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
  • C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen

Definitions

• the present invention relates to precipitation polymers obtainable by polymerization of a monomer mixture containing from 30 to 99% by weight of at least one nonionic water-soluble monomer a) and at least one monomer other than a) selected from i) monomers carrying at least one hydroxyl group, ii) anionic monomers and iii Mixtures of i) and ii), optionally a monomer c) carrying at least one amino group, optionally further monomers, where the total amount of a), b), c) and d) is 100% by weight and wherein the monomer mixture is based to the total amount of a), b), c) and d) less than 0.1 wt .-% of a monomer having at least 2 free-radically polymerizable double bonds per molecule.
• the invention further relates to the use of these polymers as rheology modifiers for aqueous compositions, to aqueous compositions containing these polymers and to the use of the polymers for thicken
• Cosmetic, pharmaceutical and technical agents often have special requirements with respect to their rheological properties. Often they can only be brought into the desired form of application with the aid of additives, so-called thickeners. Examples of customary low molecular weight thickeners are, for. As the alkali and aluminum salts of fatty acids, fatty alcohols or waxes.
• the use of the known thickening agents depending on the application of the preparation to be thickened, often associated with disadvantages. Thus, either the thickening effect of the thickener unsatisfactory, their use undesirable or their incorporation into the preparation to be thickened, for example, because of their incompatibility with the compound to be thickened difficult or impossible.
• a common further disadvantage when using polymers as thickeners for the preparation of higher-viscosity or gel-like preparations is that with increasing molecular weight of the polymer whose incorporation is generally difficult, and finally, often only a swelling of the polymer instead of the desired solution is observed , Difficulties often arise in the provision of products with a complex property profile using as small a proportion as possible or as few as possible of different active substances.
• WO 00/39176 describes a hydrophilic, cationic, ampholytic copolymer comprising from 0.05 to 20 mol% of an anionic monomer having at least one carboxyl group, from 0 to 45 mol% of a cationic monomer having at least one amino group and optionally one contains copolymerized hydrophobic monomer and / or a crosslinker, wherein the molar ratio of cationic to anionic monomer is about 2: 1 to 16: 1.
• These copolymers may u. a. to modify the rheological properties of personal care products.
• WO 97/21744 describes crosslinked anionic copolymers and their use as thickeners and dispersants in aqueous systems.
• EP-A-0 982 021 describes the use of (partially) neutralized copolymers
• DE-A-42 13 971 describes copolymers which contain at least one olefinically unsaturated acid group-containing monomer, at least one olefinically unsaturated quaternary ammonium compound, if appropriate at least one polyether (meth) acrylate and optionally at least one crosslinker in copolymerized form and whose Use as a thickener for thickening aqueous systems which may be cosmetic preparations.
• EP-A-893 1 17 and EP-A-913 143 describe crosslinked cationic copolymers and their use, and the like. a. as hair-setting gelling agents in cosmetic compositions.
• EP-A-1 064 924 describes the use of crosslinked cationic polymers in skin cosmetic and dermatological preparations, and the like. a. as a thickener.
• No. 5,015,708 describes a process for the preparation of a terpolymer from (i) a vinyl lactam, (ii) an acid group-containing monomer and (iii) a hydrophobic monomer, wherein u. a. may be an ethylenically unsaturated silicone compound, by precipitation polymerization and the preparation of powders of these polymers.
• WO 01/62809 describes a cosmetic composition containing at least one water-soluble or water-dispersible polymer which comprises a) from 5 to 50% by weight of at least one ethylenically unsaturated monomer having a tert-butyl group, b) from 25 to 90% by weight at least c) from 0.5 to 30% by weight of at least one compound having a free-radically polymerizable, ethylenically unsaturated double bond and at least one cationogenic and / or cationic group per molecule, and d) 0 to 30 wt .-% of at least one further ethylenically unsaturated compound, which may be compounds having at least one anionogenic and / or anionic group per molecule incorporated incorporated.
• WO 04/058837 describes an ampholytic copolymer which is prepared by free-radical co-polymerization of a) at least one ethylenically unsaturated compound having at least one anionogenic and / or anionic group, b) at least one ethylenically unsaturated compound having at least one cationogenic and / or cationic group, c) at least one unsaturated amide-containing compound and optionally further comonomers is obtainable.
• the polymerization can be carried out in the presence of a grafting base, which may inter alia be a polyalkylene oxide-containing silicone derivative.
• WO 07/012610 describes a silicone group-containing copolymer A) obtainable by free-radical copolymerization of a) at least one compound having a free-radically polymerizable, ethylenically unsaturated double bond and at least one ionogenic and / or ionic group per molecule, b) at least one free-radically polymerizable crosslinking compound containing at least two unsaturated double bonds per molecule, in the presence of at least one silicone compound containing a polyether group and / or a radically polymerisable olefinically unsaturated double bond c).
