sunflower oil, sesame oil, avocado oil, cocoa butter, almond oil, peach kernel oil, castor oil, cod liver oil, lard, spermaceti, sperm oil, sperm oil, wheat germ oil, macadamia nut oil, evening primrose oil, jojoba oil; Fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, cetyl alcohol; Fatty acids such as myristic acid, stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid and various saturated, unsaturated and substituted fatty acids; Waxes, such as beeswax, carnauba wax, candililla wax, spermaceti and mixtures of the aforementioned oil
• Suitable cosmetically and pharmaceutically acceptable oil or fat components B) are described in Karl-Heinz Schrader, Kunststoff und paragraphuren der Kosmetika, 2nd edition, Verlag Wegig, Heidelberg, pp. 319-355, to which reference is made here.
• Suitable hydrophilic carriers B) are selected from water, 1-, 2- orêti ⁇ conditions alcohols having preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, iso-propanol, propylene glycol, glycerol, sorbitol, etc.
• the cosmetic agents according to the invention may be skin-cosmetic, hair-cosmetic, pharmaceutical, hygienic or pharmaceutical agents. Because of their film-forming properties, the copolymers described above are particularly suitable as additives for hair and skin cosmetics.
• agents according to the invention are preferably in the form of a spray, gel, foam, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.
• the compositions have a proportion of volatile organic components of at most 80% by weight, preferably at most 55% by weight and in particular at most 30% by weight.
• a preferred article are thus means that comply with the Iow VOC standard, ie VOC 80 and VOC 55 standard.
• the cosmetically or pharmaceutically active agents according to the invention may additionally contain cosmetically and / or pharmaceutically active agents as well as excipients.
• auxiliaries may be present in the preparation of the polymers according to the invention and / or added after the polymerization.
• Another object of the invention accordingly relates to the use of the inventive acrylate polymers in cosmetic, especially hair cosmetic preparations.
• 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
• polystyrene resin e.g. Polyglycerol polyricinoleate, polyglycerol poly-12-hydroxy stearate or polyglycerol dimerate. Also suitable are mixtures of compounds of several of these substance classes;
• 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 12 to C 18 -fatty acid mono- and diesters of addition products of ethylene oxide with glycerine are known from DE-PS 2024051 as refatting agents for cosmetic preparations.
• C 8 to C 8 alkyl mono- and oligoglycosides their preparation and their dung Verwen ⁇ are known from the prior art. They are prepared in particular by reacting glucose or oligosaccharides with primary alcohols having 8 to 18 carbon atoms. With respect to the glycoside ester, both monoglycosides in which a cyclic sugar residue is glycosidically bound 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 value based on a homolog distribution which is customary 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 cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example the cocoacylaminopropyldimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3- Hydroxyethylimidazoline having in each case 8 to 18 carbon atoms in the alkyl or acyl group and the Kokosacyl- aminoethylhydroxyethylcarboxy methylglycinat.
• betaines such as the N-alkyl-N, N-dimethylammonium glycinates, for example the cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium
• fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine.
• ampholytic surfactants are understood as meaning those surface-active compounds which contain, in addition to a C 8 to C 18 -alkyl or -acyl group, at least one free amino group and at least one -COOH and / or -SO 3 H group in the molecule, and capable of forming internal salts.
• 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, cocoacylaminoethylaminopropionate and C 12 to C 18 acylsarcosine.
• quaternary emulsifiers are also suitable, with those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, being particularly preferred.
• oil bodies are Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C 6 -C 22 fatty acids with linear C 6 -C 22 fatty alcohols, esters of branched C 6 -C 13 Carboxylic acids with linear C 6 -C 22 -fatty alcohols, esters of linear C 6 -C 22 -fatty acids with branched alcohols, in particular 2-ethylhexanol, esters of hydroxycarboxylic acids with linear or branched C 6 -C 22 -fatty alcohols, in particular 2-hydroxy-succinic acid dioctyl esters, esters of linear and / or branched fatty acids with polyhydric alcohols (such as, for example, propylene glycol, dimerdiol or trimer triol) and / or guarentextholes, triglycerides based on C 6 -C 10 -fatty acids, liquid mono- / Di-
• Preservatives Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the further classes of substances listed in Appendix 6, Parts A and B of the Cosmetics Regulation.
• the cosmetic preparations may contain perfume oils.
