EP1844081A1 - Copolymeres pour agents cosmetiques, obtenus en presence de regulateurs polyfonctionnels - Google Patents

Copolymeres pour agents cosmetiques, obtenus en presence de regulateurs polyfonctionnels

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Publication number
EP1844081A1
EP1844081A1 EP06702184A EP06702184A EP1844081A1 EP 1844081 A1 EP1844081 A1 EP 1844081A1 EP 06702184 A EP06702184 A EP 06702184A EP 06702184 A EP06702184 A EP 06702184A EP 1844081 A1 EP1844081 A1 EP 1844081A1
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EP
European Patent Office
Prior art keywords
agents
acid
polymers
ethylenically unsaturated
acids
Prior art date
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Application number
EP06702184A
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German (de)
English (en)
Inventor
Gabi Winter
Lysander Chrisstoffels
Claudia Wood
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BASF SE
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BASF SE
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Publication date
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Publication of EP1844081A1 publication Critical patent/EP1844081A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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

  • Copolymers for cosmetics prepared in the presence of polyfunctional regulators
  • the present invention relates to cosmetic and pharmaceutical compositions containing a copolymer with anionogenic and / or anionic groups, which is obtainable by radical polymerization of a monomer mixture in the presence of a polyfunctional regulator having at least three functional regulatory groups.
  • the invention further relates to a process for the preparation of such a copolymer as well as the copolymers obtainable by this process.
  • Cosmetically and pharmaceutically acceptable water-soluble or water-dispersible polymers are widely used in cosmetics and medicine. For example, they are generally used as film formers and thickeners for various types of formulations, such as sprays, gels, creams, etc. Branched or crosslinked water-soluble polymers with anionic functionalities such. As crosslinked polyacrylic acid used.
  • the conditioners used are frequently crosslinked polymers having cationic functionalities which have a high affinity for the structurally negatively charged surface of the hair.
  • these include, for example, crosslinked copolymers of N-vinylpyrrolidone, quaternized N-vinylimidazole, acrylamide and diallyldimethylammonium chloride (DADMAC).
  • Difficulties are often the provision of products with a complex property profile.
  • polymers for cosmetic and pharmaceutical agents which on the one hand have good film-forming properties and, on the other hand, can be well formulated and applied.
  • the rheological properties play an important role. Role.
  • polymers for use in hair sprays which are suitable for producing formulations having the lowest possible viscosity and which have good film-forming properties are still lacking.
  • Such polymers would then also be suitable for use in other fields of application, for example in the pharmaceutical or agrochemical sector.
  • WO 94/24986 describes hair setting agents which contain copolymers based on tert-butyl acrylate or tert-butyl methacrylate as film formers.
  • Regulators for example sulfur compounds such as mercaptoethanol, can be used in the preparation of these copolymers.
  • WO 2004/058837 describes an ampholytic copolymer obtained by free-radical copolymerization of
  • WO 2004/022616 describes hair cosmetic preparations based on cationogenic / cationic polymers which are obtainable by
  • WO 2004/058831 describes an aqueous dispersion obtainable by free-radical polymerization of a) at least one N-vinyl-containing monomer, b) at least one polymeric dispersant, c) at least one polymeric precipitation agent, d) at least one crosslinker, e) optionally further monomers, f) optionally at least one regulator, g) optionally a buffer substance,
  • weight ratio of b) to c) is in the range of 1:50 to 1: 0.02. Offenbart is further the use of this dispersion in cosmetic preparations.
  • compositions containing such a polymer dispersion or a polymer obtainable by drying such a dispersion are also described.
  • this polymer dispersion is In general, the use of mono-, di- and polyfunctional regulators described.
  • WO 02/38638 describes acrylate polymers based on tert-butyl acrylate and / or tert-butyl methacrylate, which are obtained by free radical polymerization in the presence of C 14 -C 22 alkanethiols. They are characterized by their neutral odor and are suitable for cosmetic formulations that contain no additional fragrances. The use of polyfunctional regulators for the preparation of these acrylate polymers is not described.
  • the present invention is based on the object to provide such polymers. These should be especially suitable for the production of compositions for strengthening, structural improvement and / or shaping of the hair. Preferably, they should have several of the following properties: efficient hair setting, good sprayability, good washability, and the ability to formulate low gas formulations.
  • the invention therefore relates to a cosmetic or pharmaceutical agent containing
  • the invention furthermore relates to a process for the preparation of copolymers A) having anionogenic and / or anionic groups by free-radical polymerization of a monomer mixture M) comprising monomers a), b) and optionally further monomers, in the presence of at least one polyfunctional regulator c) ,
  • a further subject of the invention are the copolymers A) obtainable by this process.
  • the novel copolymers A) have very good film-forming properties and are at the same time suitable for the preparation of formulations having a low viscosity. In this case, they have better performance properties than corresponding, known from the prior art polymers with low molecular weight. Thus, they show significantly improved rheological properties over copolymers of the same composition, which were prepared in the presence of mono- or difunctional regulator with comparable strengthening effect. This manifests itself for example in an improved sprayability.
  • alkyl includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched C 1 -C 6 -alkyl, preferably C 1 -C 6 -alkyl and particularly preferably C 1 -C 4 -alkyl groups.
  • Suitable longer-C 8 -C3o alkyl or C 8 -C 3 -alkenyl groups are straight-chain and branched alkyl or alkenyl groups. These are preferably predominantly linear alkyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols, which may optionally be additionally mono-, di- or polyunsaturated. These include z.
  • Cycloalkyl is preferably C 5 -C 8 -cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Aryl includes unsubstituted and substituted aryl groups and is preferably phenyl, ToIyI, XyIyI, mesityl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl, ToIyI, XyIyI or mesityl.
  • water-soluble monomers and polymers are understood as meaning monomers and polymers which dissolve to at least 1 g / l at 20 ° C. in water.
  • Water-dispersible monomers and polymers are understood as meaning monomers and polymers which decompose into dispersible particles by means of shearing forces, for example by stirring.
  • the copolymers used according to the invention are generally water-soluble or at least water-dispersible.
  • the monomer mixture M) contains as compound a) at least one compound having a free-radically polymerizable ⁇ , ⁇ -ethylenically unsaturated double bond and having at least one anionogenic and / or anionic group per molecule.
  • the component a) is preferably used in an amount of 0.1 to 99.89 wt .-%, more preferably 0.5 to 70 wt .-%, in particular 10 to 40 wt .-%, especially 15 to 30 wt %, based on the total weight of the components used for the polymerization (ie components a), b), c) and, if present, d) to g)).
  • the compounds of component a) are generally water-soluble monomers.
  • the compounds a) are selected from monoethylenically unsaturated carboxylic acids, sulfonic acids, phosphonic acids and mixtures thereof.
  • 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. B.
  • the monomers a) also include monoethylenically unsaturated sulfonic acids and phosphonic acids, for example vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid, Acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid and allylphosphonic acid.
  • monoethylenically unsaturated sulfonic acids and phosphonic acids for example vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sul
  • the monomers a) also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts and the salts with amines.
  • the monomers a) can be used as such or as mixtures with one another.
  • the stated parts by weight are all based on the acid form.
  • component a) is selected from acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and mixtures thereof.
  • the component a) is particularly preferably selected from acrylic acid, methacrylic acid, itaconic acid and mixtures thereof.
  • Component b) is preferably used in an amount of from 0.1 to 99.89% by weight, more preferably 1 to 99% by weight, in particular 60 to 90% by weight, based on the total weight of the components used for the polymerization ( ie components a), b), c) and, if present, d) to g)).