• WO 07/010035 describes the use of an ampholytic copolymer which has a molar excess of anionogenic / anionic groups with respect to cationogenic / cationic groups or which has a molar excess of cationogenic / cationic groups with respect to anionogenic / anionic groups and which is obtainable by free-radical copolymerization of a1) at least one compound having a free-radically polymerizable, ethylenically unsaturated double bond and at least one anionogenic and / or anionic group per molecule, a2) at least one compound having a free-radically polymerizable, ethylenically unsaturated double bond and at least one cationogenic and / or cationic Group per molecule, b) at least one free-radically polymerizable crosslinking compound containing at least two ethylenically unsaturated double bonds per molecule, c) optionally in the presence of at least one polyether group and / or r
• Silicone compound as a rheology modifier for hair cosmetic compositions.
• these polymers should be converted into a solid form, preferably a powder, which can easily be incorporated into the formulations to be thickened.
• the polymers provided are intended to improve further performance properties of the compositions modified with them, in particular their sensory properties.
• polymeric thickeners for hair cosmetic compositions which are useful for formulating gel preparations. These should combine as many of the following properties as possible: the resulting gels should be as clear as possible, the resulting gels should be easy to distribute in the hair and give it good support, which can be achieved particularly well by gels with thixotropic properties, the gels obtained should themselves have film-forming properties and thus contribute to the strengthening of the hair, the gels obtained should have conditioning properties and improve the sensory properties of the hair, z. B.
• the hair treated with the gels obtained should have a good wet combability (thus, the freshly treated hair can easily bring with the comb in shape to the desired hairstyle
• the polymers are intended to allow the formulation of gels in as far as possible in all cosmetically acceptable pH ranges, especially in the pH range of about 3 to 9; the polymers are said to permit the formulation of gels whose properties are better than the pH. Be switched value, the polymers should be jointly formulated with thickeners whose molecular charge carries the same sign.
• polymers obtainable by precipitation polymerization of a monomer mixture which comprises a) from 30 to 99% by weight of at least one nonionic water-soluble monomer b) at least one monomer other than a) selected from i) bearing at least one hydroxyl group Monomers, ii) anionic monomers, iii) mixtures of i) and ii), c) optionally a monomer bearing at least one amino group, d) optionally further monomers, wherein the total amount of a), b), c) and d) is 100 wt .-% and wherein the monomer mixture, based on the total amount of a), b), c) and d) contains less than 0.1 wt .-% of a monomer having at least 2 free-radically polymerizable double bonds per molecule.
• Preferred polymers according to the invention are obtainable by precipitation polymerization of a monomer mixture which comprises a) 30 to 99% by weight of at least one nonionic water-soluble monomer b) at least one monomer other than a) selected from i) monomers carrying at least one hydroxyl group, ii) anionic monomers, iii) mixtures of i) and ii), with the proviso that the monomer mixture further contains c) at least one monomer bearing at least one amino group, if b) is selected from ii) or iii), d) optionally further monomers, wherein the total amount of a), b), c) and d) is 100% by weight and wherein the monomer mixture, based on the total amount of a), b), c) and d) contains less than 0.1% by weight of a monomer having at least 2 free-radically polymerizable double bonds per molecule.
• Particularly preferred polymers according to the invention are obtainable by precipitation polymerization of a monomer mixture which comprises a) 30 to 85% by weight of at least one nonionic water-soluble monomer, b) at least one anionic monomer, c) at least one free-radically polymerizable imidazole compound, d) optionally other monomers d), wherein
• the total amount of a), b), c) and d) is 100% by weight
• the monomer mixture based on the total amount of a), b), c) and d), contains less than 0.1% by weight of a monomer having at least 2 free-radically polymerizable double bonds per molecule and - the total amount of b) + c), based on the total amount of a), b), c) and d), in the range of 15 to 70 wt .-% is and
• the ratio of the molar amounts of b) to c) is not in the range of 1: 2 to 2: 1.
• alkyl includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched Ci-Cz-alkyl, preferably d-C ⁇ -alkyl and particularly preferably Ci-C4-alkyl groups.
• Suitable longer-chain Cs-Cso-alkyl or Cs-Cso-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 Cs-Cs-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.
• anionic means a compound which is either in anionic form or can be converted by deprotonation into an anionic form
• anionic compounds are compounds containing COOH, COO 2, or SO 2 H groups.
• cationic in the context of this invention is understood as meaning a compound which is either present in cationic form or can be converted into a cationic form by protonation or quaternization, in particular alkylation, Examples of cationic compounds are amino-containing compounds.