• perfume oils are mixtures of natural and synthetic fragrances. 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 (macis, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme ), Needles and twigs (spruce, fir, pine, pines), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
• Typical synthetic fragrance compounds are ester type products, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, 4-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, methylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallopropionate and benzylsalicylate.
• the ethers include, for example, benzyl ether ethers, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonate, to the ketones such as the ionones, cc-lsomethylionen and methyl cedryl ketone , among the alcohols anethof, citronellol, eugenol, isoeugenol, geraniol, linoleol, phenylethyl alcohol and terioneol, the hydrocarbons mainly include the terpenes and balsams.
• fragrance oils of lower volatility which are most commonly used as aroma components, are suitable as perfume oils, for example sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil.
• Superfatting agents may be substances such as lanolin and lecithin, as well as polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides, the latter ones also serving as foam stabilizers.
• 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 hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, 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 in total have at least 24 carbon atoms, especially laurone and distearyl 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 containing 12 to 22 carbon atoms and / or polyols having 2 to 15 carbon
• Suitable consistency factors are primarily fatty alcohols or hydroxy fatty alcohols having 12 to 22 and preferably 16 to 18 carbon atoms and, in addition, partial glycerides, fatty acids or hydroxyfatty acids. Preference is given to a combination of these substances with alkyl oligoglucosides and / or fatty acid N-methylglucamides of the same chain length and / or polyglycerol poly-12-hydroxystearates.
• Suitable thickening agents are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates (eg Carbopol TM from Goodrich or Synthalen Sigma), polyacrylamides, polyvinyl alcohol and polyvinylpyrrolidone, surfactants such as ethoxylated Fett Text- reglyceride, esters of fatty acids with polyols such as pentaerythritol or trimethylolpropane, fatty alcohol ethoxylates with narrow homolog distribution or Alkyloligoglucoside and electrolytes such as sodium chloride and ammonium chloride.
• polysaccharides in particular xanthan gum, guar guar, agar agar, alginates and tyloses
• Typical thickeners in such formulations are crosslinked polyacrylic acids and their derivatives, polysaccharides such as xanthan gum, agar-agar, alginates or tylo acids, cellulose derivatives, eg. Carboxymethyl cellulose or hydroxycarboxymethyl cellulose, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinylpyrrole. idon.
• Suitable thickeners are also Aculyn ® brands ticareethoxilaten of Messrs.
• Rohm and Haas as Aculyn ® 22 (copolymer of acrylates and methacrylic acid with stearyl rest (20 EO units)) and Aculyn ® 28 (copolymer of acrylates and methacrylic with Behenyl residue (25 EO units)).
• Hydrotropes such as, for example, ethanol, isopropyl alcohol, or polyols can also be used to improve the flow behavior.
• Polyols contemplated herein preferably have from 2 to 15 carbon atoms and at least two hydroxyl groups.
• Alkylene glycols such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols having an average molecular weight of from 100 to 1000 daltons; technical oligoglycerine mixtures having an intrinsic degree of condensation of from 1.5 to 10, such as technical grade diglycerine blends having a diglycerol content of from 40 to 50% by weight; Methylol compounds, in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
• Niedrigalkylglucoside in particular those having 1 to 8 carbons in the alkyl radical, such as methyl and Butylglucosid;
• Sugar alcohols with 5 to 12 carbon atoms such as sorbitol or
• mannitol Sugars having 5 to 12 carbon atoms, such as, for example, glucose or sucrose; Amino sugars, such as glucamine.
• UV-light protection The sunscreen filters used in cosmetic preparations have the task of preventing damaging effects of sunlight on human skin and human hair or at least reducing their effects. In addition, these light protection filters also serve to protect other ingredients against destruction or degradation by UV radiation. In hair cosmetic formulations damage to the keratin fibers is to be reduced by UV rays.
• Sunlight reaching the earth's surface has UV-B (280 to 320 nm) and UV-A (320 to 400 nm) radiation directly adjacent to the visible light.
• UV-B 280 to 320 nm
• UV-A 320 to 400 nm
• the influence on human skin is particularly noticeable in UVB radiation from sunburn.
• UV-A range it is important to have available filter substances, since its rays can cause reactions in photosensitive skin. It has been proven that UVA Radiation leads to damage to the elastic and collagen fibers of the Bindege ⁇ webes, which causes the skin to age prematurely, and that it can be seen as the cause of numerous phototoxic and photoallergic reactions. The harmful influence of UV-B radiation can be enhanced by UV-A radiation.
