EP2181123A1 - Procédé de production de polymères de l'acide acrylique réticulés - Google Patents

Procédé de production de polymères de l'acide acrylique réticulés

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Publication number
EP2181123A1
EP2181123A1 EP08786869A EP08786869A EP2181123A1 EP 2181123 A1 EP2181123 A1 EP 2181123A1 EP 08786869 A EP08786869 A EP 08786869A EP 08786869 A EP08786869 A EP 08786869A EP 2181123 A1 EP2181123 A1 EP 2181123A1
Authority
EP
European Patent Office
Prior art keywords
acid
polymerization
meth
polymers
cosmetic
Prior art date
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EP08786869A
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German (de)
English (en)
Inventor
Son Nguyen Kim
Wolfgang Jahnel
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BASF SE
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BASF SE
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Priority to EP08786869A priority Critical patent/EP2181123A1/fr
Publication of EP2181123A1 publication Critical patent/EP2181123A1/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
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/125—Monomers containing two or more unsaturated aliphatic radicals, e.g. trimethylolpropane triallyl ether or pentaerythritol triallyl ether
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate

Definitions

  • the present invention relates to a process for the preparation of crosslinked acrylic acid polymers, characterized in that the process is a precipitation polymerization, in a solvent containing hydrocarbyl and / or alkyl esters, at at least two different temperatures and at least two various initiators is performed.
  • the present invention furthermore relates to crosslinked polymers obtainable by the process according to the invention and to cosmetic and pharmaceutical preparations which contain such polymers.
  • Powdery rheology modification agents are known and have found application in many areas such as paint, paper, textile, hygiene, cosmetics or pharmaceutical applications.
  • EP 328725 describes a process for the preparation of a polymer by polymerization of a monomer mixture containing at least 85% by weight of the monomer mixture of at least one olefinically unsaturated carboxylic acid having from 3 to 5 carbon atoms, salts of said acid (s) and mixtures thereof, up to 15% by weight of this monomer mixture of at least one copolymerizable comonomer in the presence of a mixed reaction medium, up to 5% by weight of a crosslinking agent and less than 2.0% by weight of an initiator.
  • the reaction medium contains at least one organic solvent and at least one hydrocarbon solvent, wherein the organic solvent is selected from ketones, esters, ethers and mixtures thereof, and wherein the hydrocarbon solvent is selected from straight chain aliphatic, branched aliphatic, cyclic aliphatic and mixtures thereof wherein the relative weight ratio of the at least one organic solvent to the at least one hydrocarbon solvent is in the range of 2: 1 to 1: 2.
  • DE 3750220 describes a process carried out in the presence of less than 3% water to produce a polymer of carboxylic monomer containing less than 0.2% of unreacted monomer, wherein more than 2% and up to 10% of the carboxyl groups of the monomer are neutralized, comprising the polymerization of a monomer charge containing at least 90% of an olefinically unsaturated carboxylic acid monomer having 3 to 5 carbon atoms and its salt, in the presence of a solvent selected from the group consisting of acetone, alkyl acetates with From 1 to 6 carbon atoms in the alkyl group and mixtures thereof, in the presence of from 0.2 to 2.0% by weight of a monomer charge of a crosslinking agent and in the presence of less than 2% by weight of a monomer charge of an initiator selected from the group consisting of Peroxydicarbonaten, wherein the reaction temperature of 45 0 C to 55 0 C.
  • EP 371421 describes a process for preparing acrylic acid copolymers wherein the acrylic acid monomer is polymerized in a nonaqueous solvent selected from acetone and an alkyl acetate having 1 to 6 carbon atoms in the alkyl group and in the presence of an initiator and divinyl glycol crosslinker, said Polymer in particulate form having an average particle size of less than 10 microns without grinding is obtained, resulting in a mucous viscosity of over 50,000 mPas (cps) when measured at 1% concentration in water.
  • a nonaqueous solvent selected from acetone and an alkyl acetate having 1 to 6 carbon atoms in the alkyl group and in the presence of an initiator and divinyl glycol crosslinker
  • WO 80/01 164 describes a process for the preparation of acrylic acid polymers, wherein the acrylic acid is neutralized before the polymerization to a proportion of at least 1 mol% and the polymerization carried out as precipitation polymerization in solvents having solubility parameters of 8 to 15.
  • a disadvantage of the processes of the prior art is that the reaction times are sometimes very long, the solids contents of the polymerization mixtures are low and the amounts of residual monomers are high.
  • This object has been achieved by a process for preparing crosslinked polymers by free-radically initiated precipitation polymerization of a monomer mixture comprising anionic and / or anionogenic monomers and less than 2% by weight of cationic and / or cationogenic monomers, a. in the presence of a solvent which is or comprises at least one solvent selected from the group consisting of hydrocarbons, alkyl esters and mixtures thereof, b. in the presence of at least two different polymerization initiators, wherein at least one of the initiators is a peroxide compound, and c. the temperature of the reaction mixture is increased at least once by at least 10 ° C. during the polymerization.
  • WO 2007/010034 describes a process for the preparation of ampholytic copolymers by free-radical precipitation polymerization using two different initiators. The polymerization of monomer mixtures containing less than 2% by weight of cationic and / or cationogenic monomers is not described.
  • “during the polymerization” means the period which extends from the time at which the polymerization begins to the time at which at least 70, preferably at least 80, more preferably at least 90% by weight of the monomers used polymerize are.
  • monomer mixture is meant the total amount of all radically polymerizable compounds used in the process of the invention.
  • the process according to the invention is a precipitation polymerization.
  • solvents are used in which the starting materials for the polymerization soluble and the resulting polymer are insoluble.
  • the solvent used for the precipitation polymerization of the process according to the invention is or comprises at least one solvent selected from the group consisting of hydrocarbons, alkyl esters and mixtures thereof.
  • Preferred hydrocarbons are straight-chain, branched or cyclic hydrocarbons having 4 to 12 carbon atoms, more preferably those having 5 to 9 carbon atoms.
  • n-pentane n-hexane
  • n-heptane n-octane
  • cyclohexane cycloheptane
  • aromatic hydrocarbon such as benzene, toluene and xylene.
  • hydrocarbon component of the solvent is cyclohexane.
  • Preferred alkyl esters are esters of saturated aliphatic C 1 to C 4 carboxylic acids with monohydric saturated C 1 to C 6 alcohols. Further preferred are the esters of acetic acid with monohydric saturated C 1 to C 6 alcohols, particularly preferred are methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate and sec-butyl acetate. Most preferred are ethyl acetate, isopropyl acetate, n-butyl acetate and mixtures thereof.
  • the process according to the invention is carried out in the presence of at least two different polymerization initiators A and B, at least one of the initiators being a peroxide compound.
  • the process according to the invention is preferably characterized in that the two different polymerization initiators are water-insoluble.
  • water-insoluble means that less than 10, preferably less than 1 g of the initiator in 1 liter of water are clearly soluble to the human eye under standard conditions.
  • the inventive method is preferably characterized in that the two different polymerization initiators are selected so that their respective decomposition temperatures are at least 45 ° C.
  • the decomposition temperature is defined as the temperature at which 50% of the molecules decompose into free radicals within 1 hour, ie the half-life is 1 hour.
  • the polymerization is carried out in this procedure until completion of the precipitation of the polymer at a temperature greater than or equal to the lower decomposition temperature and less of the higher decomposition temperature, and after the precipitation, a further reaction at a temperature greater than or equal to higher decomposition temperature.
  • the process according to the invention comprises a first polymerization phase at a first polymerization temperature and a second polymerization phase at a second polymerization temperature of at least 10 ° C. above the first polymerization temperature, at least two initiators being used for the polymerization, whose half-lives at the first polymerization temperature differ so that at least one of these initiators decomposes into free radicals during the first polymerization phase and at least one of these initiators substantially does not decompose into free radicals during the first polymerization phase and decomposes into free radicals during the second polymerization.
  • the second polymerization phase essentially begins after precipitation of the polymer.
  • substantially after precipitation of the polymer is meant that the polymer is preferably at least 70% by weight, preferably at least 80 wt .-%, in particular at least 90 wt .-%, based on the total weight of the polymer, in precipitated form.