• the polymers according to the invention can advantageously be formulated as gels under normal conditions (20 ° C., 1 bar).
• "Gel-like consistency” show formulations which have a higher viscosity than a liquid and which are self-supporting, ie retain the shape given to them without a shape-stabilizing coating.
• gel formulations are easily deformed using shear forces.
• the viscosity of the gelled agent is preferably in a range of greater than 600 to about 60,000 mPas, more preferably from 6,000 to 30,000 mPas.
• water-soluble monomers and polymers are understood as meaning monomers and polymers which clearly dissolve in water at 20 ° C. for at least 1 g / l, preferably at least 10 g / l for the human eye.
• Water-dispersible monomers and polymers are understood as meaning monomers and polymers which decompose into dispersible particles with the aid of shearing forces, for example by stirring.
• Hydrophilic monomers are preferably water-soluble or at least water-dispersible.
• the copolymers used in the invention are generally water-soluble.
• Modification of rheological properties is to be understood within the scope of the present invention:
• the polymers according to the invention are generally suitable for thickening the consistency of liquid compositions in a wide range
• the rheological properties are modified by, among other things, increasing the viscosity of liquids, improving the thixotropic properties of gels, solidifying gels and waxes Understood.
• Preferred polymers according to the invention have both anionic and cationic groups.
• the oppositely charged / chargeable monomers b) and c) can be used together, ie in the form of a monomer pair ("monomer salt")
• the molar ratio of anionic groups of component b) to cationic groups of component c about 1: 1 (ie, monovalent monomers are used in substantially equimolar amounts.)
• the pairs of monomers may be prepared separately prior to their use for polymerization.
• Suitable monomers a) are, for example, N-vinyllactams and N-vinyllactam derivatives which, for.
• one or more d-C ⁇ -alkyl substituents such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl 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.
• Preferred monomers a) are N-vinylpyrrolidone and N-vinylcaprolactam.
• a) may be selected from N-vinylamides of saturated C 1 -C 5 -s
• Monocarboxylic acids primary amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives which, in addition to the carbonyl carbon atom of the amide group, have at most 8 further carbon atoms, esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diols, amides of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols having a primary or secondary amino group, polyether acrylates and mixtures thereof.
• Suitable N-vinylamide compounds as monomers a) are, for example, 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 monomers a) are also the monomers mentioned below under monomer b), if they are water-soluble, which carry at least one hydroxyl group.
• Preferred monomers a) are N-vinyllactams and their derivatives, N-vinylamides of saturated C 1 -C 5 -monocarboxylic acids and (meth) acrylic acid amides.
• Particularly preferred monomers a) are N-vinyllactams such as N-vinylpyrrodidone (hereinafter sometimes referred to as "NVP” or “VP”) and N-vinylcaprolactam (hereinafter sometimes referred to as "VCap”).
• NVP N-vinylpyrrodidone
• VCap N-vinylcaprolactam
• a) is selected from the group consisting of N-vinylpyrrolidone, N-vinylcaprolactam, (meth) acrylamide and N-vinylformamide.
• Monomer b) is different from monomer a) and is selected from i) monomers carrying at least one hydroxyl group, ii) anionic monomers, iii) mixtures of i) and ii).
• Suitable monomers b) i) are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
• Suitable further monomers b) i) are furthermore 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, 2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide, 2-hydroxypropylmethacrylamide, 3-hydroxypropylacrylamide, 3-hydroxypropylmethacrylamide, 3-hydroxybutylacrylamide, 3-hydroxybutylmethacrylamide, 4-hydroxybutylacrylamide, 4 -Hydroxybutylmethacrylamide, 6-hydroxyhexylacrylamide, 6-hydroxyhexylmethacrylamide, 3-hydroxy-2-ethylhexylacrylamide and 3-hydroxy-2-ethylhexylmethacrylamide.
• Suitable anionic monomers b) ii) are preferably selected from monoethylenically unsaturated carboxylic acids, sulfonic acids, phosphonic acids and mixtures thereof.
• B) ii) include, in particular, 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 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 b) ii) furthermore include the half-esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10, preferably 4 to 6, carbon atoms, eg. B. from Maleic acid, such as monomethyl maleate.
• the monomers b) ii) 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-acryloxy-propylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, Styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid and allylphosphonic acid.
• monoethylenically unsaturated sulfonic acids and phosphonic acids for example, vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acryl
• the monomers b) ii) also include the salts of the abovementioned acids, in particular the sodium, potassium and ammonium salts and the salts with amines.
• the monomers b) ii) can be used as such or as mixtures with one another. The stated proportions by weight are all based on the acid form.
