EP1458817A1 - Verfahren zur herstellung von polymerisaten - Google Patents
Verfahren zur herstellung von polymerisatenInfo
- Publication number
- EP1458817A1 EP1458817A1 EP02793049A EP02793049A EP1458817A1 EP 1458817 A1 EP1458817 A1 EP 1458817A1 EP 02793049 A EP02793049 A EP 02793049A EP 02793049 A EP02793049 A EP 02793049A EP 1458817 A1 EP1458817 A1 EP 1458817A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymers
- acid
- weight
- acrylate
- monomers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
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- 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
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
- A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/04—Preparations containing skin colorants, e.g. pigments for lips
- A61Q1/06—Lipsticks
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
- A61Q1/02—Preparations containing skin colorants, e.g. pigments
- A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
Definitions
- Polymers with film-forming properties are used for cosmetic preparations and are particularly suitable as additives for hair and skin cosmetics.
- polymers can have a particular effect.
- the polymers can contribute, among other things, to moisturizing and conditioning the skin and to improving the feeling on the skin.
- the skin becomes smoother and more supple.
- polymers are used to strengthen, improve the structure and shape of the hair. They increase combability and improve the feel of the hair.
- These hair treatment compositions generally contain a solution of the film former in an alcohol or a mixture of alcohol and water.
- hair treatment agents One requirement for hair treatment agents is to give the hair shine, flexibility and a natural, pleasant feel.
- Polysiloxanes are often used, but are incompatible with polar polymers and often require further additives in order to be able to be formulated at all. Demixing can cause problems both during storage of the formulation and during use. In order to prevent segregation, there has been no lack of attempts to covalently bind polysiloxane groups to the polymer.
- EP-A 408 311 describes graft copolymers with a carbon main chain to which polydimethylsiloxane side chains are bound. Only polymers are described which are produced with the aid of unsaturated monomers which carry a polysiloxane chain.
- EP-A 670 342 describes the use of alkoxylated silicones in hair care products.
- the use of polymers of unsaturated compounds in hair care products is not disclosed.
- the use of alkoxylated silicones as an additive to commercially available hair setting polymers improves their grip, but at the same time leads to a reduced setting effect.
- EP-A 412 704 and EP-A 412 707 describe polysiloxane groups in the form of macromonomers with molecular weights from 1000 to 50,000, which are polymerized with conventional hydrophobic and hydrophilic monomers. The synthesis of these monomers is extremely complex. Unreacted macromonomers and their unreactive impurities can hardly be separated from the polymers due to their high molecular weight. They represent a toxicological and allergenic risk. In addition, in order to achieve a good effect, the copolymers obtained can often only be formulated in combination with other polymers, carriers and other auxiliaries, such as the abovementioned. Teach patents.
- WO 99/04750 describes polymers which are obtainable by radical polymerization of ethylenically unsaturated monomers in the presence of silicone derivatives containing polyalkylene oxide.
- WO 99/04750 describes the preparation of polymers with the addition of ethyl hexylthioglycolate (Examples 15 to 20).
- a disadvantage of the polymers obtainable according to WO 99/04750 is above all their strong inherent odor, which in some cases increases when they are stored and / or formulated in cosmetic products. This means that the known products can only be used to a limited extent. Cosmetic formulations attempt to mask this inherent smell of the polymers by using perfume oils. Apart from the fact that the complete coverage of the Odor is not always possible, the use of perfume oils leads to undesirable allergic reactions in individual cases. This limits the use of the known polymers in cosmetic products. In addition, the polymers themselves should be less irritating than the products of the prior art and should therefore be suitable for use in anti-allergenic cosmetic preparations.
- the object of the present invention "has thus been to provide a process for disposal can be obtained in the polymers which are suitable because of their neutral odor for a wide range of applications, in particular in cosmetic compositions and in particular to formulations without the addition of It is of particular interest here that the polymers in cosmetic preparations do not develop their own odor even after storage, and there are also application properties, such as washability from the hair, compatibility with other cosmetic ingredients, in particular solubility in water-containing preparations, handle and setting The provision of polymers which are less irritating than the products of the prior art is also desirable. Another object was to provide polymers which can be used in powder form and are particularly suitable for special decorative cosmetic preparations.
- the task is solved by a method in which one
- the task is solved by a method in which one
- the polymers obtainable in this way are odorless and do not develop any odor even when stored both as individual substances and in cosmetic preparations. At the same time, the polymers obtainable in this way show good film-forming properties and good compatibility with conventional cosmetic ingredients.
- Linear and branched alkane thiols with a C chain length of C 10 to C 22 are used as alkane thiols.
- Linear alkanethiols are particularly preferred, further preferred are alkanethiols with a chain length of C 13 to C 22, in particular C 14 to C 18.