  • the half-life of an initiator can be determined by customary methods known to the person skilled in the art, such as eg. In the publication "Initiators for high polymers", Akzo Nobel, No. 10737.
  • the half-life of the first polymerization initiator at the first polymerization temperature and the second polymerization initiator at the second polymerization temperature is in a range of about 1 minute to 3 hours, more preferably 5 minutes to 2.5 hours. If desired, shorter half-lives z. From 1 second to 1 minute or longer half lives than 3 hours, as long as it is ensured that the initiator (s) decomposing at the higher temperature are essentially not during the first but during the second polymerization phase Radicals decays.
  • first and second polymerization phases may be used at different polymerization temperatures.
  • z For example, it is possible to carry out a first polymerization phase at a first polymerization temperature selected to provide controlled polymerization (i.e., eg, avoiding undesirable temperature rise by the heat of reaction, too high reaction rate, etc.). Subsequently, z. For example, add a postpolymerization at a temperature which is above the first and below the second polymerization temperature and which is selected such that the initiator (s) which decompose at the higher temperature do not essentially decompose into free radicals. After completion of this post-polymerization, to which, if desired, again the decomposing at the lower temperature initiator and / or another decomposing under the conditions of the postpolymerization initiator can be added, then the second polymerization can follow.
  • the decomposing at the lower temperature initiator has a decomposition temperature of 50 to 100 0 C.
  • the decomposing at the higher temperature initiator has a decomposition temperature of 80 to 150 0 C.
  • the method is characterized in that the decomposition temperatures of at least two polymerization initiators by at least 10 0 preferably more preferably differ by at least 14 ° C to at least 17 ° C and in particular at least 20 0 C C.
  • the initiator decomposing at the higher temperature is initially introduced at the beginning of the copolymerization or added before or during the precipitation of the copolymer.
  • the water-insoluble initiators are preferably selected from water-insoluble diazo and peroxide compounds.
  • Polymerization initiators suitable for the process according to the invention are selected, for example, from dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permalate, Benzoyl peroxide, tert-amyl peroxypivalate, cumene hydroperoxide, diisopropyl peroxydicarbamate, bis (o-toluoyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide
  • the polymerization initiators are selected from the group consisting of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, di (2-ethylhexyl) peroxydicarbonate, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, tert. -Amylperoxypivalate, dimethyl 2,2'-azobis (2-methylpropionate), tert-butyl peroxyneodecanoate, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2-methylpropionamide), 2,2'-azobis (2,4-dimethylvaleronitrile).
  • Suitable initiators are furthermore 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis [N- (2-propenyl) 2-methylpropionamide], 1 - [(cyano-1-methylethyl) azo] formamide, 2,2'-azobis (N-butyl-2-methylpropionamide), 2,2'-azobis (N-cyclohexyl-2-methylpropionamide ).
  • the above-mentioned initiators are examples example as Wako ® - commercially available or Trigonox ® brands.
  • the polymerization it is preferred for the polymerization to a date at which at least 70, preferably at least 80, particularly preferably at least 90 and in particular at least 95 wt .-% of the monomers used are polymerized as the first initiator those To select initiator whose decomposition temperature is lower by at least 10 0 C than that of the second initiator.
  • the second initiator is used in a preferred embodiment for the so-called postpolymerization.
  • the postpolymerization is carried out after at least 80, preferably at least 90, more preferably at least 95 and in particular at least 99 wt .-% of the monomers used are polymerized.
  • Crosslinkers are preferably used in an amount of from 0.01 to 2% by weight, particularly preferably 0.1 to 1% by weight, based on the total weight of the monomers used for the polymerization, including the crosslinkers.
  • 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 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-en-1, 4-diol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1, 12-dodecanediol, neopentyl glycol, 3-methylpentane-1, 5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1,4-
  • the homopolymers of ethylene oxide or propylene oxide also block copolymers of E 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 can also be used after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates.
  • the polyhydric alcohols can also be first converted by reaction with epichlorohydrin in the corresponding glycidyl ether.
  • crosslinkers are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated Cs-C ⁇ -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 are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
  • Other suitable crosslinkers are urethane diacrylates and urethane polyacrylates, as described, for. B. under the name Laromer ® are commercially available.
  • 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. As divinylbenzene, divinyltoluene, 1, 7-octadiene, 1, 9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights of 200 to 20,000.
  • crosslinkers are the acrylic acid amides, methacrylic acid amides and N-allylamines of at least dihydric amines.
  • Such amines are, for example, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,1-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 dibasic 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 divalent amides, cyanurates or urethanes, for example of urea, ethylene urea, propylene urea or tartaramide, for. N, N'-divinylethyleneurea or N, N'-divinylpropyleneurea.
  • crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane.
  • Crosslinkers used with particular preference are, for example, methylenebisacrylamide, triallylamine and triallylalkylammonium salts, divinylimidazole, pentaerythritol triallyl ether, N, N'-divinylethyleneurea, reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic acid esters and acrylic esters of polyalkylene oxides or polyhydric alcohols which are reacted with ethylene oxide and / or propylene oxide and / or epichlorohydrin have been reacted.
  • Very particularly preferred crosslinking agents are pentaerythritol triallyl ether, methylenebisacrylamide, N, N'-divinylethyleneurea, allyl (meth) acrylate, diallyl-tartaric diamide, triallylamine and triallylmonoalkylammonium salts and acrylic esters of glycol, butanediol, trimethylolpropane or glycerol or acrylic esters of with ethylene oxide and / or epichlorohydrin reacted glycol, butanediol, trimethylolpropane or glycerol.
  • “Cationogenic” in the context of this invention means a compound which can be converted into a cationic form by protonation or quaternization, in particular alkylation.
  • the monomer mixture to be polymerized comprises less than 4% by weight, preferably less than 2% by weight, particularly preferably less than 1% by weight and in particular less than 0.1% by weight, of cationic and / or cationogenic monomers. In one embodiment of the invention, the monomer mixture to be polymerized does not comprise any cationic and / or cationogenic monomers.
  • the polymers obtainable by the process according to the invention comprise compounds having a free-radically polymerizable, .alpha.,. Beta.-ethylenically unsaturated double bond and at least one anionogenic and / or anionic group copolymerized per molecule.
  • anionogenic means a compound which can be converted by deprotonation into an anionic form
  • these compounds comprise at least one compound which is selected from monoethylenically unsaturated carboxylic acids, sulfonic acids,
  • the monomers 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.
  • 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.
  • these include the half esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6 carbon atoms, for. B.
  • maleic acid such as monomethyl maleate.
  • monoethylenically unsaturated sulfonic acids and phosphonic acids for example vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid , Vinylphosphonic acid and allylphosphonic acid.
  • the anionic or anionogenic monomers can be used as such or as mixtures with one another.
  • the anionic or anionic compound is or comprises at least one compound 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, 2-acrylamido 2-methylpropanesulfonic acid, vinylphosphonic acid and mixtures thereof.
  • the anionic or anionic compound is or comprises at least one compound selected from acrylic acid, methacrylic acid and mixtures thereof. Most preferably, the anionic or anionic compound is or comprises acrylic acid.
  • anionic or anionic compounds may be used singly or in the form of any mixtures.
  • the polymers which can be prepared by the process according to the invention may contain, in copolymerized form, other monomers which are different from the anionic and / or anionogenic monomers.
  • all monomers which can be radically copolymerized with the anionic and / or anionogenic monomers are suitable for this purpose.
  • Suitable monomers are mentioned, for example, in WO 2007/010035, p. 33, Z. 20 to p. 42, Z. 22, to which reference is hereby made in their entirety.
  • the monomer mixture also comprises at least one monomer which is selected from C5-C3O (meth) acrylates, C5-C3O (meth) acrylamides, polyethers terminated with C5-C30-alkyl groups ( meth) acrylates and mixtures thereof, in particular under stearyl methacrylate, with Ci8-C22-alkyl groups-terminated polyethylene glycol (meth) acrylates and mixtures thereof.