• Oil-soluble organic UV-A filters and / or UV-B filters and / or water-soluble organic UV-A filters and / or UV-B filters can be used as UV light protection filters.
• the total amount of UV photoprotective filters is generally from 0.1 wt .-% to 30 wt .-%, preferably 0.5 to 15 wt .-%, in particular 1 to 10 wt .-%, based on the total weight of preparations.
• the UV photoprotective filters are chosen so that the preparations protect the skin from the entire range of ultraviolet radiation.
• UV protection filters are:
• UV-blocking pigments such as titanium dioxide, talc and zinc oxide.
• Light stabilizers suitable for use in the preparations according to the invention are furthermore the compounds mentioned in EP-A 1 084696 in paragraphs [0036] to [0053], to which reference is made in its entirety.
• UV light protection filters which can be used in the preparations according to the invention should of course not be limiting.
• germ-inhibiting agents can also be used in the preparations according to the invention. 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).
• Triclosan 2,4,4'-trichloro-2'-hydroxydiphenyl ether
• chlorhexidine 1,1'-hexamethylenebis [5- (4-chlorophenyl) biguanide
• TTC 3,4,4'-trichlorocarbanilide
• Quaternary ammonium compounds are also suitable in principle, but are preferably used for disinfecting soaps and washing lotions.
• fragrances have antimicrobial properties. Special combinations with particular efficacy against Gram-positive bacteria are used for the composition of so-called Deopfarums.
• a large number of essential oils or their characteristic ingredients such as clove oil (eugenol), mint oil (menthol) or thyme oil (thymol), show a pronounced antimicrobial activity.
• the antibacterial substances are usually used in concentrations of about 0.1 to 0.3 wt .-%.
• the copolymers described above are particularly suitable as additives for hair and skin cosmetics.
• agents according to the invention are preferably in the form of a spray, gel, foam, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.
• the cosmetically or pharmaceutically active agents according to the invention may additionally contain cosmetically and / or pharmaceutically active agents as well as excipients.
• Suitable cosmetically and / or pharmaceutically active agents are, for. Coloring agents, skin and hair pigmenting agents, tinting agents, tanning agents, bleaching agents, keratin-hardening substances, repellent active ingredients, hyperemic substances, keratolytic and keratoplastic substances, antidandruff active ingredients, antiphlogistics, keratinizing substances, antioxidant or active substances which are active as free radical scavengers, skin-moisturizing or moisturizing substances, moisturizing active substances, anti-erythematous or anti-allergic active substances and mixtures thereof.
• Suitable keratin-hardening substances are as a rule active ingredients, as are also used in antiperspirants, such as, for example, Potassium aluminum sulfate, aluminum hydroxychloride, aluminum lactate, etc.
• Antimicrobial agents are used to destroy microorganisms or to inhibit their growth and thus serve both as a preservative and as a deodorizing substance, which reduces the formation or intensity of body odor.
• deodorizing substances are, for. Zinc ricinoleate, triclosan, undecylenic acid alkylolamides, citric acid triethyl ester, chlorhexidine etc.
• Suitable repellent active ingredients are compounds which are able to prevent or expel certain animals, in particular insects, from humans. This includes z. B. 2-ethyl-1,3-hexanediol, N, N-diethyl-m-toluamide, etc.
• Suitable hyperemic substances which stimulate the perfusion of the skin are, for.
• essential oils such as mountain pine, lavender, rosemary, juniper berry, horse chestnut extract, birch leaf extract, hay flower extract, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil, etc.
• Suitable keratolytic and keratoplastic substances are for. Salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc.
• Suitable anti-uppen active ingredients are, for. Sulfur, Schwefelpolyethylenglykolsor- bitanmonooleat, Schwefelricinolpolyethoxylat, Zinkpyrithion, Aluminiumpyrithion, etc.
• Suitable antiphlogistics which counteract skin irritation, z. Allantoin, bisabolol, dragosantol, chamomile extract, panthenol, etc.
• the cosmetic agents according to the invention may contain as cosmetic and / or pharmaceutical active ingredient (as well as optionally as excipient) at least one cosmetically or pharmaceutically acceptable polymer.