- n-decanethiol, n-dodecanethiol, tert-dodecanethiol, n-tetradecanethiol, n are mentioned Pentadecanethiol, n-hexadecanethiol, n-heptadecanethiol, n-octadecanethiol, n-nonadecanethiol, n-eicosanethiol, n-docosanethiol. Linear, even-numbered alkane thiols are particularly preferred.
- the alkane thiols can also be used in mixtures.
- the alkane thiols are usually used in amounts of 0.1 to 5% by weight, in particular 0.25 to 2% by weight, based on the monomers to be polymerized.
- the alkanethiols are usually added to the polymerization together with the monomers.
- a subsequent hydrogen peroxide treatment is required in order to obtain odorless, neutral polymers.
- 0.01 to 2.0% by weight, in particular 0.02 to 1.0% by weight, particularly preferably 0.03 to 0.15% by weight, of hydrogen peroxide are usually used, in particular 0.1 to 1.0% by weight, based on the monomers to be polymerized. It has proven advantageous to carry out the hydrogen peroxide treatment at a temperature of 20 to 100 ° C., in particular 30 to 80 ° C.
- the hydrogen peroxide treatment is usually between 30 min. and 240 min. , in particular carried out between 45 and 90 min.
- the hydrogen peroxide treatment can be omitted. In a further embodiment of the invention, however, hydrogen peroxide treatment can also be added when alkanethiols with a chain length of C 13 to C 22 are added.
- the polymers are transferred in powder form. All methods known to those skilled in the art are suitable for this, such as spray drying, freeze drying and fluidized bed drying.
- Spray drying is particularly preferred.
- Suitable suitable polymerizable monomers (a) are ethylenically unsaturated monomers. Either single monomers or combinations of two or more monomers can be used.
- Monomers that can be polymerized with a free radical initiated reaction are preferred.
- ethylenically unsaturated means that the monomers have at least one polymerizable carbon-carbon double bond which can be mono-, di-, tri- or tetrasubstituted.
- the ethylenically unsaturated monomers (a) can be described by the following general formula:
- X is selected from the group consisting of -OH, -0M, -OR 8 , NH, -NHR 8 , N (R 8 ) 2 ;
- M is a cation selected from the group consisting of: Na +, K +, Mg ++, Ca ++, Zn ++, NH4 +, alkylammonium, dialkylammonium, trialkylammonium and tetraalkylammonium;
- radicals R 8 can be selected identically or differently from the group consisting of -H, C1-C40 linear or branched-chain alkyl radicals, N, N-dimethylaminoethyl, 2-hydroxyethyl,
- R 7 and R 6 are independently selected from the group consisting of: -H, Ci-Cs linear or branched chain alkyl chains, methoxy, ethoxy, 2-hydroxyethoxy, 2-methoxyethoxy and 2-ethoxyethyl.
- Suitable monomers (a) are, for example, acrylic acid and its salts, esters and amides.
- the salts can be of any non-toxic Metal, ammonium or substituted ammonium counterions can be derived.
- the esters can be derived from C 1 -C 40 linear, C 3 -C 4 o branched, or C 3 -C 4 carbocyclic alcohols, from multifunctional alcohols with 2 to about 8 hydroxyl groups such as ethylene glycol, hexylene glycol, glycerol , and 1, 2, 6-hexanetriol, of amino alcohols or of alcohol ethers such as methoxyethanol and ethoxyethanol or polyethylene glycols.
- N, N-dialkylaminoalkyl acrylates and methacrylates and N-dialkylaminoalkyl acrylates and methacrylamides are also suitable.
- R 9 H, alkyl with 1 to 8 C atoms
- R 11 alkylene with 1 to 24 carbon atoms, optionally substituted by alkyl,
- R 12 , R 13 C 1 -C 40 alkyl radical
- the ide can be unsubstituted, N-alkyl or N-alkylamino monosubstituted, or N, N-dialkyl-substituted or N, N-dialkylamino disubstituted, in which the alkyl or alkylamino groups of C 1 -C 40 linear, C 3 -C 4 o branched chain or C3-C40 carbocyclic units are derived.
- the alkylamino groups can be quaternized.
- Preferred monomers of formula II are N, N-dimethylaminomethyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, N, N-dimethyl-a inoethyl (meth) crylate, N, N-diethylaminoethyl (meth) acrylate.
- Monomers (a) which can also be used are substituted acrylic acids and salts, esters and amides thereof, where the substituents on the carbon atoms are in the two or three positions of acrylic acid and are selected independently of one another from the group consisting of C 1 -C 4 alkyl, -CN, COOH particularly preferably methacrylic acid, ethacrylic acid and 3-cyanoacrylic acid.