  • a particularly suitable amount range for component b) is 70 to 85 wt .-%.
  • the compounds of component b) are generally water-insoluble monomers.
  • Suitable monomers b) are methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl ethacrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, n-Octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth)
  • Suitable monomers b) are furthermore N-methyl (meth) acrylamide,
  • N-oleyl (meth) acrylamide N-linolyl (meth) acrylamide, N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-lauryl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, morpholinyl (meth) acrylamide and mixtures thereof.
  • the free-radical polymerization of the monomer mixture M) takes place according to the invention in the presence of at least one polyfunctional regulator c).
  • the regulators c) are preferably used in an amount of 0.01 to 10 wt .-%, particularly preferably from 0.05 to 5 wt .-% and in particular from 0.1 to 2.5 wt .-%, based on the Total weight of the components used for the polymerization (ie components a), b), c) and, if present, d) to g)) used.
  • Regulators are generally compounds with high transmission constants. Regulators accelerate chain transfer reactions and thus cause a reduction in the degree of polymerization of the resulting polymers without affecting the gross reaction rate. In the context of the present invention, a distinction is made between monofunctional, bifunctional or polyfunctional regulators, depending on the number of functional groups in the molecule which can lead to one or more chain transfer reactions.
  • Suitable polyfunctional regulators are compounds containing more than two halogen atoms in bonded form. Examples of these are alkyl halides, such as carbon tetrachloride, chloroform, bromotrichloromethane and bromoform.
  • Suitable polyfunctional regulators are compounds which contain more than two sulfur atoms in bonded form. Examples of these are trifunctional, tetrafunctional and higher functional mercaptans. These include the polyvalent sulfur compounds described in EP-A-1 086 980, incorporated herein by reference. Are preferred as a regulator z.
  • Suitable ⁇ -mercapto monocarboxylic acids are, for. B. 2-mercaptoacetic acid (thioglycolic acid), 3-mercapto-propionic acid, 4-mercaptobutyric acid, 5-mercaptopentanoic acid, 6-mercaptohexanoic acid, etc.
  • Suitable alcohols are, for. As glycerol, trimethylolpropane, erythritol, pentaerythritol, dipentaerythritol, etc.
  • Preferred polyfunctional regulators are polyfunctional mercaptans, e.g. As the formulas
  • n is an integer from 1 to 10 and R is Ci-C 4 alkyl.
  • Preferred trifunctional mercaptans are
  • Preferred tetrafunctional mercaptans are
  • Pentaerythritol tetrakis (2-mercaptoacetate) pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (4-mercaptobutyrate), pentaerythritol tetrakis (5-mercaptopentanoate), pentaerythritol tetrakis (6-mercaptohexanoate), and tetrathiopentaerythritol.
  • Preferred hexafunctional mercaptans are
  • Polyvalent sulfur compounds which are particularly preferred for use as regulators are:
  • Tetrathiopentaerythrit Tetrathiopentaerythrit.
  • Further polyfunctional regulators are Si compounds, as described in DE-A-102 37 378. These include oligomers based on compounds of the formula Ia and with structural elements of the formula Ib
  • n is an integer from 0 to 2
  • R 2 is C r C 18 -alkylene, cycloalkylene, preferably cyclohexylene, or arylene, preferably phenylene,
  • Z is C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl or C 2 -C 18 -alkynyl, where one or more nonadjacent carbon atoms is also bound by a heteroatom or a heteroatom-containing group selected from O, S, NR a or SiR b R ° may be replaced, wherein R a is hydrogen, alkyl, cycloalkyl or aryl and R b and R c are independently alkyl, cycloalkyl or aryl, or
  • R 3 , R 4 , R 5 and R 6 independently represent alkyl, cycloalkyl or aryl.
  • the monomer mixture M) used for the preparation of the copolymers according to the invention comprises monomers having anionogenic and / or anionic groups.
  • monomers with cationogenic and / or cationic groups may additionally be used for the polymerization (monomer d)).
  • the amount of monomers having cationogenic and cationic groups used for the polymerization is in this case dimensioned so that, based on the total monomers used for the polymerization, the molar fraction of cationogenic and cationic groups is less than the molar fraction of anionogenic and anionic groups.
  • the copolymers therefore have on average a molar excess of anionogenic / anionic groups in relation to cationogenic / cationic groups.
  • Component d) is preferably used in an amount of from 0 to 50% by weight, more preferably 0 to 40% by weight, in particular 0 to 30% by weight, based on the total weight of the components used for the polymerization (ie Components a), b), c) and, if present, d) to g)) are used. If a component d) is used, then it is preferably present in an amount of at least 0.1% by weight, more preferably at least 1% by weight, in particular at least 5% by weight. A particularly preferred amount range is 5 to 15% by weight.
  • Suitable monomers d) have a free-radically polymerizable ⁇ , ⁇ -ethylenically unsaturated double bond and additionally at least one cationogenic and / or cationic group per molecule.
  • the cationogenic or cationic groups of component d) 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 or quaternary ammonium groups.
  • Charged cationic groups can be prepared from the amine nitrogens either by protonation, e.g.
  • monohydric or polybasic carboxylic acids such as lactic or tartaric acid, or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, or by quaternization, e.g. With alkylating agents such as CrC 4 alkyl halides or sulfates. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Suitable compounds d) are, for. As the esters of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols.
  • Preferred amino alcohols are C 2 -C 12 aminoalcohols which are 8- dialkylated on the amine nitrogen CrC.
  • acid component of these esters are z.
  • N, N-dimethylaminomethyl (meth) acrylate 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.
  • Suitable monomers d) 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. Preference is given as monomers d) N- [2- (dimethylamino) ethyl] acrylamide,
  • Suitable monomers d) are furthermore N, N-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts and quaternization products.
  • Alkyl is preferably C 1 -C 24 -alkyl. Preference is given to N, N-diallyl-N-methylamine and N, N-diallyl-N, N-dimethylammonium compounds, such as. As the chlorides and bromides.
  • Suitable monomers d) are also vinyl- and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole and derivatives thereof, vinyl- and allyl-substituted heteroaromatic compounds, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof ,
  • Preferred monomers d) are the N-vinylimidazole derivatives of the general formula (II) in which R 1 to R 3 are hydrogen, C 1 -C 4 -alkyl or phenyl
  • the monomer mixture M) may additionally comprise at least one further monomer e) copolymerizable therewith and copolymerizable therewith from the abovementioned monomers a), b) and d).
  • Component e) is preferably used in an amount of from 0 to 50% by weight, particularly preferably 0 to 40% by weight, in particular 0 to 30% by weight, based on the total weight of the components used for the polymerization (ie components a ), b), c) and, if present, d) to g)). If a component e) is used, then it is preferably present in an amount of at least 0.1% by weight, more preferably at least 1% by weight, in particular at least 5% by weight.
  • the additional monomers e) are preferably selected from N-vinyllactams, open-chain N-vinylamide compounds, esters of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with CrCeo-alkanediols, amides of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with C 2 C 3 o-aminoalcohols having a primary or secondary amino group, primary amides of ⁇ , ß-ethylenically unsaturated monocarboxylic acids, esters of vinyl alcohol and allyl alcohol with d-Cao monocarboxylic acids, vinyl ethers, vinyl aromatics, vinyl halides, vinylidene halides, d -Cs monoolefins, non-aromatic hydrocarbons having at least two conjugated double bonds and mixtures thereof.