  • Suitable C5-C3o (meth) acrylates are, for example, pentyl (meth) acrylate, 2-pentyl (meth) acrylate, 3-pentyl (meth) acrylate, isopentyl acrylate, neopentyl acrylate, 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 (
  • Suitable C5-C3o (meth) acrylamides are, for example, N- (n-pentyl) (meth) acrylamide, N- (n-hexyl) (meth) acrylamide, N- (n-heptyl) (meth) acrylamide, N- ( n-octyl) (meth) acrylamide,
  • N-ethylhexyl (meth) acrylamide N- (n-nonyl) (meth) acrylamide
  • N- (n-decyl) (meth) acrylamide N- (n-undecyl) (meth) acrylamide
  • N-nonadecyl (meth) acrylamide N-arrachinyl (meth) acrylamide
  • N-cerotinyl (meth) acrylamide N-melissinyl (meth) acrylamide
  • a preferred process is characterized in that the monomer mixture contains i) 90 to 99.98% by weight of acrylic acid, ii) 0 to 10% by weight of further monomers, iii) 0.02 to 2% by weight of crosslinker with the proviso that the sum i) to iii) is 100% by weight.
  • the post-polymerization is preferably carried out at a temperature higher than the temperature at which the main polymerization has been carried out.
  • the temperature at which the post-polymerization is carried out at least 5 ° C, preferably at least 10 0 C, more preferably at least 15 and in particular at least 20 0 C higher than the temperature of the main polymerization.
  • the amount of the initiator preferably used for the main polymerization is preferably from 0.001 to 2.0, more preferably from 0.01 to 1.5, particularly preferably from 0.05 to 1.0, and in particular from 0.1 to 0.5% by weight. , based on the total amount of monomers used:
  • the amount of the at least one initiator preferably used for the postpolymerization is preferably from 0.001 to 2.5, more preferably from 0.01 to 2.0, particularly preferably from 0.1 to 1.5, and in particular from 0.3 to 1.0 Wt .-%, based on the total amount of the monomers used.
  • the amount by weight of the initiator which is preferably used for the postpolymerization is greater than the amount by weight of the initiator which is preferably used for the main polymerization.
  • the amount by weight of the initiator which is preferably used for the postpolymerization is at least 1.5 times, more preferably at least 2 times, particularly preferably at least 3 times the amount by weight of the initiator which is preferably used for the main polymerization ,
  • the main polymerization (first reaction stage) is carried out in the temperature range from 40 to 110 0 C, preferably in the range of 50 to 100 0 C, particularly preferably in the range of 55 to 85 ° C. It is usually carried out under atmospheric pressure, but can also be carried out under reduced or elevated pressure, preferably from 1 to 5 bar.
  • the post-polymerization (second or higher reaction stage) is carried out in the temperature range of 50 to 200 0 C, preferably in the range of 70 to 160 0 C, particularly preferably in the range of 75 to 130 ° C. It is usually carried out under atmospheric pressure, but can also be carried out under reduced or elevated pressure, preferably from 1 to 5 bar.
  • the solvent or solvent mixture determined by the corresponding boiling temperatures, the maximum reaction temperature if polymerized under atmospheric pressure. However, polymerizations under pressure are also possible.
  • Monomers and initiator are generally added in a time of 1 to 10 hours, preferably from 2 to 5 hours.
  • polymers such as polyamides, polyurethanes, polyesters, homo- and copolymers of ethylenically unsaturated monomers may also be present in the preparation of the polymers.
  • examples of such inserted part also in cosmetics polymers are those known under the trade names polymers Amerhold ®, Ultrahold ®, Ultrahold ® Strong, Luviflex ® VBM, Luvimer ®, Acronal ®, Acudyne ®, Stepanhold ®, Lovocryl ®, Versatyl ®, Amphomer.RTM ® or Eastman AQ ®, Luvi- set ® brands, Sokalan ® brands, Luviquat.RTM ® brands.
  • the precipitated polymer is isolated from the reaction mixture after the postpolymerization step, for which any conventional method of isolating the polymers in conventional precipitation polymerization can be used. Such methods are filtration, centrifugation, evaporation of the solvent or combinations of these methods.
  • the polymer may be washed.
  • the same solvents as they are suitable for the polymerization.
  • the polymer is to be dried, it is advisable to carry out a solvent exchange after the polymerization and to use low-boiling solvents for the drying.
  • the process is characterized in that the precipitation polymerization is carried out in the presence of at least one surface-active substance.
  • this substance has an HLB value less than or equal to 10.
  • HLB hydrophilic-lipophilic balance
  • Suitable surface-active substances having an HLB value of less than or equal to 10 are described, for example, in Karl-Heinz Schrader, Kunststoffn und Japaneseuren der Kosmetika, 2nd edition, Verlag Wegig, Heidelberg, pp. 395-397, to which reference is made in its entirety ,
  • the determination of the HLB value of emulsifiers is known to the person skilled in the art and described, for example, on page 394 of the aforementioned reference.
  • Further suitable surface-active substances with an HLB value less than or equal to 10 are listed, for example, in US Pat. No. 4,375,533, column 7, lines 26-60, to which reference is made in its entirety.
  • the use of surface-active substances in the precipitation polymerization of crosslinked polyacrylic acid is already described in US 4420596 and US 4375533.
  • B is a hydrophobic moiety having a molecular weight M w of from 300 to 60,000, having a solubility in water at 25 ° C. of less than 1% by weight, and being covalently bound to A;
  • C and D are end groups which may be A or B and the same group or different groups; w is 0 or 1; x is an integer greater than or equal to 1, y is 0 or 1, and z is 0 or 1.
  • the invention further provides a process as described above, wherein the precipitation polymerization is carried out in the presence of at least one surface active substance of random comb copolymers represented by the following formula:
  • Ri and R2 are end groups and may be the same or different and are different from Z and Q, Z is a hydrophobic moiety having a solubility in water of less than 1% by weight of 25 ° C.,
  • Q is a hydrophilic moiety having a solubility in water at 25 0 C of more than 1 wt .-%, and m and n are integers greater than or equal to 1 and are selected such that the
  • Molar mass M w 100 to 250,000.
  • Particularly preferred surface-active substances are 12-hydroxystearic acid block copolymers, more preferably 12-hydroxystearic acid block copolymers with polyethylene oxide. Most preferably, the 12-hydroxystearic acid block copolymers are ABA block copolymers.
  • Hypermer ® B239 block copolymer of polyhydroxy fatty acid (PFA) and polyethylene oxide (PEO) with Mw of about 3500
  • Hypermer ® B246 Block copolymer of polyhydroxy fatty acid (PFA) and polyethylene oxide (PEO) with Mw of approx. 7500.
  • Hypermer ® B261 block copolymer of a polyhydroxy fatty acid (PFA) and polyethylene oxide (PEO) with Mw of about 9600th
  • Hypermer ® 2234 non-ionic polymeric surface-active compound
  • Hypermer ® LP6 polymeric fatty acid ester with M w of approx. 4300.
  • Hypermer IL2296 ® nonionic polymeric surface-active compound
  • Hypermer A-109 ® block copolymer of a fatty acid or a long-chain alkylene radical with ethylene oxide is shown in FIG. 7 .
  • EP 584771 B1 describes the use of such surface-active substances in the production of polyacrylic acid.
  • the surface-active substance is selected from the group consisting of
  • Examples of commercially available copolymers of polydimethylsiloxanes and organic glycols which may be used according to the invention are substances having
  • Dimethicone PEG-7 phospha te (INCI) be mentioned, for example Pecosil ® PS-100.
  • Kahl Wachs 6635 Kahl & Co.
  • Examples of commercially available natural waxes which may be used according to the invention are mixtures of fatty acid esters, fatty acids and fatty alcohols such as, for example, beeswax, berry wax, rice wax (Kahl & Co).
  • Suitable bee waxes are, in particular, those with the CAS numbers 8006-40-4 (White) or 8012-89-3.
  • Suitable bee waxes bear the INCI (EU) names Cera Alba, Synthetic beeswax, PEG-7 Dimeticone beeswax.
  • Particularly suitable bee waxes are those with the INCI EU name Cera Alba.
  • Suitable soft waxes are for example those with the INCI name Rhus verniciflua Peel Wax (Berry 6290 Wax (Kahl & Co) or Botaniwax OT ® (Botanigenics, Ine)).
  • Suitable rice waxes are in particular those with CAS number 8016-60-2 or the INCI name Oryza Sativa (Rice) Bran Wax.