• hair cosmetic preparations are hair treatments, hair lotions, hair rinses, hair emulsions, top fluids, perming agent for permanent waving, hot oil treatment preparations, conditioners, curl relaxers, styling wrap alloys, setting lotions, shampoos, hair waxes, pomades, hair foams, Hair dyes or hair sprays.
• hair cosmetic preparations for strengthening hairstyles which are in the form of spray preparations and / or hair foams.
• the polymers contained in the hair cosmetic preparations according to the invention are distinguished by their high compatibility with the nonpolar propellants in spray preparations, in particular with hydrocarbons such as n-propane, isopropane, n-butane, isobutane, n-pentane and mixtures thereof and especially due to the excellent sprayability as a pump spray or aerosol.
• the polymers are furthermore very well tolerated with other additives customary in hair cosmetics, have a good hair-firming action, form films with very good mechanical properties, are easy to wash out and are characterized by the fact that they practically do not stick to the hair.
• the polymers display excellent results in the performance properties in hair cosmetic preparations. They are clearly soluble in alcohols such as ethanol or isopropanol and in mixtures of these alcohols with water. The clarity of the solutions is retained even when the solutions in standard spray formulations are used together with blowing agents such as dimethyl ether. In particular, they are clearly formu lable in aqueous low-VOC preparations with at most 55% by weight of volatile organic constituents (VOC-55).
• the hair cosmetic preparations according to the invention are perfectly washable out of the hair. Treated hair has increased suppleness and a pleasant natural feel.
• the strengthening effect is at the same time high, so that in principle a reduction of the required amount of film former in the hair spray formulation is possible. Due to the odorlessness of the polymers can be dispensed with if necessary to add odor masking perfume oils.
• the hair cosmetic preparations usually comprise from 0.1 to 20% by weight, preferably from 0.5 to 10% by weight, in particular from 2 to 10% by weight, of the partially or completely neutralized polymers, based on the preparation.
• wt .-% preferably 0.5 to 15 wt .-%, in particular 1 to 10 wt .-% of the partially or completely neutralized polymer 0 to 99.9 wt .-%, preferably 1 to 50 wt %, in particular 10 to 20 wt .-% water - 0 to 95 wt .-%, preferably 20 to 60 wt .-%, in particular 25 to
• a conventional organic solvent such as especially ethanol, isopropanol and dimethoxymethane and also acetone, n-propanol, n-butanol, 2-methoxypropan-1-ol, n-pentane, n-hexane, cyclohexane, n- Heptane, n-octane or dichloromethane or mixtures thereof - 0 to 90 wt .-%, preferably 30 to 80 wt .-%, in particular 45 to
• a conventional organic solvent such as especially ethanol, isopropanol and dimethoxymethane and also acetone, n-propanol, n-butanol, 2-methoxypropan-1-ol, n-pentane, n-hexane, cyclohexane, n- Heptane, n-octane or dichloromethane or mixtures thereof - 0 to
• a customary propellant such as n-propane, isopropane, n-butane, isobutane, 2,2-dimethylbutane, n-pentane, isopentane, dimethyl ether, difluoroethane, fluorotrichloromethane, dichlorodifluoromethane or dichlorotetrafluoroethane, HFC 152A or their mixtures.
• Alkanolamines are used to neutralize various types of acids and to adjust the pH of cosmetic products.
• Examples are aminomethyl propanol, diethanolamines, diisopropanolamines, ethanolamines, methylethanolamines, N-lauryl diethanolamines, triethanolamines, triisopropanolamines, etc.
• alkali metal hydroxides eg NaOH, KOH
• other bases can be used for neutralization (eg histidine, Arginine, lysine or Ethylenediami- ne, diethylenetriamine, melamine, benzoguanamine). All stated bases can be used alone or as a mixture with other bases for the neutralization of acid-containing cosmetic products.
• Propellants Propellant Gases
• the propellants (propellants) used are in particular the hydrocarbons, in particular propane, n-butane, n-pentane and mixtures thereof, as well as dimethyl ether and difluoroethane, of the compounds mentioned.
• 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 particularly 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.
• copolymers according to the invention are particularly suitable as setting agents in hairstyling preparations, in particular hairsprays (aerosol sprays and pump sprays without propellant gas) and hair foams (aerosol foams and pump foams without propellant gas).
• spray formulations contain
• 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.