  • additional monomers e) are N-vinyl lactams and derivatives thereof, the z.
  • one or more C 1 -C 6 -alkyl substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc., may have. These include 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.
  • Preference is given to using N-vinylpyrrolidone and N-vinylcaprolactam.
  • Suitable open-chain N-vinylamide compounds as monomers e) are N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl N-methylpropionamide and N-vinylbutyramide.
  • Suitable additional monomers e) are furthermore 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate , 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylate, etc.
  • Suitable additional monomers e) are furthermore acrylamide and methacrylic acid amide.
  • Suitable additional monomers e) are also vinyl acetate, vinyl propionate, vinyl butyrate and mixtures thereof.
  • Suitable additional monomers e) are furthermore ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • the aforementioned additional monomers e) can be used individually or in the form of any desired mixtures.
  • copolymers of the invention may optionally comprise at least one crosslinker, i. in copolymerized form contain a compound having two or more than two ethylenically unsaturated, non-conjugated double bonds.
  • crosslinking agents in an amount of 0.01 to 3 wt .-%, particularly preferably 0.1 to 2 wt .-%, based on the total weight of the components used for the polymerization (ie components a), b), c) and if present, d) to g)).
  • Suitable crosslinkers f) are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols.
  • the OH groups of the underlying alcohols may be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.
  • Examples of the underlying alcohols are dihydric alcohols such as 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 2,3-butanediol, 1, 4-butanediol , But-2-ene-1, 4-diol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1 , 12-dodecanediol, neopentyl glycol, 3-methylpentane-1, 5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol
  • Examples of underlying alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, triethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose.
  • the polyhydric alcohols can also be used after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates.
  • the polyhydric alcohols can also be first converted by reaction with epichlorohydrin in the corresponding glycidyl ether.
  • crosslinkers f) 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.
  • esterify the monohydric, unsaturated alcohols with polybasic carboxylic acids for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • crosslinkers f) are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
  • Also suitable as monomers f) are straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which may not be conjugated with aliphatic hydrocarbons, eg. B. divinylbenzene, divinyltoluene, 1, 7-octadiene, 1, 9-decadiene,
  • crosslinking agents are the acrylic acid amides, methacrylic acid amides and N-allylamines of at least divalent amines.
  • amines are, for example, 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 carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least divalent carboxylic acids, as described above.
  • triallylmethylammonium chloride or methyl sulfate as crosslinker f) suitable.
  • N-vinyl compounds of urea derivatives at least divalent amides, cyanurates or urethanes, for example of urea, ethylene urea, propyleneurea or tartaramide, for. N, N'-divinylethyleneurea or N, N'-divinylpropyleneurea.
  • crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane.
  • Crosslinkers f) 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 have been reacted with ethylene oxide and / or propylene oxide and / or epichlorohydrin.
  • Very particularly preferred crosslinkers f) are pentaerythritol triallyl ether, methylenebisacrylamide, N, N'-divinylethyleneurea, triallylamine and triallylmonoalkylammonium salts and acrylic esters of glycol, butanediol, trimethylolpropane or glycerol or acrylates of glycol, butanediol, trimethylolpropane reacted with ethylene oxide and / or epichlorohydrin or glycerin.
  • Suitable regulators are described, for example, in detail by K.C. Berger and G. Brandrup in J. Brandrup, E.H. Immergut, Polymer Handbook, 3rd ed., John Wiley & Sons, New York, 1989, pp. 11/81 - 11/141.
  • the regulators g) are preferably used in an amount of 0 to 10 wt .-%, particularly preferably from 0 to 8 wt .-% and in particular from 0 to 5 wt .-%, based on the total weight of the components used for the polymerization (ie Components a), b), c) and, if present, d) to g)) are used. If a component g) is used, then preferably in an amount of at least 0.01% by weight, particularly preferably at least 0.02% by weight and in particular at least 0.05% by weight. A particularly preferred amount range is 0.2 to 1 wt .-%.
  • Suitable monofunctional regulators g) are, for example, aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde.
  • formic acid its salts or esters, such as ammonium formate, 2,5-diphenyl-1-hexene, hydroxylammonium sulfate, and hydroxylammonium phosphate.
  • halogen compounds having one or two halogen atoms, for.
  • dichloromethane, 1, 2-dichloroethane, allyl bromide, and benzyl compounds such as benzyl chloride or benzyl bromide.
  • Suitable regulators are allyl compounds, such as. Allyl alcohol, functionalized allyl ethers such as allyl ethoxylates, alkyl allyl ethers, or glycerol monoallyl ethers.
  • Compounds of this type are, for example, inorganic hydrogen sulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides and sulfones.
  • di-n-butyl sulfide di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl trisulfide, dimethyl sulfoxide, dialkyl sulfide, Dialkyl disulfide and / or diaryl sulfide.
  • organic compounds containing sulfur in bonded form are particularly preferred.
  • Preferred compounds used as polymerization regulators are thiols (compounds which contain sulfur in the form of SH groups, also referred to as mercaptans).
  • Preferred regulators are mono-, bi- and polyfunctional mercaptans, mercaptoalcohols and / or mercaptocarboxylic acids.
  • Examples of these compounds are allyl thioglycolates, ethyl thioglycolate, cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropane-1, 2-diol, 1, 4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, thioacetic acid , Thiourea and alkylmercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan.
  • Particularly preferred thiols are cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropane-1, 2-diol, thioglycerol, thiourea.
  • bifunctional regulators containing two sulfur in bonded form are bifunctional thiols such as. Dimercaptopropanesulfonic acid (sodium salt), di-mercaptosuccinic acid, dimercapto-1-propanol, dimercaptoethane, dimercaptopropane, dimercaptobutane, dimercaptopentane, dimercaptohexane, ethylene glycol bis-thioglycolates and butanediol bis-thioglycolate.
  • Another object of the invention is a process for the preparation of a copolymer with anionogenic and / or anionic groups, by free radical polymerization of a monomer mixture M) containing
  • the monomer mixture M) can be polymerized by conventional methods known in the art, for.
  • solution, precipitation, suspension or emulsion polymerization Preference is given to the preparation by emulsion or solution polymerization.
  • the polymerization is generally carried out at temperatures in a range from 0 to 150 ° C., preferably from 20 to 100 ° C., particularly preferably from 30 to 95 ° C.
  • the polymerization is preferably carried out at atmospheric pressure, but is also possible a polymerization under elevated pressure, for example in a pressure-tight reactor under the autogenous pressure of the components used for the polymerization.
  • a suitable pressure range is between 1 and 5 bar.
  • the monomers can be polymerized by means of free-radical initiators.
  • initiators for the radical polymerization the peroxo and / or azo compounds customary for this purpose can be used, for example alkali or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permalate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl
  • initiator mixtures or redox initiator systems such as. As ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / sodium hydroxy methanesulfinate, H 2 O 2 / Cu '.
  • the solvent is preferably selected from water and / or polar organic solvents.
  • 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-hexanol and cyclohexanol and also 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 having number average molecular weights up to about 3000, glycerol and dioxane.
  • Particularly preferred is the polymerization in an alcohol or alcohol mixture.
  • the copolymers by the process of free-radical aqueous emulsion polymerization.
  • Suitable aqueous solvents or dispersants are those mentioned above in the solution polymerization.
  • water is used.
  • the emulsion polymerization can be carried out either as a batch process or in the form of a feed process, including the stepwise and gradient processes.