  • Such rice waxes are commercially available as Cerewax ® (Chemyunion Quimica LTDA), ESP ® Rice Bran Wax (Earth Sup- plied Products, LLC), Florabeads ® RBW (FLORATECH Americas), Naturebead ® R20 (Micro Powders, Inc.
  • Oryza soft ® "COS” Cosmetochem International Ltd.
  • ORYZA ® Wax Ichimaru Pharcos Company, Ltd.
  • Ricebran Wax SP 8000 Strahl & Pitsch, Inc.
  • Rice Wax No.1 Tn-K Industries
  • Rice wax 281 1 available.
  • the amount of surfactants present during the precipitation polymerization is in the range of 0.001 to 50, preferably 0.01 to 20, and more preferably in the range of 0.1 to 10 wt%, based on the total amount of 100 wt%.
  • the polymerizable compounds i) to iii) as defined above are in the range of 0.001 to 50, preferably 0.01 to 20, and more preferably in the range of 0.1 to 10 wt%, based on the total amount of 100 wt%.
  • the polymers obtainable by the process according to the invention can be used as the only gelling agent in cosmetic preparations due to their thickening effect. Moreover, they are also suitable for use in combination with conventional gel formers.
  • the anionic and / or anionic monomers can be provided in, preferably partially, neutralized form for the polymerization.
  • the neutralization can be carried out, for example, with an anhydrous, in particular a tertiary amine, such as triethanolamine, methyldiethanolamine, N, N-dimethyltriethanolamine or with an anhydrous base, such as Na 2 CO 3, K 2 CO 3.
  • the degree of neutralization is preferably less than 20 mol%.
  • the polymerization with partially neutralized acrylic Acid has already been proposed in numerous patents such as US 3915921, US 4066583, US 4758641 or US 4267103.
  • the polymers obtainable by the process according to the invention are effective as thickeners in aqueous solution after at least partial neutralization.
  • alkali or ammonium carbonate or bicarbonate are suitable.
  • the neutralization can also be carried out 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 Triisopropanolamin, 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-ethyl-propane-1,3-diol, or a primary, secondary or tertiary alkylamine with a total of 5 to 10
  • Carbon atoms for example N, N-diethylpropylamine or 3-diethylamino-1-propylamine, - with N, N, N ', N' - tetrakis (2-hydroxypropyl) ethylenediamine (Neutrol ® TE).
  • alkali metal hydroxides for neutralization are sodium or potassium and ammonium hydroxide. Often, good neutralization results are obtained with 2-amino-2-methylpropanol, triethanolamine, 2-amino-2-ethylpropane-1,3-diol, N, N-dimethylaminoethanol or 3-diethylamino-1-propylamine.
  • Neutralization is preferred for a gel until reaching a degree of neutralization in the range of 90 to 100 mol% or until reaching a pH in the range of 6.5 to 7.5.
  • This neutralization of the polymers is preferably carried out using hydroxylamines such as AMP (aminomethylpropanol), TEA (triethanolamine), methyldiethanolamine and / or an inorganic base such as NaOH or KOH.
  • amino-containing silicone polymers are also suitable.
  • Suitable amino-containing silicone polymers are, for example, the silicone
  • Polyaminopolyalkylene oxide block copolymers of WO 97/32917 the products Silsoft ® A-843 (dimethicone bisamino hydroxypropyl copolyol) and Silsoft ® A-858 (trimethylsilyl A- modimethicone copolymer) (both Fa. 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 polymer obtainable by the process according to the invention can be used wherever conventional thickeners based on polyacrylic acid are used.
  • the polymers obtainable by the process according to the invention can be used as thickeners in aqueous preparations in the household, personal care, building industry, textile, paper coating, pigment pastes, aqueous paints, leather treatment, cosmetic formulations, pharmaceuticals and agrochemicals.
  • Another object of the invention is the use of the polymers obtainable by the process according to the invention in cosmetic and / or pharmaceutical preparations.
  • Another object of the invention are cosmetic and / or pharmaceutical preparations containing polymers obtainable by the process according to the invention.
  • Another object of the invention are cosmetic or pharmaceutical preparations, containing
  • compositions according to the invention preferably have a cosmetically or pharmaceutically acceptable carrier B), which is selected from
  • esters of C 1 -C 24 -monoalcohols with C 1 -C 22 -monocarboxylic acids such as isopropylisostearate, 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, dotriacontanyl stearate, tetratriacontanyl stearate; Salicylates, such as C1-C10 salicylates, e.g.
  • Octyl salicylate Benzoate esters, such as cio-cis alkyl benzoates, benzyl benzoate; other cosmetic esters, such as fatty acid triglycerides, propylene glycol monolaurate, polyethylene glycol monolaurate, C 10 -C 16 -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 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, 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.
  • oils, fats and / or waxes are selected which are described on page 28, line 39 to page 34, line 22 of WO 2006/106140.
  • the content of said text is hereby incorporated by reference.
  • the content of further oils, fats and waxes is at most 50, preferably 30, more preferably at most 20% by weight, based on the total weight of the composition.
  • Suitable hydrophilic carriers B) are selected from water, mono-, di- or polyhydric alcohols having preferably 1 to 8 carbon atoms, such as ethanol, n-propanol, isopropanol, propylene glycol, glycerol, sorbitol, etc.
  • the cosmetic preparations according to the invention may be skin-cosmetic, hair-cosmetic, dermatological, hygienic or pharmaceutical preparations. Because of their film-forming properties, the polymers obtainable by the process according to the invention are particularly suitable as thickeners for hair and skin cosmetics.
  • the preparations according to the invention are preferably in the form of a gel, foam, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, liposomes or microspheres can also be used.
  • the cosmetically or pharmaceutically active preparations according to the invention may additionally comprise cosmetically and / or dermatologically active agents and auxiliaries.
  • the cosmetic preparations according to the invention preferably comprise at least one polymer A) obtainable by the process according to the invention, at least one carrier B as defined above and at least one different constituent selected from cosmetically active ingredients, emulsifiers, surfactants, preservatives, perfume oils, further thickeners , Hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaching agents, gelling agents, care products, colorants, tinting agents, tanning agents, dyes, pigments, bodying agents, moisturizers, restockers, collagen, protein hydrolysates, lipids, antioxidants, Defoamers, antistatic agents, emollients and plasticizers.
  • the cosmetic preparations according to the invention can be used as aqueous or aqueous-alcoholic solutions, O / W and W / O emulsions, hydrodispersion formulations, solids-stabilized formulations, stick formulations, PIT formulations, in the form of creams, foams, sprays (pump spray or Aerosol), gels, gel sprays, lotions, oils, oil gels or mousses and accordingly formulated with conventional further excipients.
  • Particularly preferred cosmetic preparations in the context of the present invention are gels, shampoos, washing and bath preparations and hair care products.
  • the Accordingly, the invention also relates to preparations for the cleaning and / or care of the hair and the skin.
  • the invention relates to hair care products selected from the group consisting of styling gels, hairdressing gels, shampoos, hair conditioners, hair balms, pomades, hairdressing creams, hairdressing lotions, hairdressing gels, lace fluids, hot oil treatments.
  • the invention relates to cosmetic preparations which are selected from gels, gel creams, hydroformulations, stick formulations, cosmetic oils and oil gels, mascara, self-tanner, face care, personal care products, after-sun preparations.
  • Further cosmetic preparations according to the invention are skin-cosmetic preparations, in particular those for the care of the skin. These are especially in the form of W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-wrinkle creams, facial expressions, moisturizing creams, bleaching creams, vitamin creams, skin lotions, body lotions and moisturizing lotions.
  • the polymers obtainable by the process according to the invention are suitable as thickeners for skin cosmetic preparations, face masks, cosmetic lotions and for use in decorative cosmetics, for example for masking, theatrical paints, in mascara and eye shadows, lipsticks, kohl pencils, eyeliners, make-up , Primers, rouges and powders and eyebrow pencils.
  • preparations according to the invention can be used in anti-aging, repellents, shaving, hair removal, personal hygiene, foot care and baby care products.
  • Further preferred preparations according to the invention are washing, showering and bath preparations which contain the polymers obtainable by the process according to the invention.