• emulsifiers all emulsifiers commonly used in hair foams can be used. Suitable emulsifiers may be nonionic, cationic or anionic or amphoteric.
• Propellants particularly suitable for aerosol foams are mixtures of dimethyl ether and, optionally halogenated, hydrocarbons, such as propane, butane, pentane or HFC-152a.
• nonionic emulsifiers are Laurethe, z. B. Laureth-4; Cetethe, z. Cetheth-1, polyethylene glycol cetyl ether; Cetearethe, z. Cethethreeth-25, polyglycol fatty acid glycerides, hydroxylated lecithin, lactyl esters of fatty acids, alkylpolyglycosides.
• a standard aqueous spray formulation has, for example, the following composition:
• alcohol all alcohols customary in cosmetics are to be understood, for.
• ethanol isopropanol, n-propanol.
• Other polymers
• the setting polymers For the targeted adjustment of the properties of the hair cosmetic preparations, it may be advantageous to use the setting polymers as a mixture with other polymers.
• Suitable conventional polymers include, for example, anionic, cationic, amphoteric and neutral polymers.
• Copolymers of acrylic acid, methyl methacrylate, octylacrylamide, butylaminoethylmethyl acrylate and hydroxypropyl methacrylate
• preparations containing the polymers in combination with these other polymers have unexpected properties.
• the preparations according to the invention are superior to the preparations of the prior art, in particular with regard to their hair cosmetic properties. Furthermore, they have very good film-forming and firming properties.
• Copolymers of ethyl acrylate and methacrylic acid are available, for example, as commercial products Luviflex Soft ® (BASF).
• Polyvinylpyrrolidones for example, are among the bottles ⁇ Luviskol ® K, Luviskol ® K 30 TM (BASF) and PVP K (ISP) name available.
• Polyvinylcaprolactams (INCI: Polyvinylcaprolactams) are for example available under the trade name Luviskol ® Plus TM (BASF).
• Polyurethanes (INCI: Polyurethane-1) are for example available under the trade name Luviset ® PUR.
• Copolymers of acrylic acid, methyl methacrylate, octyl acrylamide, methyl acrylate butylaminoethyl methacrylate, hydroxypropyl methacrylate are known for example under the trade name Amphomer ® 28-4910 and Amphomer ® LV-71 (National Starch).
• Copolymers of vinyl acetate and crotonic acid are available for example under the trade name Luviset CA 66 ® (BASF), Resyn ® 28-1310 (Na ⁇ tional Starch) and Aristoflex ® A (Celanese).
• Copolymers of vinyl acetate, crotonic acid and (vinyl) neodecanoate are available for example under the trade names Resyn ® 28-2930 (National Starch) and Luviset ® CAN (BASF).
• Copolymers of vinyl acetate and N-vinylpyrrolidone are available for example under the trade name Luviskol VA ® (BASF), and PVP / VA (ISP).
• Carboxy-functional copolymers of vinylpyrrolidone, t-butyl acrylate, methacrylic acid are available for example, under the trade name Luviskol ® VBM (BASF).
• Copolymers of tert-butyl acrylate, methacrylic acid and dimethicone copolyol are bei ⁇ piellust under the trade name Luviflex Silk ® (BASF).
• Suitable further polymers are, for example, anionic polymers.
• anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or salts thereof, copolymers of acrylic acid and acrylamide and salts thereof, sodium salts of polyhydroxycarboxylic acids, copolymers of acrylic acid and methacrylic acid with, for example, the novel (meth) acrylate polymers hydrophobic monomers, such as C 4 -C 30 -alkyl esters of (meth) acrylic acid, C 4 - C 30 -Alkylvinylester, C 4 -C 30 -alkyl and hyaluronic acid and further under the trade names Amerhold DR-25, Ultrahold ®, Luviset ® PUR, Acronal ®, ® Acudyne, Lovocryl ®, ® Versatyl, Amphomer ® (28-4910, LV-71), Placise ® L53, Gantrez ® ES
• additional polymers are water-soluble or water-dispersible polyesters, polyureas, co-polyurethane ureas, maleic anhydride copolymers optionally reacted with alcohols or anionic polysiloxanes.