  • the polymerization is carried out as a feed process in which one submits a portion of the polymerization mixture and the remaining components completely or partially, batchwise or continuously, together or in separate feeds to the template.
  • At least a portion of the aqueous medium and optionally a portion of the monomers used, regulators and / or surface-active substances in a polymerization zone heated to the polymerization, optionally this template (if it contains monomer) polymerized, and then the remainder of the polymerization fed to one or more spatially separate feeds while maintaining the polymerization of the polymerization.
  • polymerization initiator and monomers are added in separate feeds.
  • the feeding of the monomers can take place individually or in the form of mixtures, in pure or in aqueous medium dissolved or in emulsified form.
  • the addition of the initiator is generally carried out via a separate feed, generally in the aqueous phase, but monomer feed and initiator feed can be combined prior to entry into the reaction zone.
  • polyfunctional regulator and optionally further regulators may be carried out in admixture with a monomer feed, in admixture with the initiator feed or separately.
  • the formation of the emulsion can be carried out in the reaction zone by using suitable mixing devices.
  • suitable mixing devices Preferably, at least a portion of the components are already emulsified prior to entry into the reaction zone.
  • the mixers are preferably selected from stirred kettles, rotor-stator systems, preferably colloid mills or toothed-ring dispersing machines, ultrasonic homogenizers, high-pressure homogenizers, continuous tube mixers, jet dispersers, shear gap mixers, etc.
  • Suitable surface-active additives are the protective colloids and emulsifiers conventionally used as dispersants in the emulsion polymerization, as described, for example, in US Pat. B.
  • Suitable additional protective colloids are z.
  • polyvinyl alcohols and partially hydrolyzed polyvinyl acetates polyacrylates, polyvinylpyrrolidone, cellulose and cellulose derivatives, such as. For example, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, starch and starch derivatives, such as.
  • methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, starch and starch derivatives such as.
  • Suitable emulsifiers are both anionic, cationic and nonionic emulsifiers.
  • Emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 3500 daltons, are preferably used as surface-active substances.
  • nonionic emulsifiers are araliphatic (alkylated aromatics) or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO degree: 3 to 50, alkyl radical: C 4 -C 10 ), ethoxylates of long-chain alcohols (EO degree: 3 to 50, alkyl: C 8 -C 36 ) and polyethylene oxide / polypropylene oxide block copolymers.
  • Ethoxylates of long-chain alkanols alkyl radical
  • Ci O -C 22 average degree of ethoxylation 10 to 50) and including particularly preferred those having a linear C 2 -C 18 - alkyl radical and a mean degree of ethoxylation of 10 to 50 and ethoxylated monoalkylphenols.
  • Suitable anionic emulsifiers are for example alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 -C 22), ethoxylated sulfuric acid monoesters of alkanols (EO degree: from 2 to 50, alkyl radical: C 12 -C 8) and ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: C 4 -C 9 ), of alkylsulfonic acids (alkyl radical: C 12 -C 18 ) and of alkylarylsulfonic acids (alkyl radical: C 9 -C 18 ).
  • emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208).
  • anionic emulsifiers are bis (phenoylsulfonic acid) ethers or their alkali metal or ammonium salts which carry a C 4 -C 24 -alkyl group on one or both aromatic rings. These compounds are well known, for. From US-A-4,269,749, and commercially available, for example as Dowfax® 2A1 (Dow Chemical Company).
  • Suitable cationic emulsifiers are preferably quaternary ammonium halides, eg. B. trimethylcetylammonium chloride, methyltriocetylammonium chloride, benzyl triethylammonium chloride or quaternary compounds of NC 6 -C 2 o-alkylpyridines, -morpholines or -imidazoles, z. B. N-Laurylpyridinium chloride.
  • the amount of emulsifier is generally about 0 to 10 wt .-%, preferably 0.01 to 5 wt .-%, based on the amount of monomers to be polymerized.
  • polymeric dispersants can be used for the preparation. These additional polymeric dispersants are generally used in amounts of 0 to 10 wt .-%, preferably 0.01 to 5 wt .-%, based on the amount of monomers to be polymerized.
  • the additional polymeric dispersants generally contain at least one functional group selected from carboxyl, carboxylate, ether, hydroxyl, sulfate ester, amino, imino, tertiary amino, and / or quaternary ammonium groups .
  • Such compounds are: polyacrylic acids, polyvinyl acetate, polyalkylene glycols, in particular polyethylene glycols, polyvinyl alcohol, polyvinylpyridine, polyethyleneimine, polyvinylimidazole, polyvinylsuccinimide and polydiallmethylammonium chloride, polyvinylpyrrolidone, polymers containing at least 5% by weight of vinylpyrrolidone units, polymers containing at least 50 wt .-% of vinyl alcohol units, oligosaccharides, polysaccharides, oxidatively, hydrolytically or enzymatically degraded polysaccharides, chemically modified oligo- or polysaccharides such as carboxymethylcellulose, water
  • the reaction mixtures formed in the course of the polymerization in the form of solutions, dispersions, etc. can be subjected to a physical or chemical aftertreatment following the polymerization process.
  • Such methods are, for example, the known methods for residual monomer reduction such.
  • aqueous polymer dispersion before or after a Nachpolymerisations suits inert gas and / or Wasserstrampfstrippung.
  • This stripping process preferably takes place after the postpolymerization step.
  • partial neutralization of the dispersion to a pH in the range of 5 to 7, preferably to a pH in the range of 5.5 to 6.5 before the physical deodorization may be advantageous.
  • the reaction mixtures obtained in the polymerization can be partially or completely neutralized before or after a post-treatment. In particular, for use of the polymers in hair cosmetic preparations, such a partial or complete neutralization is advantageous.
  • the anionogenic groups contained in the polymers are preferably neutralized to at least 10%, particularly preferably at least 30%, very preferably at least 40%, in particular at least 50%, especially at least 70%, especially at least 95%.
  • a substantially complete neutralization takes place, ie at least 99% and in particular 100%.
  • alkali metal bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate or potassium bicarbonate and alkaline earth metal bases such as calcium hydroxide, calcium oxide,
  • Magnesium hydroxide or magnesium carbonate and ammonia can be used.
  • Ci-C 10 -alkylamines C 5 -C 10 preferably - alkylamines, such as N, N-diethylpropylamine, N, N-dipropylmethylamine and 3-diethylamino-1 -propylamine.
  • mono-, di- and trialkanolamines which preferably have 2 to 5 carbon atoms in the alkanol radicals.
  • the alkanol radicals can also be present in etherified form. Preference is given to mono-, di- and triethanolamine, mono-, di- and tri-n-propanolamine, mono-, di- and tri-isopropanolamine, 2-amino-2-methylpropanol, di (2-methoxyethyl) amine and Mixtures thereof.
  • alkanediolamines which preferably have 2 to 5 carbon atoms in the alkanediol radicals. These include 2-amino-2-methylpropane-1, 3-diol and 2-amino-2-ethyl-propane-1,3-diol. Particularly good results, in particular when using the polymers in cosmetic compositions, are achieved by neutralization with 2-amino-2-methyl-1-propanol, triisopropanolamine, N, N-dimethylaminoethanol or 3-diethylamino-1-propylamine.
  • the neutralization of the acid groups can also be carried out with the aid of mixtures of several of the abovementioned bases.
  • aqueous buffer solutions such as, for example, buffers based on alkali metal and ammonium carbonates or alkali metal and ammonium bicarbonates, are also suitable.