• b) ii) 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.
• Particularly preferred comprises or is b) ii) (meth) acrylic acid.
• the monomer mixture comprises preferably from 1 to 50, preferably from 3 to 40,% by weight of the anionic monomer b) ii), based on the total weight of all monomers a) to d).
• Monomer c) is a monomer carrying at least one amino group and is sometimes referred to below as a cationic monomer.
• monomer c) comprises at least one free-radically polymerizable imidazole compound and optionally further cationic monomers.
• Preferred free-radically polymerizable imidazole compounds are compounds of the general formula (II)
• R 5 to R 7 are independently hydrogen, Ci-C 4 -AlkVl or phenyl.
• Suitable radically polymerizable imidazole compounds are, for example, compounds of the formula
• R 5 to R 7 independently of one another represent hydrogen, C 1 -C 4 -alkyl or phenyl.
• R 5 to R 7 are hydrogen.
• Suitable radically polymerizable imidazole compounds are also the compounds obtainable by protonation or quaternization of the abovementioned compounds. Examples of such charged monomers c) are quaternized vinylimidazoles, in particular 3-methyl-1-vinylimidazolium chloride and methosulfate.
• Suitable acids or alkylating agents for protonation or quaternization are listed below.
• the preferred radically polymerizable imidazole compound is or includes N-vinylimidazole.
• the amino groups of the cationic monomers c) are primary, secondary and / or tertiary amino groups and quaternary ammonium groups.
• the amino groups are preferably tertiary amino groups or quaternary ammonium groups.
• Charged cationic groups can be prepared from neutral amino groups by protonation or by quaternization, e.g. produce with acids and / or alkylating agents. Suitable acids are e.g. Carboxylic acids such as lactic acid or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid.
• Suitable alkylating agents are, for example, C 1 -C 4 -alkyl halides or sulfates, such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. Protonation or quaternization can generally be carried out both before and after the polymerization.
• Suitable monomers c) are also the esters of o ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols.
• Preferred aminoalcohols are C 2 -C 12 -amino alcohols which are alkylated on the amino nitrogen C 1 -C 6 -dial.
• the acid component of these esters are z.
• the acid component used is preferably acrylic acid, methacrylic acid and mixtures thereof.
• Preferred monomers c) are 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 c) are furthermore the amides of the abovementioned ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group.
• diamines having a tertiary and a primary or secondary amino group.
• Suitable monomers c) are, for example, N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N - [4- (dimethylamino) cyclohexyl] acrylamide and N- [4- (dimethylamino) cyclohexyl] methacrylamide.
• Suitable monomers c) are furthermore N, N-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts and quaternization products.
• Alkyl is preferably Ci-C24-alkyl.
• chlorides and bromides include in particular N, N-diallyl-N, N-dimethylammonium chloride (DADMAC).
• Suitable monomers c) are also various vinyl- and allyl-substituted nitrogen heterocycles, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.
• the abovementioned monomers c) can each be used individually or in the form of any desired mixtures.
• the monomer mixture comprises preferably from 1 to 50, preferably from 3 to 40,% by weight of the cationic monomer c), based on the total weight of all monomers a) to d).
• monomer c) comprises a free-radically polymerizable imidazole compound and optionally further cationic monomers.
• monomer c) comprises a free-radically polymerizable imidazole compound and an N 1 N- dialkylamino (meth) acrylates such as N 1 N-dimethylaminoethyl (meth) acrylate.
• monomer c) comprises a free-radically polymerizable imidazole compound and a N 1 N- dialkylamino (meth) acrylklarealkylamid such as N- [3- (dimethylamino) propyl] acrylamide.
• the total amount of b) + c) is preferably in the range from 10 to 70, particularly preferably in the range from 20 to 50% by weight, based on the total weight of all monomers a) to d).
• Monomers d) are preferably selected from
• esters of vinyl alcohol and allyl alcohol with C 1 -C 8 monocarboxylic acids are esters of vinyl alcohol and allyl alcohol with C 1 -C 8 monocarboxylic acids
• Ci-Cs monoolefins non-aromatic hydrocarbons having at least two conjugated double bonds fertilize and
• Suitable additional monomers d) are also methyl (meth) acrylate, methyl acrylate, ethyl (meth) acrylate, ethyl methacrylate, n-butyl (meth) acrylate, 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)
• Suitable additional monomers d) are furthermore N- (n-octyl) (meth) acrylamide,
• N- (n-nonyl) (meth) acrylamide N- (n-decyl) (meth) acrylamide
• N-Arrachinyl (meth) acrylamide N-behenyl (meth) acrylamide
• N-lignocerenyl (meth) acrylamide N-cerotinyl (meth) acrylamide
• N-melissinyl (meth) acrylamide N-palmitoleinyl (meth) acrylamide
• N-Oleyl (meth) acrylamide N-linolyl (meth) acrylamide, N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-lauryl (meth) acrylamide.