- These salts, esters and amides of these substituted acrylic acids can be as above described for the salts, esters and amides of acrylic acid.
- Suitable monomers (a) are vinyl and allyl esters of C 1 -C 40 linear, C 3 -C 4 o branched-chain or C 3 -C 4 o carbocyclic carboxylic acids (for example: vinyl acetate, vinyl propionate, vinyl neonononate, vinyl neoundecanoic acid or t- Vinyl butyl benzoate); Vinyl or allyl halides, preferably vinyl chloride and allyl chloride, vinyl ether, preferably methyl, ethyl, butyl or dodecyl vinyl ether, vinylformamide, vinyl methylacetamide, vinylamine; Vinyl lactams, preferably vinyl pyrrolidone and vinyl caprolactam, vinyl or allyl-substituted heterocyclic compounds, preferably vinyl pyridine, vinyl oxazoline and allyl pyridine.
- N-vinylimidazoles of the general formula III are suitable, in which R 14 to R 15 independently of one another are hydrogen, C 1 -C 4 -alkyl or phenyl:
- R 17 C 1 -C 24 alkyl
- Suitable monomers (a) are vinylidene chloride; and hydrocarbons with at least one carbon-carbon double bond, preferably styrene, alpha-methylstyrene, tert-butylstyrene, butadiene, isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene, isobutylene, vinyltoluene, and mixtures of these monomers.
- Particularly suitable monomers (a) are acrylic acid, methacrylic acid, ethyl acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, Propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, methyl ethacrylate, ethyl ethacrylate, n-butyl ethacrylate, iso-butyl ethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decyl
- vinyl ether for example: methyl, ethyl, butyl or dodecyl vinyl ether
- vinyl formamide vinyl methylacetamide
- vinylamine Methyl vinyl ketone
- maleimide vinyl pyridine
- vinyl imidazole vinyl furan
- styrene styrene sulfonate
- allyl alcohol and mixtures thereof.
- acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, maleic anhydride and its half esters methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, isobutyl acrylate, isobutyl acrylate are particularly preferred acrylate, 2-ethylhexyl acrylate, Nt-butylacrylamide, N-octylacrylamide, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkylene glycol (meth) acrylates, unsaturated sulfonic acids such as, for example, acrylamidopropanesulfonic acid, vinyl ether pyrrol
- Monomers with a basic nitrogen atom can be quaternized in the following way:
- alkyl halides with 1 to 24 carbon atoms in the alkyl group e.g. Methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and benzyl halides, especially benzyl chloride and benzyl bromide.
- Other suitable quaternizing agents are dialkyl sulfates, especially dimethyl sulfate or diethyl sulfate.
- the quaternization of the basic amines can also be carried out with alkylene oxides such as ethylene oxide or propylene oxide in the presence of acids.
- alkylene oxides such as ethylene oxide or propylene oxide
- Preferred quaternizing agents are: methyl chloride, dimethyl sulfate or diethyl sulfate.
- (meth) acrylates are used as monomers (a).
- the quaternization can be carried out before the polymerization or after the polymerization.
- reaction products of unsaturated acids such as acrylic acid or methacrylic acid
- Examples include: (meth) acryloyloxyhydroxy-propyltrimethylammonium chloride and (meth) acryloyloxyhydroxypropyltriethylammonium chloride.
- the basic monomers can also be cationized by reacting with mineral acids such as e.g. Sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid, or with organic acids, e.g. Formic acid, acetic acid, lactic acid, or citric acid can be neutralized.
- mineral acids such as e.g. Sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid or nitric acid
- organic acids e.g. Formic acid, acetic acid, lactic acid, or citric acid can be neutralized.
- macromonomers such as, for example, silicone-containing macromonomers with one or more radical-polymerizable groups or alkyloxazoline macromonomers as described, for example, in EP 408 311 can be used as monomers (a).
- crosslinking compounds or compounds which regulate the molecular weight can be used in combination or alone.
- sulfur compounds e.g. mercaptoethanol, 2-ethylhexylthioglycolate, thioglycolic acid or dodecyl mercaptan
- tribromochloromethane or other compounds which have a regulating effect on the molecular weight of the polymers obtained can be used as regulators.
- silicone compounds containing thiol groups can also be used. Silicone-free controllers are preferably used.
- Crosslinking monomers which can be used are compounds having at least two ethylenically unsaturated double bonds, for example esters of ethylenically unsaturated carboxylic acids, such as acrylic acid or methacrylic acid and polyhydric alcohols, ethers of at least dihydric alcohols, for example vinyl ether or allyl ether. Also suitable are straight-chain or branched, linear or cyclic aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated to the aliphatic hydrocarbons.