  • the neutralizing agents are then preferably added as a dilute aqueous solution for polymer dispersion.
  • copolymers of the invention can also be neutralized with other cosmetically or pharmaceutically acceptable polymers.
  • Polymers suitable for neutralization are e.g. cationic polymers with the name Polyquaternium according to INCI, z.
  • vinylimidazole-containing copolymers such as Luvitev® VPI, Luviset Clear®, copolymers of vinylpyrrolidone, vinylcaprolactam and vinylimidazole, as well as copolymers of vinylpyrrolidone, methacrylamide, vinylimidazole and N-vinylimidazolium salts.
  • Suitable cationic (quaternized) polymers are also Merquat® (polymer based on dimethyldiallylammonium chloride), Gafquat® (quaternary polymers which are formed by reaction of polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR (hydroxyethylcellulose with cationic groups) and cationic polymers on vegetable Base, z.
  • guar polymers such as the Jaguar® brands of Fa. Rhodia.
  • silicone polymers with cationogenic groups are used for neutralization.
  • Suitable silicone polymers are available under the INCI trademark Amodimethicone. These include the products commercially available under the names Wacker-Belsil® ADM 652, ADM 653, ADM 656, ADM 1 100, ADM 1600 and ADM 1650.
  • Suitable amino-containing polymers are also the silicone-aminopolyalkylene oxide block copolymers described in WO 97/32917.
  • dimethicone bisamino-hydroxypropyl copolyols sold by Witco / OSi under the name Silsoft® A-843 and trimethylsilyl-amodimethicone copolymers marketed under the name Silsoft® A-858.
  • silicone-containing polymers described in EP-A-1035144 for neutralization are also suitable.
  • the polymers according to the invention contain monomers d) in copolymerized form and still have free cationogenic groups, these can be converted, as described above, partially or completely into cationic groups by protonation or by quaternization.
  • the liquid reaction mixtures can by various drying methods, such as. As spray drying, fluidized spray drying, drum drying or freeze drying and dried z. B. be transferred in powder form. Preferably, 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 aqueous media. Powdered copolymers have the advantage of a better shelf life, easier transport and usually show a lower propensity for microbial attack.
  • conventional preservatives can be used for stabilization and preservation of polymer solutions and dispersions conventional preservatives can be used. Hydrogen peroxide is preferably used.
  • Another object of the invention are obtainable by the process according to the invention copolymers.
  • copolymers are outstandingly suitable for the preparation of cosmetic and pharmaceutical compositions. They serve z.
  • a polymeric film former in preparations for personal care, which includes the application of cosmetic preparations on keratinous surfaces such as skin, hair, nails and oral care preparations. They can be used universally in a wide variety of cosmetic preparations and formulated and compatible with the usual components.
  • formulations based on the copolymers according to the invention generally show significantly lower viscosities than corresponding preparations based on polymers known from the prior art, in particular those which have been prepared only in the presence of mono- and / or difunctional regulators of cosmetic and pharmaceutical agents in the form of sprays, which are characterized by very good spray properties.
  • the invention completely neutralized copolymers have as a 5 wt .-% solution in water / ethanol (40/55) preferably has a viscosity (determined at 25 0 C using a rotational viscometer) in the range of 5-20 mPas, most preferably from 7 up to 14 mPas.
  • the K values of the copolymers of the invention are preferably in a range of 20 to 80, particularly preferably from 25 to 40 (measured according to K. Fikentscher, Cellulose Chemistry Vol 13, pp. 58 - 64 (1932) at 25 0 C as 1% solution in ethanol).
  • compositions of the invention have a cosmetically or pharmaceutically acceptable carrier B), which is selected from i) water,
  • oils iii) oils, fats, waxes,
  • An oil or fat component B) selected from: low polarity hydrocarbons such as mineral oils; linear saturated hydrocarbons, preferably having more than 8 C atoms, such as tetradecane, hexadecane, octadecane, etc .; cyclic hydrocarbons, such as decahydronaphthalene; branched hydrocarbons; animal and vegetable oils; To grow; Wax esters; Petroleum jelly; Esters, preferably esters of fatty acids, such as.
  • esters of C r C 24 monoalcohols with d-Csa monocarboxylic acids such as isopropyl isostearate, n-propyl myristate, isopropyl myristate, n-propyl palmitate, isopropyl palmitate, hexacosanyl palmitate, octacosanyl palmitate, triacontanyl palmitate, dotriacontanyl palmitate, tetratriacontanyl palmitate , Hexacosanyl stearate, octacosanyl stearate, triacontanyl stearate, dicron acontanyl stearate, tetratriacontanyl stearate; Salicylates, such as d-Cio-salicylates, z.
  • Octyl salicylate Benzoate esters 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. B. linear polydimethylsiloxanes,
  • Poly (methylphenylsiloxanes), cyclic siloxanes and mixtures thereof are preferably in a range of about 1,000 to 150,000 g / mol.
  • Preferred cyclic siloxanes have 4- to 8-membered rings. Suitable cyclic siloxanes are, for. B. under the name 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, ricin oil, cod liver oil, lard, spermaceti, sperm oil, sperm oil, wheat germ oil, ma- cadamia nut oil, evening primrose oil, jojoba oil; Fatty alcohols, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl 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 or fat
  • 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.
  • Preferred supports B) are hydrophilic supports B).
  • Suitable hydrophilic carriers are selected from water, 1-, 2- or polyhydric alcohols having preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol, etc., and mixtures thereof
  • Preferred carriers B) are furthermore blowing agents.
  • Suitable blowing agents B) are those commonly used for hair sprays 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.
  • the cosmetic agents according to the invention may be skin-cosmetic, hair-cosmetic, dermatological, hygienic or pharmaceutical agents. Because of their film-forming properties, the copolymers described above are particularly suitable as additives for hair and skin cosmetics.
  • the agents according to the invention are preferably in the form of a gel, foam, spray, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.
  • the agents according to the invention are particularly preferably in the form of a spray.
  • compositions according to the invention are especially a hair treatment agent in spray form.
  • the cosmetic or pharmaceutical compositions according to the invention may additionally contain cosmetically and / or dermatologically active agents and adjuvants.
  • the cosmetic compositions according to the invention preferably comprise at least one copolymer as defined above, at least one carrier B as defined above and at least one different constituent selected from among cosmetically active substances, emulsifiers, surfactants, preservatives, perfume oils, thickeners, hair polymers, hair dyes. and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaching agents, gelling agents, conditioners, colorants, tinting agents, tanning agents, dyes, pigments, bodying agents, moisturizers, backfats, collagen, protein hydrolysates, lipids, antioxidants, defoamers, antistat - ka, emollients and plasticizers.
  • Typical thickeners in such formulations are crosslinked polyacrylic acids and their derivatives, polysaccharides and their derivatives, such as xanthan gum, agar-agar, alginates or tyloses, cellulose derivatives, eg. As carboxymethylcellulose or hydroxy-carboxymethylcellulose, fatty alcohols, monoglycerides and fatty acids, polyvinyl alcohol and polyvinylpyrrolidone.
  • Nonionic thickeners are preferably used.
  • Suitable cosmetically and / or dermatologically active agents are, for.
  • coloring agents skin and hair pigmentation agents, tinting agents, tanning agents, bleach, keratin-hardening substances, antimicrobial agents, light filtering agents, repellent, hyperemic substances, keratolytic and keratoplastic substances, antidandruff, antiphlogistics, keratinizing substances, antioxidant or as Radical scavengers active ingredients, skin moisturizing or moisturizing substances, moisturizing agents, antierythimatös or antiallergically active ingredients and mixtures thereof.