• Suitable additional monomers d) are also vinyl acetate, vinyl propionate, vinyl butyrate and mixtures thereof. Suitable additional monomers d) are furthermore ethylene, propylene, isobutylene, butadiene, styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
• polyether (meth) acrylates which in the context of this invention are generally understood to mean esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with polyetherols.
• Suitable polyetherols are linear or branched, terminal hydroxyl-containing substances containing ether bonds. In general, they have a molecular weight in the range of about 150 to 20,000.
• Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers.
• Suitable alkylene oxides for the preparation of alkylene noxidcopolymeren are z.
• alkylene oxide copolymers may contain randomly distributed alkylene oxide units or in copolymerized form in the form of blocks.
• Preferred are ethylene oxide / propylene oxide copolymers.
• Preferred as component d) are poly (meth) acrylates of the general formula
• H 2 C C- ⁇ CY - (CH £ CH 2 O) k (CH 2 CH (CH 3) O) ⁇ - R a
• sequence of the alkylene oxide units is arbitrary, k and I independently of one another are an integer from 0 to 1000, the sum of k and I being at least 5,
• R a is hydrogen, C 1 -C 30 -alkyl or C 5 -C 8 -cycloalkyl
• R b is hydrogen or C 1 -C 8 -alkyl
• Y is O or NR b , where R b is hydrogen, C 1 -C 30 -alkyl or C 5 -C 8 -cycloalkyl,
• k is an integer from 1 to 500, in particular 3 to 250.
• I is an integer from 0 to 100.
• R b is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular for hydrogen, methyl or ethyl.
• R a is C 8 -C 30 -alkyl, especially C 12 -C 30 -alkyl, such as decyl, undecyl, tridecyl, myristyl, pentadecyl, palmityl, lauryl, stearyl, etc.
• Y is O or NH.
• Suitable polyether (meth) acrylates are, for.
• Suitable polyetherols can readily be prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichloroethane. lorhydrin with a starter molecule, such as water or a short-chain alcohol R a -OH.
• the alkylene oxides can be used individually, alternately in succession or as a mixture.
• Suitable polyether acrylates can also be prepared by transesterification of the esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with polyetherols.
• product mixtures result which contain both the esters used as starting materials and the polyether (meth) acrylates formed by transesterification. These mixtures can generally be used without prior separation for the preparation of the polymers according to the invention.
• the polyether (meth) acrylates can be used alone or in mixtures for the preparation of the polymers according to the invention.
• the proportion of monomers d) is preferably from 0 to 15% by weight, particularly preferably from 0.1 to 10% by weight, based on the total weight of the monomers a) to d) used for the polymerization.
• the polymers of the invention are preferably substantially linear, that is, neither branched nor crosslinked. Accordingly, the polymers according to the invention contain less than 0.1, preferably less than 0.05, more preferably less than 0.01, more preferably less than 0.001 and especially less than 0.0001% by weight of a monomer having at least 2 radically copolymerized polymerizable double bonds per molecule. Most preferably, the polymers of the invention contain no such monomers in copolymerized form.
• the polymers according to the invention are prepared by the precipitation polymerization method.
• Another object of the invention is therefore a process for the preparation of the polymers according to the invention, characterized in that it is a precipitation polymerization in the polymerization.
• At least two free-radical initiators are used for the preparation of the polymers according to the invention whose decomposition temperatures and / or their half-lives are different from one another at a certain polymerization temperature.
• copolymers can be achieved with particularly low residual monomer contents. This is especially the case when the higher temperature decomposing initiator is added before completion of the precipitation of the polymer, preferably before the precipitation of the polymer.
• the monomers used are soluble in the reaction medium comprising the monomers and the solvent, but not the resulting polymer.
• the resulting polymer becomes insoluble under the chosen polymerization conditions and precipitates.
• copolymers can be obtained with higher molecular weights than after other polymerization processes, eg. B. by solution Polymerization.
• Such copolymers having higher molecular weights are particularly advantageous as rheology modifiers, in particular as thickeners.
• the precipitation polymerization is preferably carried out in a solvent in which each of the monomers used at 20 0 C and 1 bar in an amount of at least 10 wt .-% is clearly soluble to the human eye.
• the precipitation polymerization is carried out, for example, in an ester such as ethyl acetate or butyl acetate and / or a hydrocarbon such as cyclohexane or n-heptane as solvent.
• the resulting polymer particles precipitate out of the reaction solution and can be isolated by conventional techniques such as vacuum filtration.