  • washing, showering and bathing preparations comprise soaps of liquid to gel-like consistency, such as transparent soaps, luxury soaps, deodorants, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, pasty soaps, greases and washing pastes, liquid detergents, shower and bath preparations, such as washing lotions, shower baths and gels, bubble baths, oil baths and scrub preparations, shaving foams, lotions and creams understood. Suitable further ingredients for these inventive washing, showering and bathing preparations are described below.
  • the preparations comprise, in addition to the polymeric thickeners obtainable by the process according to the invention, further cosmetically acceptable additives such as, for example, emulsifiers and coemulsifiers, solvents, surfactants, oil particles, preservatives, perfume oils, cosmetic care agents and active ingredients such as AHA acids, fruit acids, ceramides, Phytantriol, collagen, vitamins and provitamins, for example vitamins A, E and C, retinol, bisabolol, panthenol, natural and synthetic sunscreens, natural products, opacifiers, solubilizers, repellents, bleaches, colorants, tints, tanning agents (eg dihydroxyacetone), micropigments such as titanium oxide or zinc oxide, superfatting agents, pearlescent waxes, bodying agents, further thickeners, solubilizers, complexing agents, fats, waxes, silicone compounds, hydrotropes, dyes, stabilizers, pH regulators, reflectors, proteins and protein hydrolysates (
  • the cosmetic preparations according to the invention contain the polymers obtainable by the process according to the invention in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, particularly preferably 0.1 to 1.5% by weight. , based on the weight of the preparation.
  • the shower gels according to the invention, washing, showering and bathing preparations as well as shampoos and hair-care preparations furthermore contain at least one surfactant.
  • the shampoos and hair care compositions according to the invention further comprise, in addition to the polymers, at least one oil and / or fat phase and one surfactant.
  • surfactants it is possible to use anionic, cationic, nonionic and / or amphoteric surfactants.
  • Sarcosinates for example myristoyl sarcosine, TEA-lauroyl sarcosinate, sodium lauroyl sarcosinate and sodium cocoyl sarcosinate,
  • Acyl isethionates for example sodium or ammonium cocoyl isethionate
  • Sulfosuccinates for example dioctyl sodium sulphosuccinate, disodium laureth sulphosuccinate, disodium lauryl sulphosuccinate and disodium undecylenamido MEA sulphosuccinate, disodium PEG-5 lauryl citrate sulphosuccinate and derivatives,
  • Alkyl ether sulfates for example sodium, ammonium, magnesium, MIPA, TIPA laureth sulfate, sodium myreth sulfate and sodium C12-13 pareth sulfate, - Alkyethersulfonate, for example, sodium C12-15 Pareth-15 sulfonate
  • Alkyl sulfates for example sodium, ammonium and TEA lauryl sulfate. Further advantageous anionic surfactants are
  • Taurates for example sodium lauroyl taurate and sodium methyl cocoyl taurate, ether carboxylic acids, for example sodium laureth-13 carboxylate and sodium PEG-6 cocamide carboxylate, sodium PEG-7 olive oil carboxylate
  • Phosphoric acid esters and salts such as, for example, DEA-oleth-10-phosphate and dilaureth-4-phosphate,
  • Alkyl sulfonates for example sodium coconut monoglyceride sulfate, sodium C 12-14 olefin sulfonate, sodium lauryl sulfoacetate and magnesium PEG-3 cocamide sulfate,
  • Acylglutamates such as di-TEA-palmitoylaspartate and sodium caprylic / capric glutamate,
  • Acyl peptides for example palmitoyl hydrolyzed milk protein, sodium cocoyl-hydrolysed soy protein and sodium / potassium cocoyl-hydrolyzed collagen, and carboxylic acids and derivatives such as lauric acid, aluminum stearate, magnesium alkoxide and zinc undecylenate, ester carboxylic acids, for example calcium stearyl lactate, laureth-6 citrate and sodium PEG-4 Lauramidcarboxylate
  • Advantageous washing-active cationic surfactants for the purposes of the present invention are quaternary surfactants. Quaternary surfactants contain at least one N atom covalently linked to 4 alkyl or aryl groups. For example, alkylbetaine, alkylamidopropylbetaine and alkylamidopropylhydroxysultaine are advantageous. Further advantageous cationic surfactants for the purposes of the present invention are furthermore - alkylamines,
  • washing-active amphoteric surfactants for the purposes of the present invention are acyl / dialkylethylenediamines, for example sodium acylamphoacetate, disodium adenylphphate dipropionate, disodium alkylamphodiacetate, sodium acylamphohydroxypropylsulphonate, disodium acylamphodiacetate, sodium acylamphopropionate, and
  • amphoteric surfactants are N-alkylamino acids, for example aminopropylalkylglutamide, alkylaminopropionic acid, sodium alkylimidodipropionate and lauroamphocarboxyglycinate.
  • Alkanolamides such as cocamide MEA / DEA / MIPA, esters which are formed by esterification of carboxylic acids with ethylene oxide, glycerol, sorbitan or other alcohols, Ethers, for example ethoxylated alcohols, ethoxylated lanolin, ethoxylated polysiloxanes, propoxylated POE ethers, alkyl polyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside, glycosides having an HLB value of at least 20 (for example BeififG 128V (Wacker)).
  • Further advantageous nonionic surfactants are alcohols and amine oxides, such as cocoamidopropylamine oxide.
  • Preferred anionic, amphoteric and nonionic shampoo surfactants are mentioned, for example, in "Cosmetics and Hygiene from Head to Toe", ed. W. Limbach, 3rd Edition, Wiley-VCH, 2004, pp. 311-134, whereupon this In full reference.
  • alkyl ether sulfates sodium alkyl ether sulfates based on di- or tri-ethoxylated lauryl and myristyl alcohol are particularly preferred. They clearly outperform the alkyl sulfates with regard to their resistance to water hardness, colourability, low solubility and, in particular, skin and mucous membrane compatibility. They can also be used as sole washing raw materials for shampoos. Lauryl ether sulfate has better foam properties than myristyl ether sulfate, but it is inferior in mildness. Alkyl ether carboxylates are often used in combination with alkyl ether sulfates and amphoteric surfactants in shampoos.
  • Sulfosuccinic acid esters are mild and foaming surfactants are preferably used only in neutral or well-buffered products because of their poor thickenability preferably only together with other anionic and amphoteric surfactants and because of their low hydrolysis stability.
  • Amidopropylbetaines are practically insignificant as sole washing raw materials, since their foaming behavior and their thickenability are only moderately pronounced.
  • these surfactants have an excellent skin and eye mucosa compatibility.
  • anionic surfactants their mildness can be synergistically improved.
  • Preferred is the use of cocamidopropyl betaine.
  • amphoteric surfactants amphoacetates / amphodiacetates have a very good skin and mucous membrane compatibility and can have a hair conditioning effect or increase the care effect of additives. They are similar to the betaines used to optimize alkyl ether sulfate formulations. Most preferred are sodium cocoamphoacetate and disodium cocoamphodiacetate.
  • Alkyl polyglycosides are nonionic washing raw materials. They are mild, have good universal properties, but lather weakly. For this reason, they are preferably used in combination with anionic surfactants. Sorbitan esters also belong to the nonionic washing raw materials. Because of their excellent mildness, they are preferred for use with baby shampoos. As weak foaming agents, they are preferably used in combination with anionic surfactants. It is advantageous to choose the detergent surfactant or surfactants from the group of surfactants having an HLB value of more than 25, particularly advantageous ones having an HLB value of more than 35.
  • Polysorbates can also advantageously be incorporated into the preparations according to the invention as detergent-active agents.
  • advantageous polysorbates are, for example
  • the polysorbates are used advantageously in a concentration of 0.1 to 5 and in particular in a concentration of 1, 5 to 2.5 wt .-%, based on the total weight of the preparation individually or as a mixture of polysorbates several.
  • conditioners for the cosmetic preparations according to the invention those conditioning agents are preferably selected, which are described on page 34, line 24 to page 37, line 10 of WO 2006/106140. The content of said text is hereby incorporated by reference.
  • the polymers obtainable by the process according to the invention have a sufficient, very good thickening effect.
  • thickening agents may additionally be used in the preparations according to the invention.
  • Thickeners suitable for gels, shampoos and hair care products are mentioned in "Cosmetics and hygiene from head to toe", ed. W. Limbach, 3rd edition, Wiley-VCH, 2004, pages 235-236, to which reference is made in its entirety becomes.