• suitable polymers which are furthermore suitable include, for example, cationic polymers with the INCI name Polyquaternium, for example
• Copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts for example, available under the trade name Luviquat ® Hold
• - copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate available, for example under the trade name Luviquat ® PQ 11
• cationic cellulose derivatives Polyquaternium-4 and -10
• acrylamide copolymers Polyquaternium-7
• - Styleeze ® CC-10 Aquaflex ® SF-40
• Guar hydroxypropyltrimethylammonium chloride (INCI: hydroxypropyl guar hydroxypropyltrimonium chlorides), polyethyleneimines and their salts, polyvinylamines and their salts.
• hair cosmetic polymers which are also suitable are neutral polymers, such as polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinylpropionate, polysiloxanes, polyvinylcaprolactam and copolymers with N-vinylpyrrolidone, cellulosic derivatives, polyaspartic acid salts and derivatives.
• neutral polymers such as polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinylpropionate, polysiloxanes, polyvinylcaprolactam and copolymers with N-vinylpyrrolidone, cellulosic derivatives, polyaspartic acid salts and derivatives.
• neutral polymers such as polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinylpropionate, polysilox
• biopolymers i. Polymers obtained from naturally renewable raw materials and constructed from natural monomer building blocks, e.g. Cellulose derivatives, chitin, chitosan, DNA, hyaluronic acid and RNA derivatives.
• Suitable polymers include betaine polymers such as Yukaformer (R205, SM) and diaformer.
• the hair cosmetic preparations if necessary, all previously mentioned cosmetic ingredients may be added.
• the cosmetic preparation is a product for styling.
• a preparation suitable for styling gels according to the invention can be composed, for example, as follows:
• gelling agents may be advantageous to adjust for specific theological or other performance properties of the gels.
• Gelbuch ⁇ ner all customary in cosmetics gelling agents can be used. These include slightly crosslinked polyacrylic acid, for example carbomer (INCI), cellulose derivatives, eg. Hydroxypropyl cellulose, hydroxyethyl cellulose, cationic modified celluloses, polysaccharides, e.g.
• Xanthan gum caprylic / capric triglyceride, sodium acrylate copolymers
• a further preferred embodiment of the invention are products for the hair, which are selected from hair shampoo and hair products, which are rinsed or not rinsed off and applied before or after shampooing, dyeing, decolorization, perming or wrinkling.
• the cosmetic preparation is packaged in an atomizer, pump bottle or aerosol container in order to obtain a spray, a lacquer or a foam.
• Another object of the invention is a method for the treatment of hair, characterized in that the hair is brought into contact with the cosmetic preparation according to the invention and optionally rinsed with water.
• copolymers according to the invention can preferably be used in shampoo formulations as setting and / or conditioning agents.
• Another object of the invention is the use of the copolymer of the invention in cosmetic preparations.
• Another object of the invention is the use of the copolymer of the invention as auxiliaries in pharmacy, preferably as or in coating agent (s) for solid dosage forms, for the modification of theological properties, as surface-active compound, as or in adhesives (n ) as well as in or in coating agent (s) for the textile, paper, printing and leather industries.
• the polymers can be prepared by conventional methods known to those skilled in the art. Preference is given to the solution polymerization in alcohol and / or water, and particularly preferably the emulsion polymerization.
• Example 1 Ethyl Methacrylate / Methacrylic Acid 75/25 w / w
• reaction mixture was stirred for a further hour at 80 0 C and then cooled to 60 °.
• feed III (see below) was added. It was then cooled to 35 ° C and while maintaining the Matterstempe ⁇ temperature feed IV (see below) was added.
• Feed Il is an aqueous monomer emulsion prepared from:
• Tween TM 80 can be used as the nonionic emulsifier.
• the total amount of the 15% strength by weight aqueous solution of sodium lauryl sulfate and then the total amount of the nonionic emulsifier are added to the initially introduced deionized water with stirring.
• the corresponding amounts of ethyl methacrylate, methacrylic acid and n-dodecylmercaptan are added in the order given to the homogeneous solution which is stirred further.
• Feed III 2 g 30% strength by weight solution of hydrogen peroxide in deionized water
• Example 2 The polymers of the following Examples 2 to 20 were synthesized analogously to Example 1, wherein Feed II for each example was chosen as indicated below.
• Emulsifier / asser / batch size / emulsion preparation / controller analogous to example 1.