• the polymerization temperatures are preferably in a range from about 30 to 120 ° C., particularly preferably 40 to 100 ° C.
• the polymerization is usually carried out under atmospheric pressure, but it may also take place under reduced or elevated pressure.
• a suitable pressure range is between 1 and 5 bar.
• the customary peroxo and / or azo compounds can be used, for example alkali metal or ammonium peroxidisulfates, 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 peracetate, di-tert .
• alkali metal or ammonium peroxidisulfates diacetyl peroxide, dibenzoy
• initiator mixtures or redox initiator systems e.g. Ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert. Butyl hydroperoxide / sodium hydroxymethanesulfinate, H2O2 / Cu (l).
• the polymerization can be carried out in the presence of at least one regulator.
• Regulators may be the usual compounds known to those skilled in the art, e.g. Sulfur compounds, e.g. Mercaptoethanol, 2-ethylhexyl thioglycolate, thioglycolic acid or dodecyl mercaptan and Tribromchlor- methane or other compounds which act to regulate the molecular weight of the resulting polymers are used.
• a preferred regulator is cysteine.
• a postpolymerization step can be added to the polymerization (main polymerization).
• the post-polymerization can be carried out in the presence of the same or a different initiator system as the main polymerization.
• the postpolymerization is preferably carried out at least at the same, preferably at a higher temperature than the main polymerization.
• the temperature in the main and the postpolymerization on is preferably at most 100 0 C (main reaction) and 130 0 C (postpolymerization).
• the precipitated polymer is isolated from the reaction mixture after the postpolymerization step, for which any customary method for isolating the polymers in the conventional precipitation polymerization can be used. Such methods are filtration, centrifugation, evaporation of the solvent or combinations of these methods. For further purification of the polymer from unpolymerized constituents, the polymer may be washed. In principle, one can use the same solvents as are suitable for the polymerization.
• the polymer dry powders preferably obtained can advantageously be converted into an aqueous solution or dispersion by dissolving or redispersing in water. Powdered copolymers have the advantage of better storage stability and easier transportation and generally show a lower tendency for microbial attack.
• the acid groups of the polymers can be partially or completely neutralized with a base.
• a base for the neutralization of the polymers can alkali metal bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate or
• Kaliumhydrogencarbonat and alkaline earth metal bases such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate and amines can be used.
• Suitable amines are, for. B. C1-C6-alkylamines, preferably n-propylamine and n-butylamine, dialkylamines, preferably diethylpropylamine and dipropylmethylamine, trialkylamines, preferably triethylamine and triisopropylamine.
• amino alcohols e.g.
• Tri- alkanolamines such as triethanolamine, alkyl dialkanolamines, such as methyl or ethyldiethanolamine and dialkylalkanolamines, such as dimethylethanolamine and 2-amino-2-methyl-1-propanol.
• 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-propane-1,3-diol, diethylaminopropylamine and triisopropanolamine have proved particularly suitable for use in hair treatment agents for neutralizing the polymers containing acid groups.
• the neutralization of the acid groups can also be carried out with the aid of mixtures of several bases, for.
• Charged cationic groups can be prepared, for example, from the amino groups either by protonation, for.
• mono- or polybasic carboxylic acids such as lactic acid or tartaric acid, or with mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid, or by quaternization, for.
• alkylating agents such as C1 to C4 alkyl halides or sulfates. Examples of such alkylating agents are ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate.
• the polymers according to the invention can be used, in particular as thickeners, in aqueous preparations in the household, personal care, construction industry, textile, paper coating slips, pigment printing pastes, aqueous paints, leather treatment compositions, cosmetic formulations, pharmaceutical products and agrochemicals.
• Another object of the invention are therefore cosmetic and / or pharmaceutical preparations containing the polymers of 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 nolaurate, polyethylene glycol monolaurate, iso-C 1-6 alkyl lactates, etc., and mixtures thereof.
• the oil component B) may also be selected from silicone oils such.
• silicone oils such as linear polydimethylsiloxanen, poly (methylphenyl) siloxanes, cyclic siloxanes and mixtures thereof.
• the number-average molecular weight of the polydimethylsiloxanes and poly (methylphenyl) siloxanes is preferably in a range from about 1000 to 150000 g / mol.
• Preferred cyclic siloxanes have 4- to 8-membered rings.
• Suitable cyclic siloxanes are, for. B. commercially available under the name cyclomethicone.
• 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, and mixtures of the aforementioned oil or fat components.
• Suitable cosmetically and pharmaceutically acceptable oil or fat components B) are also described in Karl-Heinz Schrader, Kunststoffn 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, for example, 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.