  • Suitable further thickening agents for the cosmetic preparations according to the invention are also described, for example, on page 37, line 12 to page 38, line 8 of WO 2006/106140. The content of said text is hereby incorporated by reference.
  • the cosmetic preparations according to the invention may also contain preservatives.
  • Compositions with high water contents must be reliably protected against microbial contamination.
  • Suitable preservatives for the cosmetic compositions according to the invention are described, for example, on page 38, line 10 to page 39, line 18 of WO 2006/106140. The content of said text is hereby incorporated by reference.
  • Complexing agents As the raw materials and many cosmetic products themselves are mainly produced in steel equipment, the end products may contain trace amounts of iron (ions). In order to prevent these impurities from adversely affecting the product quality via reactions with dyes and perfume oil components, complexing agents such as salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodisuccinic acid or phosphates are added.
  • UV photoprotective filter In order to stabilize the ingredients contained in the compositions of the invention such as dyes and perfume oils against changes by UV light, UV light protection filters, such as. As benzophenone derivatives are incorporated. Suitable UV photoprotective filters for the cosmetic compositions according to the invention are described, for example, on page 39, line 20 to page 41, line 10 of WO 2006/106140. The content of said text is hereby incorporated by reference.
  • antioxidant compositions of the invention A content of the antioxidant compositions of the invention is generally preferred. According to the invention, all antioxidants suitable or used for cosmetic applications can be used as antioxidants. Suitable antioxidants for the cosmetic compositions according to the invention are described, for example, on page 41, line 12 to page 42, line 33 of WO 2006/106140. The content of the text mentioned is hereby incorporated by reference in its entirety.
  • Buffers ensure the pH stability of the compositions. Predominantly used are citrate, lactate and phosphate buffers.
  • Solubilizers They are used to clearly dissolve nourishing oils or perfume oils and to keep them clear even in the cold.
  • the most common mediators are ethoxylated nonionic surfactants, eg. B. hydrogenated and ethoxylated castor oils.
  • Germ-inhibiting agents can also be used. These generally include all suitable preservatives having specific activity against Gram-positive bacteria, e.g. Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether), chlorhexidine (1,1'-hexamethylenebis [5- (4-chlorophenyl) biguanide), and TTC (3,4,4'-trichlorocarbanilide). Quaternary ammonium compounds are also suitable in principle and are preferably used for disinfecting soaps and detergents. Also numerous fragrances have antimicrobial properties. Also, a large number of essential oils or their characteristic ingredients such. 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 .-%.
  • Dispersant When in the compositions of the invention insoluble active ingredients, e.g. Antidandruff active ingredients or silicone oils, dispersed and kept in suspension in the long term, must dispersants and thickeners such. As magnesium aluminum silicates, bentonites, fatty acyl derivatives, polyvinylpyrrolidone or hydrocolloids, z. As xanthan gum or carbomers are used. According to the invention, preservatives are contained in a total concentration of at most 2, preferably at most 1, 5 and particularly preferably at most 1% by weight, based on the total weight of the composition.
  • preservatives are contained in a total concentration of at most 2, preferably at most 1, 5 and particularly preferably at most 1% by weight, based on the total weight of the composition.
  • compositions may optionally contain the additives customary in cosmetics, for example perfumes, dyes, replenishing agents, complexing and sequestering agents, pearlescing agents, plant extracts, vitamins, active ingredients, pigments which have a coloring action, softening, moisturizing and / or moisturizing substances, or other conventional ingredients of a cosmetic or dermatological formulation, such as alcohols, polyols, polymers, organic acids for pH adjustment, foam stabilizers, electrolyte, organic solvents or silicone derivatives.
  • further ingredients known to the person skilled in the art for the compositions reference is made to "Cosmetics and hygiene from head to toe", ed. W. Umbach, 3rd edition, Wiley-VCH, 2004, pp. 123-128, whereupon at this point, reference is made in full.
  • compositions of the invention such as gels, shampoos and hair care agents optionally contain ethoxylated oils selected from the group of ethoxylated glycerol fatty acid esters, more preferably PEG-10 olive oil glycerides, PEG-1 1 avocado oil glycerides, PEG-1 1 cocoa butter glycerides, PEG-13 sunflower - Nölglyceride, PEG-15 Glyceryl Isostearate, PEG-9 Coconut Fatty Acid Glycerides, PEG-54 Hydrogenated Castor Oil, PEG-7 Hydrogenated Castor Oil, PEG-60 Hydrogenated Castor Oil, Jojoba Oil Ethoxylate (PEG-26 Jojoba Grease Acids, PEG-26 Jojoba Alcohol), Glycereth-5 co-coat, PEG-9 coconut fatty acid glycerides, PEG-7 glyceryl cocoate, PEG-45 palm kernel oil glycerides, PEG-35 castor oil, olive oil PEG-7 ester, PEG-6 capry
  • Preferred ethoxylated oils are PEG-7 glyceryl cocoate, PEG-9 coconut glycerides, PEG-40 hydrogenated castor oil, PEG-200 hydrogenated glyceryl palmat.
  • Ethoxylated glycerol fatty acid esters are used in aqueous cleaning formulations for various purposes. Glycerol fatty acid esters with a degree of ethoxylation of about 30-50 serve as solubilizers for non-polar substances such as perfume oils. Highly ethoxylated glycerol fatty acid esters are used as thickeners.
  • compositions of the invention a variety of active ingredients with different solubility can be incorporated homogeneously.
  • Advantageous active ingredients in the cosmetic compositions according to the invention are described, for example, on page 44, line 24 to page 49, line 39 of WO 2006/106140. The content of said text is hereby incorporated by reference.
  • UV light protection preparations in particular in the form of creams, lotions and sprays. These contain UV sunscreen to protect the skin and / or hair. Suitable UV light stabilizers are described in detail in WO 2006/1061 14, S.24, Z.4 to S.27, Z.27, to which reference is hereby fully made.
  • the compositions contain substances which absorb UV radiation in the UVB range and substances which absorb UV radiation in the UVA range, the total amount of the filter substances being, for example, 0.1 to 30% by weight, preferably 0.5 to 20% by weight %, in particular 1 to 15% by weight, based on the total weight of the compositions, in order to provide cosmetic compositions which protect the skin from the entire range of ultraviolet radiation.
  • sunscreen agents in the human epidermis cosmetic or dermatological compositions consist of compounds which absorb UV light in the UV-B range.
  • the proportion of UV-A absorbers to be used according to the invention is from 10 to 90% by weight, preferably 20 to 50 wt .-% based on the total amount of UV-B and UV-A absorbing substances.
  • Pearlescent Wax Suitable pearlescent waxes for the cosmetic compositions according to the invention are described, for example, on page 50, line 1 to line 16 of WO 2006/106140. The content of said text is hereby incorporated by reference.
  • compositions of the invention may further contain glitter and / or other effect substances (e.g., color streaks).
  • the cosmetic compositions according to the invention are present in the form of emulsions in a preferred embodiment of the invention.
  • the preparation of such emulsions is carried out by known methods.
  • Suitable emulsifiers for the emulsions according to the invention are described, for example, on page 50, line 18 to page 53, line 4 of WO 2006/106140. The content of said text is hereby incorporated by reference.
  • perfume oils are to be added to the cosmetic compositions according to the invention, suitable perfume oils are described, for example, on page 53, line 10 to page 54, line 3 of WO 2006/106140. The content of said text is hereby incorporated by reference.
  • the cosmetic compositions of the invention further contain pigments.
  • the pigments are usually present in undissolved form in the product and may be present in an amount of from 0.01 to 25% by weight, particularly preferably from 0.5 to 15% by weight.
  • the preferred particle size is 0.01 to 200 .mu.m, in particular 0.1 to 150 .mu.m, particularly preferably 1 to 100 microns.
  • Suitable pigments for the compositions according to the invention are described, for example, on page 54, line 5 to page 55, line 19 of WO 2006/106140. The content of the above text is hereby incorporated by reference in its entirety.
  • the cosmetic compositions according to the invention comprise, in addition to the polymers obtainable by the process according to the invention, further polymers.
  • Preferred further polymers are water-soluble or water-dispersible polymers.