  • Artificial skin tanning agents that are suitable for tanning the skin without natural or artificial irradiation with UV rays, z.
  • Suitable keratin-hardening substances are generally active ingredients, as used in antiperspirants, such as.
  • antiperspirants such as.
  • Antimicrobial agents are used to destroy or inhibit their growth microorganisms and thus serve both as a preservative and as a deodorizing substance, which reduces the formation or intensity of body odor. These include z.
  • Suitable deodorizing substances are, for.
  • Suitable light-filtering agents are substances which absorb UV rays in the UV-B and / or UV-A range. Suitable UV filters are z.
  • 2,4,6-TriaryM 3,5-triazines, in which the aryl groups may each bear at least one substituent, which is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and mixtures thereof.
  • substituents which is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and mixtures thereof.
  • substituent is preferably selected from hydroxy, alkoxy, especially methoxy, alkoxycarbonyl, especially methoxycarbonyl and ethoxycarbonyl and mixtures thereof.
  • p-aminobenzoic acid esters cinnamic acid esters, benzophenones, camphor derivatives and UV-radiation-stopping pigments, such as titanium dioxide, talc and zinc oxide.
  • Suitable repellent agents are compounds capable of preventing or repelling certain animals, particularly insects, from humans
  • Suitable hyperemic substances which stimulate the circulation 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 such as salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc.
  • Suitable antidandruff agents are, for.
  • the cosmetic agents according to the invention may contain as cosmetic and / or pharmaceutical active substance (as well as optionally as adjuvant) at least one cosmetically or pharmaceutically acceptable polymer which differs from the polymers which form the polyelectrolyte complex used according to the invention.
  • cosmetically or pharmaceutically acceptable polymer which differs from the polymers which form the polyelectrolyte complex used according to the invention.
  • These include, in general, cationic, amphoteric and neutral polymers.
  • Suitable polymers are e.g. the cationic polymers previously described for neutralization, to which reference is hereby made.
  • polystyrene resins are also neutral polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose derivatives, Polyaspartic acid salts and derivatives.
  • neutral polymers such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose derivatives, Polyaspartic acid salts and derivatives.
  • Luviflex® Swing partially sapon
  • Suitable polymers are also nonionic, water-soluble or water-dispersible polymers or oligomers, such as polyvinyl caprolactam, z. B. Luviskol® Plus (BASF), or polyvinylpyrrolidone and their copolymers, especially with vinyl esters such as vinyl acetate, e.g. B. Luviskol® VA 37 (BASF); Polyamides, z. B. based on itaconic acid and aliphatic diamines, as z. B. in DE-A-43 33238 are described.
  • nonionic, water-soluble or water-dispersible polymers or oligomers such as polyvinyl caprolactam, z. B. Luviskol® Plus (BASF), or polyvinylpyrrolidone and their copolymers, especially with vinyl esters such as vinyl acetate, e.g. B. Luviskol® VA 37 (BASF); Polyamides, z. B. based on itaconic acid and
  • Suitable polymers are also amphoteric or zwitterionic polymers, such as those available under the names Amphomer® (National Starch) octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers and zwitterionic polymers, as described for example in German patent applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451 are disclosed.
  • Copolymers and their alkali metal and ammonium salts are preferred zwitterionic polymers.
  • Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, which are commercially available under the name Amersette® (AMERCHOL), and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N, N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon®).
  • Suitable polymers are also nonionic, siloxane-containing, water-soluble or -dispersible polymers, for.
  • polyether siloxanes such as Tegopren® (Goldschmidt) or Belsil® (Wacker).
  • the formulation base of pharmaceutical agents according to the invention preferably contains pharmaceutically acceptable excipients.
  • Suitable auxiliaries may be: lubricants, wetting agents, emulsifying and suspending agents, preserving agents, antioxidants, anti-irritants, chelating agents, emulsion stabilizers, film formers, gelling agents, odor masking agents, resins, hydrocolloids, solvents, solubilizers, neutralizing agents, permeation accelerators, pigments, quaternary ammonium compounds, Rest grease and superfatting agents, ointment, cream or oil bases, silicone derivatives, stabilizers, sterilants, blowing agents, drying agents, opacifiers, thickeners, waxes, emollients, white oils.
  • a related embodiment is based on expert knowledge, as shown for example in Fiedler, HP Lexicon of excipients for pharmacy, cosmetics and related fields, 4th ed., Aulendorf: ECV Editio Kantor Verlag, 1996.
  • the active ingredients may be mixed or diluted with a suitable excipient (excipient).
  • Excipients may be solid, semi-solid or liquid materials which may serve as a vehicle, carrier or medium for the active ingredient. If desired, the admixing of further auxiliaries takes place in the manner known to the person skilled in the art.
  • the polymers P) and dispersions Pd) are suitable as auxiliaries in pharmacy, preferably as or in coating agent (s) or binder (s) for solid dosage forms. They can also be used in creams and as tablet coatings and tablet binders.
  • the agents according to the invention are a skin cleanser.
  • Preferred skin cleansing agents are soaps of liquid to gel consistency, such as transparent soaps, luxury soaps, deep soaps, cream soaps, baby soaps, skin soaps, abrasive soaps and syndets, pasty soaps, greases and washing pastes, liquid detergents, shower and bath preparations such as washing lotions, shower gels and gels , Bubble baths, oil baths and scrub preparations, shaving foams, lotions and creams.
  • the agents according to the invention are cosmetic agents for the care and protection of the skin, nail care preparations or preparations for decorative cosmetics.
  • Suitable skin cosmetic agents are, for.
  • Means for use in decorative cosmetics include, for example, masking pens, theatrical paints, mascara and eye shadows, lipsticks, kohl pencils, eyeliners, rouges, powders, and eyebrow pencils.
  • copolymers of the invention can be used in nasal strips for pore cleansing, in anti-acne agents, repellents, shaving agents, hair removal agents, personal care products, foot care products and in baby care.
  • the skin care compositions according to the invention are in particular W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-wrinkle creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, skin lotions and moisturizing lotions.
  • the polymers may be used inter alia Moisturizing and conditioning of the skin and improve the skin feel contribute.
  • the polymers may also act as thickeners in the formulations.
  • Skin cosmetic and dermatological compositions preferably comprise at least one copolymer according to the invention in a proportion of about 0.001 to 30 wt .-%, preferably 0.01 to 20 wt .-%, most preferably 0.1 to 12 wt .-%, based on the Total weight of the agent.
  • compositions of the invention in a form suitable for skin care such. B. as cream, foam, gel, pen, mousse, milk, spray (pump spray or propellant spray) or lotion can be applied.
  • the skin-cosmetic preparations may, in addition to the copolymers according to the invention and suitable carriers, contain further active ingredients and auxiliaries customary in skin cosmetics, as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaching agents, colorants, toners, tanning agents, collagen, protein hydrolysates, stabilizers, pH Regulators, dyes, salts, thickeners, gelling agents, consistency regulators, silicones, humectants, moisturizers and other conventional additives.
  • active ingredients and auxiliaries customary in skin cosmetics as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamins A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaching agents, color
  • Preferred oil and fat components of the skin cosmetic and dermatological agents are the aforementioned mineral and synthetic oils, such as.
  • copolymers according to the invention can also be mixed with conventional polymers if special properties are to be set.
  • the skin cosmetic and dermatological preparations may additionally contain conditioning substances based on silicone compounds.
  • Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
  • the preparation of the cosmetic or dermatological preparations is carried out by customary methods known to the person skilled in the art.
  • the cosmetic and dermatological agents are preferably in the form of emulsions, in particular as water-in-oil (W / O) or oil-in-water (O / W) emulsions.
  • W / O water-in-oil
  • O / W oil-in-water
  • Emulsions are prepared by known methods.
  • the emulsions generally contain customary constituents, such as fatty alcohols, fatty acid esters and especially fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
  • customary constituents such as fatty alcohols, fatty acid esters and especially fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils or waxes and emulsifiers in the presence of water.
  • a suitable emulsion for.
  • a skin cream, etc. generally contains an aqueous phase which is emulsified by means of a suitable emulsifier in an oil or fat phase.
  • a copolymer of the invention can be used.
  • Preferred fat components which may be included in the fat phase of the emulsions are: hydrocarbon oils such as paraffin oil, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in these oils; animal or vegetable oils, such as sweet almond oil, avocado oil, calophilum oil, lanolin and derivatives thereof, castor oil, seed oil, olive oil, jojoba oil, karite oil, hoplostethus oil; Mineral oils whose beginning of distillation under atmospheric pressure at about 250 0 C and their distillation end point at 410 0 C, such as. Vaseline oil; Esters of saturated or unsaturated fatty acids, such as alkyl myristates, e.g.
  • i-propyl, butyl or cetyl myristate hexadecyl stearate, ethyl or i-propyl palmitate, octanoic or Decanklandretriglyceride and Cetylricinoleat.
  • the fat phase may also contain other oil-soluble silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
  • oils such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer, fatty acids and fatty alcohols.
  • waxes can be used, such as. Carnauba wax, candililla wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.
  • an emulsion of the invention may be present as O / W emulsion.
  • Such an emulsion usually contains an oil phase, emulsifiers that stabilize the oil phase in the water phase, and an aqueous phase that is usually thickened.
  • Suitable emulsifiers are preferably O / W emulsifiers, such as polyglycerol esters, sorbitan esters or partially esterified glycerides into consideration.
  • the agents according to the invention are a shower gel, a shampoo formulation or a bathing preparation.
  • Such formulations comprise at least one polyelectrolyte complex A) and usually anionic surfactants as base surfactants and amphoteric and / or nonionic surfactants as cosurfactants.
  • suitable active ingredients and / or auxiliaries are generally selected from lipids, perfume oils, dyes, organic acids, preservatives and antioxidants as well as thickeners / gelling agents, skin conditioners and humectants.
  • formulations preferably contain from 2 to 50% by weight, preferably from 5 to 40% by weight, particularly preferably from 8 to 30% by weight, of surfactants, based on the total weight of the formulation.
  • Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isothionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, in particular the alkali metal and alkaline earth metal salts, eg. As sodium, potassium, magnesium, calcium, and ammonium and
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule. These include z. Sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecyl benzene sulfonate, triethanolamine dodecyl benzene sulfonate.
  • Suitable amphoteric surfactants are, for. Alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or -propionates, alkylamphodiacetates or -dipropionates.
  • cocodimethylsulfopropyl betaine cocodimethylsulfopropyl betaine, lauryl betaine, cocamidopropyl betaine or sodium cocamphopropionate can be used.
  • Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 C atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and / or propylene oxide.
  • the amount of alkylene oxide is about 6 to 60 moles per mole of alcohol.
  • alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkylpolyglycosides or sorbitan ether esters are also suitable.
  • washing, showering and bathing preparations may contain conventional cationic surfactants, such as. B. quaternary ammonium compounds, such as cetyltrimethyl ammonium chloride.
  • shower gel / shampoo formulations thickener, such.
  • cooking salt PEG-55, propylene glycol oleate, PEG-120-Methylglucose dioleate and others, as well as preservatives, other active ingredients and excipients and water.
  • the agents according to the invention are a hair treatment agent.
  • Hair treatment compositions according to the invention preferably contain at least one copolymer according to the invention in an amount in the range from about 0.1 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the composition.
  • the hair treatment compositions of the present invention are in the form of a mousse, hair mousse, hair gel, shampoo, hair spray, hair mousse, top fluid, perming, hair dyeing and bleaching or hot oil treatments.
  • the hair cosmetic preparations can be applied as (aerosol) spray, (aerosol) foam, gel, gel spray, cream, lotion or wax.
  • Hairsprays include both aerosol sprays as also pump sprays without propellant.
  • Hair foams include both aerosol foams and pump foams without propellant gas.
  • Hair sprays and hair foams preferably comprise predominantly or exclusively water-soluble or water-dispersible components.
  • the compounds used in the hair sprays and hair foams according to the invention are water-dispersible, they can be used in the form of aqueous microdispersions with particle diameters of usually from 1 to 350 nm, preferably from 1 to 250 nm.
  • the solids contents of these preparations are usually in a range of about 0.5 to 20 wt .-%.
  • these microdispersions do not require emulsifiers or surfactants for their stabilization.
  • alcohol all alcohols customary in cosmetics are to be understood, for.
  • ethanol isopropanol, n-propanol.
  • Further constituents are understood to mean the additives customary in cosmetics, for example propellants, defoamers, surface-active compounds, ie surfactants, emulsifiers, foaming agents and solubilizers.
  • the surface-active compounds used can be anionic, cationic, amphoteric or neutral.
  • Other common ingredients may also be z.
  • perfume oils, opacifiers, active ingredients, UV filters, care agents such as panthenol, collagen, vitamins, protein hydrolysates, alpha- and beta-hydroxycarboxylic acids, stabilizers, pH regulators, dyes, viscosity regulators, gel formers, salts, humectants, moisturizers , Complexing agents and other common additives.
  • this includes all known in cosmetics styling and Conditionerpoly- mers, which can be used in combination with the polymers of the invention, if very special properties are to be set.
  • Suitable conventional hair cosmetic polymers include, for example, the abovementioned cationic, anionic, neutral, nonionic and amphoteric polymers, to which reference is hereby made.
  • the preparations may additionally contain conditioning substances based on silicone compounds.
  • Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes, silicone resins or dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).
  • copolymers A) according to the invention can be used in cosmetic preparations as setting and / or conditioning agents. They are particularly suitable as setting agents in hairstyling preparations, in particular hair sprays (aerosol sprays and pump sprays without propellant gas) and hair foams (aerosol foams and pump foams without propellant gas).
  • the agents according to the invention are present in a preferred embodiment as a spray. They then preferably comprise a device for generating aerosols, comprising
  • compositions of the invention when they contain in a first embodiment, a sufficient amount of a propellant.
  • propellants are fluorohydrocarbons, such as 1,1-difluoroethane (HFC-152a).
  • the blowing agents used are preferably hydrocarbons (LPG), in particular propane, n-butane, n-pentane and mixtures thereof.
  • Suitable hydrocarbon mixtures are propane / butane mixtures.
  • Dimethyl ether is particularly suitable as an alternative to the hydrocarbon blowing agents.
  • Further preferred blowing agents are compressed gases, such as nitrogen, air or carbon dioxide.
  • the copolymers A) used in the compositions according to the invention have a high propellant gas compatibility, in particular a high compatibility with dimethyl ether, and can be converted into products with a high propellant gas content of, for example, min. at least 40 wt .-%, preferably at least 50 wt .-%, based on the total weight of the agent formulate. In general, however, it is also possible to keep the blowing agent content low in order to formulate products with a low VOC content. In such products, the propellant gas content is then generally not more than 55% by weight, based on the total weight of the composition.