• the cosmetic preparations according to the invention may be skin-cosmetic, hair-cosmetic, dermatological, hygienic or pharmaceutical preparations. Due to their properties, the polymers 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, spray, ointment, cream, emulsion, suspension, lotion, milk or paste. te ago. 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) 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, other thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaches, gelling agents, conditioners, colorants, tints, tanning agents, dyes, pigments, bodying agents, moisturizers, fats, collagen, protein hydrolysates, lipids, antioxidants, defoamers, antistatic agents, emollients and softeners.
• cosmetically active ingredients emulsifiers, surfactants, preservatives, perfume oils, other thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or dispersible silicone-containing polymers, light stabilizers, bleaches, gelling agents, conditioners, colorants,
• 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. Accordingly, the invention also relates to preparations for 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 as W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-aging creams, mimic creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, body lotions and moisturizing lotions.
• the polymers according to the invention are furthermore suitable as thickeners for skin cosmetic preparations, face masks, cosmetic lotions and for use in decorative cosmetics, for example for masking, theatrical paints, mascara and eye shadows, lipsticks, kohl pencils, eye liners, make-up, foundations, blushes 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.
• washing, showering and bathing preparations containing the polymers 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.
• the preparations according to the invention preferably comprise 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 vitamin A, E and C, retinol, bisabolol, panthenol, natural and synthetic light stabilizers, natural substances, opacifiers, solubilizers, repellents,
• 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 vitamin A, E and C, retinol, bisabolol, panthenol, natural and synthetic light stabilizer
• Bleaching agents colorants, tinting agents, browning 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 (eg wheat, almond or pea proteins), ceramide, protein hydrolysates, salts, gelling agents, bodying agents, silicones, humectants (eg 1, 2-pentanediol), moisturizers, UV light protection filters and other customary additives.
• other polymers may also be present to adjust the particular desired properties.
• the cosmetic preparations according to the invention contain the polymers of the invention in an amount of 0.01 to 10 wt .-%, preferably 0.05 to 5 wt .-%, particularly preferably 0.1 to 1, 5 wt .-%, based on the Weight of the preparation.
• shower gels, washing, shower and bath preparations as well as shampoos and hair-care preparations according to the invention furthermore contain at least one surfactant.
• shampoos and hair-care preparations according to the invention additionally contain, 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, which is 4 Covalently bonded alkyl or aryl groups.
• 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, alkylpolyglycosides such as lauryl glucoside, decyl glycoside and cocoglycoside, glycosides having an HLB value of at least 20 (for example BeififG 128V (Wacker)).
• nonionic surfactants are alcohols and amine oxides, such as cocoamidopropylamine oxide.
• Preferred anionic, amphoteric and nonionic shampoo surfactants are mentioned, for example, in "Kosmetik und Hygiene von Kopf bisfite", 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 this is inferior in mildness. Alkyl ether carboxylates of moderate and especially higher degree of ethoxylation are among the mildest surfactants ever, but show poor foam and viscosity behavior.
• 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. In combination with anionic surfactants, their mildness can be synergistically improved.
• 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.
• 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. It is inventively advantageous if one or more of these surfactants in a concentration of 1 to 30% by weight, preferably in a concentration of 5 to 25% by weight and most preferably in a concentration of 10 to 20% by weight, respectively be used based on the total weight of the preparation.
• Polysorbates can also advantageously be incorporated into the preparations according to the invention as detergent-active agents.
• advantageous polysorbates are, for example
• polystyrene foam a polyoxyethylene (20) sorbitan monostearate (Tween ® 60, CAS 9005-67-8 number.).
• the polysorbates are advantageously used 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 several polysorbates.
• 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 rheology of the preparations according to the invention can be adjusted to the desired value by addition of the polymers according to the invention.
• further 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.
• compositions with high water contents must be reliably protected against microbial contamination.
• the cosmetic preparations according to the invention preferably also contain preservatives. 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 light protection filters for the erfindungsge-
• 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 said text is hereby incorporated by reference.
• 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 solubilizers 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 washing lotions. 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 efficacy.
• Triclosan 2,4,4'-trichloro-2'-hydroxydiphenyl ether
• chlorhexidine (1,1'-hexamethylenebis [5- (4-chlorophenyl)
• 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 persistent in
• Hydrocolloids e.g. As xanthan gum or carbomers are used.
• 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.
• the 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, electrolytes, organic solvents or silicone derivatives.
• 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 fatty 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
• 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.
• Active ingredients with different solubilities can be incorporated homogeneously into the compositions according to the invention.
• 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.
• compositions according to the invention contain UV light stabilizers for protecting the skin and / or the hair.