  • Further polymers suitable for the compositions according to the invention are described, for example, on page 55, line 21 to page 63, line 2 of WO 2006/106140. The content of said text is hereby incorporated by reference. Particular mention may be made here of N-vinylpyrrolidone polymers such as poly-N-
  • the polymers obtainable by the process according to the invention are particularly suitable for the preparation of hair setting agents and hair gels.
  • the combination with so-called styling polymers is preferred.
  • Examples of such styling gels are mentioned in EP 1435226 B1, paragraphs [0020] to [0050], to which reference is hereby made in its entirety.
  • These styling polymers are present in the formulations preferably in an amount of 0.1 to 20 wt .-%, more preferably from 0.5 to 15 wt .-%, based on the preparation.
  • a preferred embodiment of the invention are hair shampoos containing the polymers obtainable by the process according to the invention.
  • Shampoos may have additional requirements depending on hair quality or scalp problem. The mode of action of the preferred shampoo types with the most important additional effects or important special objectives is described below.
  • Shampoos for normal or fast-greasy or damaged hair, antidandruff shampoos, baby shampoos and 2-in-1 shampoos are preferred according to the invention.
  • Hair shampoos according to the invention are intended to rid the hair and scalp of the skin fat formed in sebaceous glands, the inorganic salts, sweat glands with water, amino acids, urea and lactic acid, shed skin particles, environmental dirtiness, odors and possibly residues of hair cosmetic treatments.
  • Normal hair means short to shoulder-length hair, which is only slightly damaged. Accordingly, the proportion of conditioning adjuvants should be optimized for this type of hair.
  • Shampoos for fast-greasy hair according to the invention an increased production of the oil of the sebaceous glands of the scalp results in a lank, unsightly hairstyle only 1-2 days after shampooing. Oil and waxy skin fat components complicate the hair and reduce the friction from hair to hair and thus reduce the hairstyle hold.
  • the actual hair cosmetic problem with fast greasy hair is therefore the premature collapse of voluminous hairstyles. To avoid this, one must prevent the hair surface from being weighted and becoming too smooth and supple. This is preferably achieved by the surfactant base of well-cleansing and particularly less substantively pronounced wash raw materials. Additional care Substances that would add to the skin fat, such as moisturizing substances are not used in shampoos for fast-greasy hair or only with great caution. Inventive volumizing shampoos for fine hair can be formulated in a comparable manner.
  • Shampoos according to the invention for dry, damaged (damaged) hair The structure of the hair is damaged in the course of hair growth by mechanical influences such as combing, brushing and, above all, toupieren (combing the direction of growth), by the action of UV radiation or visible light and altered by cosmetic treatments, such as perming, bleaching or coloring.
  • the cuticle of the hair has an increasingly strained appearance from root to tip; in extreme cases, it is completely worn away at the top, and the hair tips are split (hair splitting). Damaged hair can basically no longer be returned to the state of healthy hair growth. However, it is possible to come very close to this ideal state in terms of grip, gloss and combability by using shampoos according to the invention with optionally high levels of care substances (conditioning agents).
  • a hair care composition according to the invention for example in the form of a rinse or spa treatment after shampooing.
  • Flushing or curative compositions for hair which comprise polymers obtainable by the process according to the invention are likewise in accordance with the invention.
  • 2-in-1 shampoos according to the invention are especially highly nourishing shampoos, in which the additional benefit of care is provided equally to the basic benefits of cleaning as a "shampoo and rinse in one.”
  • 2-in-1 compositions according to the invention contain increased amounts Anti-dandruff shampoos: Anti-dandruff shampoos according to the invention have the advantage, in comparison to antidandruff hairs, that they reduce the formation of new visible dandruff and prevent them from being used for long periods by means of appropriate antidandruff agents, but also shed off already exfoliated dandruff after shampooing However, the wash liquor remains only a small but adequate proportion of the active ingredients on the scalp and hair There are various anti-dandruff active ingredients that can be incorporated into the shampoo compositions according to the invention, such as, for example, zinc pyrithione, ketone okonazole, elubiol, clotrimazole, climbazole or piroctone olamine. In addition, these substances have a normalizing the Absc
  • the basis of antidandruff shampoos is largely the formulation of shampoos for normal hair with good cleansing effect.
  • Baby shampoos in a preferred embodiment of the invention, the shampoo preparations according to the invention are baby shampoos. These are optimally skin and mucous membrane compatible. Combinations of washing raw materials with very good skin compatibility form the basis of these shampoos. Additional substances for further improvement of the skin and mucous membrane compatibility and the care properties shadows are advantageously added, such as. Nonionic surfactants, protein hydrolysates and panthenol or bisabolol. All necessary raw materials and auxiliaries, such as preservatives, perfume oils, dyes, etc., are selected in terms of high compatibility and mildness.
  • Dry scalp shampoos in another preferred embodiment of the invention, are shampoo for dry scalp.
  • the primary goal of these shampoos is to prevent dehydration of the scalp, as dry scalp can cause itching, redness and inflammation.
  • combinations of washing raw materials with very good skin compatibility form the basis of these shampoos.
  • moisturizers and humectants such as. As glycerol or urea, are used.
  • the shampoo compositions according to the invention can also be present as shampoo concentrates with increased surfactant contents of 20-30% by weight. They are based on special washing raw material combinations and consistency regulators, which ensure the good dispensing capacity and the spontaneous foaming capacity, even for a small application quantity.
  • a particular advantage is, for example, the ability to reach the yield of 200 ml of shampoo with a 100 ml bottle.
  • compositions according to the invention are stored in and / or used in a bottle or squeeze bottle. Accordingly, bottles or squeeze bottles which contain a composition according to the invention are also according to the invention.
  • the polymers obtainable by the process according to the invention, as defined above, can preferably be used in shampoo formulations, in particular as conditioning agents. Contain preferred shampoo formulations
  • compositions according to the invention which contain the polymers obtainable by the process according to the invention are, for example, soaps and syndets.
  • Soap is formed in the reaction of a (neutral) fat or derived fatty acids or fatty acid methyl ester with sodium or potassium hydroxide (saponification) .
  • Soap is chemically the alkali salt of fatty acids in the composition Mixture with coconut oil or palm kernel oil and, more rarely, other natural oils or greases used in the production of soaps, whereby the quality of the starting fats is strongly influencing the quality of the soap obtained therefrom.
  • the fat components Important for the selection of the fat components is the distribution of the chain lengths of the corresponding fatty acids. Normally, C12-C18 fatty acids are in particular demand. Since laurate soap foams particularly well, lauric-rich coconut oil or similarly-built palm kernel oil is usually used in higher proportions (up to 50% of the neutral fat mixture) for soaps where much foam is desired in use.
  • the sodium salts of said fatty acid mixtures are solid, while the potassium salts are soft and pasty.
  • caustic soda is preferably used as the alkaline component for the preparation of solid soaps
  • potassium hydroxide solution is preferably used for liquid-pasty soaps.
  • saponification the ratio of lye to fatty acid is chosen so that at most a minimal excess of alkali (max.0.05%) is present in the finished soap bar.
  • the soaps are usually toilet, core, transparent, luxury, cream, freshness / deodorant, baby, skin protection, Abrasiv-, swimming and liquid soaps and wash pastes and soap flakes counted.
  • soaps according to the invention advantageously also contain antioxidants, complexing and humectants as well as optionally fragrances, dyes and other cosmetically acceptable ingredients.
  • antioxidants such as antioxidants, complexing and humectants as well as optionally fragrances, dyes and other cosmetically acceptable ingredients.
  • Syndets (from English, synthetic detergent) are alternatives to the traditional soap, which has certain advantages due to its different composition compared to soap, where soap has rather disadvantages. Syndets contain washing-active substances (surfactants) as foam and cleaning components, which are obtained by chemical synthesis. Soaps, however, are - as described - salts of naturally occurring fatty acids.
  • fatty acid isethionates sodium cocoyl isethionate
  • sulfosuccinic acid half esters sodium lauryl sulfosuccinates
  • alkyl polyglucosides decyl glucosides
  • amphoteric surfactants for example sodium cocoamphoacetate
  • monoglyceride sulfate and ether carboxy latee occasionally play a role.