• Example 2 Ethyl methacrylate / t-butyl acrylate / methacrylic acid 50/25/25 w / w / w
• Example 3 n-butyl methacrylate / methacrylic acid 75/25 w / w (comparative example)
• Example 4 t-butyl methacrylate / methacrylic acid 75/25 w / w (comparative example)
• Example 6 The polymers of the following Examples 6 to 20 were synthesized analogously to Example 1, wherein feed Il was chosen as appropriate for each example as indicated below.
• Emulsifiers / water / batch size / emulsion preparation / controller analogous to example 1.
• Example 21 Ethyl methacrylate / acrylic acid / methacrylic acid 75/5/2 w / w / w
• reaction mixture was stirred for a further hour at 80 0 C and then cooled to 60 °.
• feed III While maintaining the temperature of 60 °, feed III (see below) was added. The mixture was then cooled to 35 0 C and temperature while maintaining the Matterstempe ⁇ feed IV (see below) was added.
• Feed Il is an aqueous monomer emulsion prepared from:
• TweenTM 80 can be used as a non-ionic emulsifier, for example, TweenTM 80 can be used.
• the total amount of the 15% strength by weight aqueous solution of sodium lauryl sulfate and then the total amount of the nonionic emulsifier are added to the initially introduced deionized water with stirring.
• the corresponding amounts of ethyl methacrylate, methacrylic acid and n-dodecylmercaptan are added in the order given to the homogeneous solution which is stirred further.
• Example 22 The polymers of Examples 22 to 25 were synthesized analogously to Example 21, wherein feed Il for each example was chosen as indicated below.
• the K values are measured according to Fikentscher, Cellulose Chemistry, Vol. 13, pp. 58 to 64 (1932) at 25 ° C. in aqueous / ethanolic or ethanolic solution and represent a measure of the molecular weight.
• the aqueous / ethanolic or ethanolic solution The polymer contains 1 g of polymer in 100 ml of solution.
• appropriate amounts of the dispersion are made up to 100 ml with ethanol, so that the concentration of 1 g of polymer in 100 ml of solution arises ,
• the K value is measured in a Micro Ubbelohde capillary type M Ic from Schott.
• the droplet size distribution was determined using Particle Size Measurement System for Detecting Liquid Aerosols " Malvern® Master Sizer X” (Malvern Instruments Inc., Southborough MA, USA).
• the measuring system is based on the method of laser light diffraction on the particle, which is used not only for spray analysis (aerosols, pump sprays) but also for sizing
• Solids, suspensions and emulsions in the size range of 0.1 microns to 2000 microns is suitable.
• the aerosol cans were fixed to a fixed holding device before each measurement, thus ensuring that all the aerosols to be tested were measured at exactly the same distance.
• the aerosol was sprayed into the test room.
• the entire particle volume was recorded and evaluated over a test period of 2 s.
• the evaluation contains a tabular representation over 32 class widths from 0.5 .mu.m to 2000 .mu.m and in addition a graphic representation of the Generalchenieren ⁇ distribution.
• this value is between 30 ⁇ m and 80 ⁇ m, depending on the polymer content, valve, spray head geometry, solvent ratio and propellant charge.
• Consolidation (flexural strength): The consolidation of polymeric film formers was measured physically as well as objectively by physical judgment as flexural stiffness of thin strands of hair which were treated with the polymer solution and dried again. In this case, a force transducer determines the force required for bending, while the entire measurement runs under standardized conditions in a climatic room at 65% relative humidity.
• the tests were mit ⁇ in a climatic chamber at 20 0 C and 65% relative humidity means of a train / pressure tester performed.
• the lock of hair was placed symmetrically on two cylindrical rollers of the sample holder. Exactly in the middle of the strand was now bent from above with a rounded punch 40 mm (Bre ⁇ chen of the polymer film).
• the required force was measured with a load cell (50 N) and reported in Newton.
• the values determined were set to those of a commercially available comparative polymer (Amphomer ® LV 71 as standard 100% as given an ⁇ ) in relation.
• the hair tress was in an approximately 37 ° C warm Texapon ® NSO - solution (6ml of Texapon ® NSO (28%) in 11 hot water) for about 15 seconds by ⁇ maliges immersing and squeezing washed. The hair strand was then rinsed and treated again in the same way. Thereafter, the lock of hair was well squeezed out on filter paper and allowed to dry overnight. The dry strand of hair was screwed in and examined for residues.

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• 2004
  • 2004-10-22 DE DE102004051647A patent/DE102004051647A1/de not_active Withdrawn
• 2005
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