• UV light stabilizers are described in detail in WO 2006/106114, p. 24, Z.4 to p. 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 filter substances being e.g. 0.1 to 30% by weight, preferably 0.5 to 20% by weight, especially 1 to 15% by weight, based on the total weight of the compositions, of providing cosmetic compositions comprising the skin protect the entire range of ultraviolet radiation.
• Most of the 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 the UV-A absorbers to be used according to the invention is from 10 to 90% by weight, preferably from 20 to 50% by weight, 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.
• the 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 contained in an amount of 0.01 to 25% by weight, particularly preferably 0.5 to 15% by weight.
• the preferred particle size is 0.01 to 200 .mu.m, in particular 0.02 to 150 .mu.m, particularly preferably 0.05 to 100 .mu.m.
• 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 said text is hereby incorporated by reference.
• compositions according to the invention comprise water-insoluble nanoparticles, that is to say particles with a particle size in the range from 1 to 200, preferably from 5 to 100 nm.
• Preferred nanoparticles are nanoparticles of metal oxides, in particular of zinc oxide and / or titanium dioxide.
• the cosmetic compositions according to the invention contain, in addition to the polymers according to the invention, further polymers.
• Preferred further polymers are water-soluble or water-dispersible polymers, with water-soluble polymers being particularly preferred.
• 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.
• a preferred embodiment of the invention are hair shampoos containing the polymers of 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.
• Hair shampoos for normal or fast-greasy or damaged hair 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 dirt, 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 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 constituents Renew the hair and reduce the friction from hair to hair and thus reduce hairstyle.
• the actual hair cosmetic problem with fast greasy hair is therefore the premature collapse of voluminous hairstyles.
• 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, teasing (combing against 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 for hair containing polymers of the invention are also according to 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
• anti-dandruff active ingredients that can be incorporated into the shampoo compositions according to the invention, such as, for
• 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 to further improve the skin and mucous membrane compatibility and the care properties are advantageously added, such.
• 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 wash raw material combinations and consistency regulators, which ensure the good spreadability and the spontaneous foaming ability of 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 according to the invention can preferably be used in shampoo formulations, in particular as conditioning agents. Contain preferred shampoo formulations
• cationic polymers with the name Polyqua- Ternium according to INCI, in particular copolymers of vinylpyrrolidone / vinylimidazolium N- (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 salts (Luviquat Hold ®); cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7).
• conditioning agents are, for example, the compounds designated as polyquaternium according to INCI (in particular Polyquaternium-1 to Polyquaternium-87).
• INCI Polyquaternium-1 to Polyquaternium-87.
• Table gives a non-exhaustive overview of conditioners which are used in combination with the polymers according to the invention:
• 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).
• compositions according to the invention which comprise the polymers according to the invention are, for example, soaps and syndets.
• Soap is formed in the reaction of a (neutral) fat or fatty acids or fatty acid methyl esters with sodium or potassium hydroxide solution (saponification) .
• Soap is chemically the alkali salt of fatty acids in the composition.
• the neutral fats are usually beef tallow or palm oil mixed with Coconut oil or palm kernel oil and, less commonly, other natural oils or fats used in soap making, wherein the quality of the starting fats is a major determinant of 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 the fatty acid mixtures mentioned are solid, while the potassium salts are soft and pasty. For this reason, caustic soda is preferably used as the alkaline component for the preparation of solid soaps, and potassium hydroxide solution is preferably used for liquid-pasty soaps. In 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.
• Synthetic detergents are alternatives to the traditional soaps, which have certain advantages due to their different composition from soap, where soap has its drawbacks.
• 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.
• surfactants for Syndets, skin-friendly, readily biodegradable surfactants are used, preferably fatty acid isethionates (sodium cocoyl isethionate), sulfosuccinic acid half esters (disodium 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). Due to the more intensive cleaning / degreasing power of the base surfactants, 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.
• Wash lotions should be referred to "Cosmetics and hygiene from head to toe", ed. W. Limbach, 3rd edition, Wiley-VCH, 2004, pp. 128-134, to which reference is made at this point.
• Another object of the invention is the use of a polymer according to the invention as a thickener in pharmacy for the modification of rheological properties.
• the polymers according to the invention are furthermore 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:
• the polymers according to the invention can be used as gel formers alone or together with further customary gel formers.
• Such other customary gel formers are slightly crosslinked polyacrylic acid, for example carbomer (INCI), cellulose derivatives, eg hydroxypropylcellulose, hydroxyethylcellulose, cationically modified cellulose, polysaccharides, eg xanthum rubber, caprylic / capric triglycerides, sodium acrylate copolymer, polyquaternium.
• Trigonox ® 101 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane

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• 2009
  • 2009-01-28 EP EP09706844A patent/EP2240524A2/de not_active Withdrawn
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