  • compositions according to the invention are also suitable according to a second embodiment for preparations without the addition of blowing agents.
  • the aerosol device additionally comprises a pressure generating device, e.g. a pumping device.
  • spray formulations contain
  • Emulsifiers which can be used are all emulsifiers customarily used in hair foams. Suitable emuigators may be nonionic, cationic or anionic or amphoteric.
  • nonionic emuigators 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.
  • cationic emuigators are cetyldimethyl-2-hydroxyethylammonium dihydrogenphosphate, cetyltrimonium chloride, cetyltrimmonium bromide, cocotrimonium methylsulfate, quaternium-1 to x (INCI).
  • Anionic emulsifiers may, for example, be selected from the group of alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isothionates, Aikylphosphate, alkyl ether, alkyl ether, alpha-olefinsulfonates, especially the alkali and alkaline earth metal salts, eg. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.
  • copolymers A) according to the invention can furthermore be used in shampoo formulations. Contain preferred shampoo formulations
  • Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isothionates, Aikylphosphate, Alkyletherphospha- te, Alkylethercarboxylate, alpha-olefinsulfonates, especially the alkali and alkaline earth metal salts, eg. As sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.
  • Suitable examples are sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl sulfate, ammonium lauryl ether sulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.
  • Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or -propionates, alkylamphodiacetates or -dipropionates.
  • alkylbetaines alkylamidopropylbetaines
  • alkylsulfobetaines alkylglycinates
  • alkylcarboxyglycinates alkylamphoacetates or -propionates
  • alkylamphodiacetates or -dipropionates alkylamphodiacetates or -dipropionates.
  • cocodimethylsulfopropyl betaine, lauryl betaine, cocamidopropyl betaine or sodium cocamphopropionate can be used.
  • Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 C atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and / or propylene oxide.
  • the amount of alkylene oxide is about 6 to 60 moles per mole of alcohol.
  • alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters are also suitable.
  • the shampoo formulations may contain conventional cationic surfactants, such as.
  • quaternary ammonium compounds for example Cetyltrimethylammoni- umchlorid.
  • Conventional conditioning agents in combination with the polyelectrolyte complexes A) can be used in the shampoo formulations to achieve certain effects.
  • these include, for example, the abovementioned cationic polymers with the name Polyquaternium according to INCI, in particular copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Gare), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ 11), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold); cationic cellulose derivatives (polyquaternium-4 and -10), acrylamide copolymers (
  • egg white hydrolysates and also conditioning substances based on silicone compounds for example polyalkyl siloxanes, polyaryl siloxanes, polyaryl alkyl siloxanes, polyether siloxanes or silicone resins.
  • silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).
  • CTFA dimethicone copolyols
  • ICI cationic guar derivatives
  • Another object of the invention is the use of a polyelectrolyte complex, as defined above, as auxiliaries in pharmacy, preferably as or in coating agent (s) for solid dosage forms, for modifying rheological properties, as a surface-active compound, as or in adhesives (n ) as well as in or coating agent (s) for the textile, paper, printing and leather industries.
  • a polyelectrolyte complex as defined above, as auxiliaries in pharmacy, preferably as or in coating agent (s) for solid dosage forms, for modifying rheological properties, as a surface-active compound, as or in adhesives (n ) as well as in or coating agent (s) for the textile, paper, printing and leather industries.
  • reaction mixture is cooled to 60 0 C and 2 g of an aqueous, 30% hydrogen peroxide solution are added.
  • the polymerization batch is then adjusted to a pH of 6.5 with a 10% by weight solution of ammonium bicarbonate in deionized water. This is followed by a 30-minute steam distillation.
  • TMPTMA 1, 1-tris- (hydroxymethyl) -propane-tris- (2-mercaptoacetate
  • TMPTMP 1, 1-tris- (hydroxymethyl) -propane-tris- (3-mercaptopropionate)
  • Polymers which are prepared with multifunctional regulators according to the invention are advantageously suitable as a solidifying polymer for formulations with a high water content (Iow-VOC). They are characterized by good consolidation and a good spray pattern.
  • the measuring system is based on the laser light diffraction on the particle. Apart from spray analysis (aerosols, pump sprays), this method is also suitable for determining the size of solids, suspensions and emulsions in the size range from 0.1 ⁇ m to 2000 ⁇ m.
  • the aerosols were sprayed at a distance of 29.5 cm to the laser beam.
  • the spray cone entered at right angles to the laser beam.
  • the aerosol cans were fixed to a fixed fixture 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 total particle volume was recorded and evaluated over a test period of 2 seconds.
  • the evaluation contained a tabular representation over 32 class widths from 0.5 ⁇ m to 2000 ⁇ m and additionally a graphic representation of the particle size distribution. Since the spraying tests were evenly distributed, the mean diameter "Mean Diameter" D (v, 0.5) was reported.
  • this value is below 120 ⁇ m, preferably below 100 ⁇ m, particularly preferably in the range from 30 ⁇ m to 70 ⁇ m.
  • valve A Seaquist Perfect
  • the consolidation of polymeric film-forming agents is measured, in addition to the subjective judgment, physically as the bending stiffness of thin strands of hair which have been treated with the polymer solution and dried again.
  • 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 carried out in a climatic chamber at 20 0 C and 65% relative humidity by means of a tensile / pressure tester.
  • the lock of hair was placed symmetrically on two cylindrical rollers of the sample holder. Right in the middle of the strand was now bent from above with a rounded punch 40 mm (breaking the polymer film).
  • the required force was measured with a load cell (50 N) and reported in Newton. Stiff effect on the hair
  • the viscosity of the polymer was assessed in an ethanol / water mixture of the following composition:
  • the polymers preferably have a viscosity of from 5 to 20 mPas, very particularly preferably a viscosity of from 7 to 14 mPas.
  • the following aerosol formulation was prepared in compressed gas containers made of glass.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne des agents cosmétiques et pharmaceutiques contenant un copolymère à groupes anionogènes et/ou anioniques, lequel copolymère peut être obtenu par polymérisation radicalaire d'un mélange de monomères en présence d'un régulateur polyfonctionnel possédant au moins trois groupes régulateurs fonctionnels. Cette invention concerne également un procédé de production d'un copolymère de ce type ainsi que les copolymères obtenus selon ledit procédé.
EP06702184A 2005-01-21 2006-01-20 Copolymeres pour agents cosmetiques, obtenus en presence de regulateurs polyfonctionnels Withdrawn EP1844081A1 (fr)

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DE102005003010A DE102005003010A1 (de) 2005-01-21 2005-01-21 Copolymere für kosmetische Mittel, hergestellt in Gegenwart polyfunktioneller Regler
PCT/EP2006/000516 WO2006077144A1 (fr) 2005-01-21 2006-01-20 Copolymeres pour agents cosmetiques, obtenus en presence de regulateurs polyfonctionnels

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NL2001793C2 (en) * 2008-07-11 2010-01-12 Parvus Beheer B V Method for the preparation of a biocompatible hydrogel.
CA2894802C (fr) * 2012-12-11 2020-12-22 Akzo Nobel Coatings International B.V. Compose a fonction thiol

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DE3935137A1 (de) * 1989-10-21 1991-04-25 Hoechst Ag Urethangruppen enthaltende copolymerisate auf der basis von ethylenisch ungesaettigten monomeren, verfahren zu ihrer herstellung und ihre verwendung

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