  • Fatty alcohol sulfate eg sodium lauryl sulphate
  • the basic surfactants are combined with builders, lipid repellents and other additives into formulations that can be processed according to standard soap technology and produce pieces that are as "soap-like" as possible, but without the mentioned disadvantages of the soap.They foam at every water hardness and have a very high good cleaning power Your pH is adjustable in a wide range (usually between 4 and 8).
  • the proportion of surfactant in the syndet is usually significantly lower, the proportion of superfatting agents significantly higher than in soaps, without the foaming power being reduced. Syndets are especially recommended for cleansing sensitive skin, youthful impure skin and for facial cleansing.
  • Combars derived from Combination bar. These are pieces that contain both soap and syndettenside. Combars contain 10 to 80 wt .-% soap. They represent a compromise between soaps and syndets for the criteria of cost, foamability, skin feel and compatibility. When washing with a Combar, depending on its soap content, a pH of about 7 to 9 sets.
  • Another object of the invention is the use of a polymer obtainable by the process according to the invention as a thickener in pharmacy for the modification of rheological properties.
  • a preferred subject of the invention are cosmetic preparations in the form of a hair gel or a shampoo which contain the polymers obtainable by the process according to the invention.
  • the polymers obtainable by the process according to the invention are particularly suitable as thickeners in hair gels, in particular so-called styling gels.
  • a preparation suitable for styling gels according to the invention can be composed, for example, as follows:
  • polymers obtainable by the process according to the invention can be used as gel formers alone or together with further customary gel formers.
  • Such other conventional gelling agents are slightly crosslinked polyacrylic acid, for example carbomer (INCI), cellulose derivatives, e.g. Hydroxypropyl cellulose, hydroxyethyl cellulose, cationic modified celluloses, polysaccharides, e.g.
  • the polymers obtainable by the process according to the invention can be used excellently in shampoo formulations as thickeners.
  • Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoxy sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin sulfonates, especially the alkali and alkaline earth metal salts, e.g. Sodium, potassium, magnesium, calcium, and ammonium and triethanolamine salts.
  • the alkyl ether sulfates, alkyl ether phosphates and alkyl ether carboxylates can have between 1 to 10 ethylene oxide or propylene oxide units, preferably 1 to 3 ethylene oxide units in the molecule.
  • Suitable examples are sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl sulfate, ammonium lauryl ether sulfate, sodium lauroyl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate.
  • Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or -propionates, alkylamphodiacetates or -dipropionates.
  • cocodimethylsulfopropyl betaine cocodimethylsulfopropyl betaine, lauryl betaine, cocamidopropyl betaine or sodium cocamphopropionate can be used.
  • Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols having 6 to 20 C atoms in the alkyl chain, which may be linear or branched, with ethylene oxide and / or propylene oxide.
  • the amount of alkylene oxide is about 6 to 60 moles per mole of alcohol.
  • alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, alkylpolyglycosides or sorbitan ether esters are also suitable.
  • the shampoo formulations may contain conventional cationic surfactants, e.g. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • conventional cationic surfactants e.g. quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
  • customary conditioning agents can be used in combination with the polymers obtainable by the process according to the invention to achieve certain effects.
  • these include, for example, cationic polyme- re with the INCI name Polyquaternium, in particular copolymers of vinylpyrrolidone / N-vinylimidazolium salts (Luviquat ® FC, Luviquat ® HM, Luviquat ® MS, Luviquat Care ®), copolymers of N-vinylpyrrolidone / dimethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat ® (PQ 1: 1), copolymers of N-vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium Luviquat Hold ®); cationic cellulose derivatives (polyquaternium-4 and -10), acrylamide copolymers (polyquaternium),
  • protein hydrolysates can be used, as well as conditioning substances based on silicone compounds, for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
  • silicone compounds for example polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
  • suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA).
  • Preferred preparations containing the polymer obtainable by the process according to the invention are: shampoos
  • Trigonox ® 101 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane
  • Hypermer ® B 246 polyethylene glycol-polyester block copolymer
  • Wax rice wax 2811 (Kahl)
  • Butyl acetate 400 g The original was heated to about 60 ° C. while passing through nitrogen and stirring. Feed 1 was added within 4 hours. After about 15 minutes, initial turbidity was observed. 30 minutes after the start of feed 1 feed 2 was added within 4.5 hours. 60 minutes after the start of feed 1 feed 3 was added within 4 hours. After the end of feed 2 was heated to 70 0 C and stirred for 3 hours. It was then heated to 80 ° C and stirred at this temperature for a further 3 hours. Subsequently, the suspension was polymerized at 90 0 C for 2 hours. The product was isolated by filtration and dried at about 70 0 C for 20 hours.
  • Analog was polymerized in Experiment S1 in ethyl acetate with Wako V59 ® at a temperature of 80 ° C.
  • the original was heated to about 60 ° C. while passing through nitrogen and stirring. Feed 1 was added within 4 hours. After about 15 minutes, initial turbidity was observed. 30 minutes after the start of feed 1 feed 2 was added within 4.5 hours. 60 minutes after the start of feed 1 feed 3 was added within 4 hours. After the end of feed 2 was heated to 70 0 C and stirred for 3 hours. It was then heated to 80 0 C and stirred at this temperature for a further 3 hours. Subsequently, the suspension was added Postpolymerization 90 0 C for 2 hours. The product was isolated by filtration and dried at about 70 0 C for 20 hours.
  • the original was heated to about 60 ° C. while passing through nitrogen and stirring. Feed 1 was added within 4 hours. After about 15 minutes, initial turbidity was observed. 30 minutes after the start of feed 1 feed 2 was added within 4.5 hours. After the end of feed 2 was heated to 75 ° C and stirred for a further 3 hours. It was then heated to 90 0 C and stirred at this temperature for a further 3 hours. Subsequently, the suspension was polymerized at 90 0 C for 2 hours. The product was isolated by filtration and dried at about 70 0 C for 20 hours.
  • Trigonox ® 101 2.5 g
  • the original was heated to about 75 ° C. while passing through nitrogen and stirring. Feed 1 was added within 4 hours. After about 15 minutes, initial turbidity was observed. 30 minutes after the start of feed 1 feed 2 was added within 4.5 hours. After the end of feed 2 was heated to 75 ° C and stirred for a further 3 hours. It was then heated to 80 0 C and stirred at this temperature for a further 2 hours. Subsequently, the suspension was polymerized at 120 0 C for 1 hour. The product was isolated by filtration and dried at about 70 0 C for 20 hours.
  • Examples 22, 24 and 25 were carried out in a printing apparatus.

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Abstract

L'invention concerne un procédé de production de polymères de l'acide acrylique réticulés, lequel procédé se caractérise en ce qu'il consiste en une polymérisation par précipitation mise en oeuvre dans un solvant contenant un hydrocarbure et/ou un alkylester à au moins deux températures différentes et avec au moins deux amorceurs différents. L'invention concerne également des polymères réticulés pouvant s'obtenir par ledit procédé ainsi que des préparations cosmétiques et pharmaceutiques contenant de tels polymères.
EP08786869A 2007-08-21 2008-08-05 Procédé de production de polymères de l'acide acrylique réticulés Withdrawn EP2181123A1 (fr)

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EP07114682 2007-08-21
PCT/EP2008/060258 WO2009024457A1 (fr) 2007-08-21 2008-08-05 Procédé de production de polymères de l'acide acrylique réticulés
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EP2511331A1 (fr) 2011-04-12 2012-10-17 Basf Se Polymère pauvre en peroxyde comprenant un composé phosphore
US9023931B2 (en) 2011-04-12 2015-05-05 Basf Se Oxidation-sensitive, low-peroxide polymer comprising at least one inorganic phosphorus compound
DE202011005055U1 (de) 2011-04-12 2011-09-12 Basf Se Peroxidarmes Polymer enthaltend Phosphorverbindung
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US9260546B2 (en) 2012-08-08 2016-02-16 Basf Se Producing aqueous solutions of vinyllactam polymers and powders thereof
EP2890736A1 (fr) 2012-08-28 2015-07-08 Basf Se Mélanges de conservateurs et solutions polymères stabilisées au moyen de ceux-ci
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JP2019506464A (ja) * 2015-12-08 2019-03-07 ケミラ・オー・ウー・イィー 液体状ポリマー組成物
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