- Amides of acrylic and methacrylic acid and N-allylamines of at least divalent amines such as (1, 2-diaminoethane, 1,3-diamino-propane) are also suitable.
- triallylamine or corresponding ammonium salts N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes.
- More suitable Crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane.
- crosslinking agents are, for example, methylene bisacrylamide, triallylamine and triallylammonium salts, divinyl imidazole, N, N'-divinylethylene urea, reaction products of polyhydric alcohols with acrylic acid or methacrylic acid, methacrylic acid esters and acrylic acid esters of polyalkylene oxides or polyhydric alcohols with ethylene oxide and / or propylene / or epichlorohydrin have been implemented.
- the monomers (a) according to the invention can be partially or completely neutralized with acids or bases before or after the polymerization in order, for example, to adjust the water solubility or dispersibility to a desired level.
- mineral bases such as sodium carbonate, alkali hydroxides and ammonia
- organic bases such as amino alcohols, especially 2-amino-2-methyl-1-propanol, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, tri [(2 -hydroxy) 1-propyl] amine, 2-A ino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1, 3-propanediol and diamines such as lysine can be used.
- mineral acids such as hydrochloric acid, sulfuric acid or phosphoric acid
- organic acids such as carboxylic acids, lactic acid, citric acid or others can be used as neutralizing agents for monomers bearing cationizable groups.
- Particularly suitable polyalkylene oxide-containing silicone derivatives (b) are those which contain the following structural elements:
- R 1 can be identical or different and either come from the group of aliphatic hydrocarbons with 1 to 20 carbon atoms, are cyclic aliphatic hydrocarbons with 3 to 20 C atoms, are aromatic in nature or are equal to R 5 , where:
- radicals R 1 , R 2 or R 3 are a radical containing polyalkylene oxide as defined above, and n is an integer from 1 to 6,
- x and y are integers such that the molecular weight of the polysiloxane block is between 300 and 30000,
- a, b can be integers between 0 and 50, with the proviso that the sum of a and b is greater than 0 and C is 0 or 1.
- Preferred radicals R 2 and R 5 are those in which the sum of a + b is between 5 and 30.
- the groups R 1 are preferably selected from the following group: methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, octyl, decyl, dodecyl and octadecyl, cycloaliphatic radicals, especially cyclohexyl, aromatic groups, especially phenyl or naphthyl, mixed aromatic-aliphatic radicals such as benzyl or phenylethyl as well as tolyl and xylyl and R 5 .
- R 1 -CH 3
- R 4 -H; -C0CH 3 , alkyl with C ⁇ -C 4
- n 1 to 6, in particular 2 to 4, preferably 3
- x and y are integers such that the molecular weight of the polysiloxane block is between 1000 and 10,000,
- a, b can be integers between 0 and 50, with the proviso that the sum of a and b is greater than 0.
- silicone derivatives which are available under the trade names Belsil DMC 6032 TM (Wacker) and Dow Coming 190 TM (Dow Chemicals).
- the monomers (a) of the polysiloxane-containing polymers of the present invention can make up from 50 to 99.9% by weight, preferably 70 to 99% by weight, particularly preferably 85 to 98% by weight. If the ethylenically unsaturated monomers (a) are used as a combination of two monomers (al and a2), it has proven advantageous
- the silicone derivatives (b) are generally present in the polymer according to the invention in amounts of 0.1 to 50, preferably 0.5 to 20, particularly preferably 2 to 20 15% by weight.
- a monomer mixture is used
- R 1 -CH 3
- R 4 -H; -C0CH 3 , alkyl with C 1 -C 4
- n 1 to 6, in particular 2 to 4, preferably 3
- 5 x and y are integers such that the molecular weight of the polysiloxane block is between 1000 and 10,000,
- a, b can be integers between 0 and 50 with the proviso that the sum of a and b is greater than O.
- silicone compounds (b) are not present during the polymerization but are mixed in after the polymerization, generally very soft, sticky films are obtained which are suitable for the applications according to the invention in cosmetics for skin and hair
- polymerizable it is meant that the monomers used can be polymerized using any conventional synthetic method.
- this can be solution polymerization, emulsion polymerization, reverse emulsion polymerization, suspension polymerization, reverse suspension polymerization or precipitation polymerization, without the methods which can be used being restricted thereto.
- solution polymerization water, conventional organic solvents or the silicone derivatives according to the invention themselves or mixtures of the solvents mentioned can be used as solvents.
- the polymers according to the invention preferably have a K value (according to Fickentscher, Cellulosechemie, Vol. 13, pp. 58-64 (1932) at 40-25 ° C., measured in 1% by weight ethanolic solution) of 30 to 50, preferably 37 to 41.
- K value accordinging to Fickentscher, Cellulosechemie, Vol. 13, pp. 58-64 (1932) at 40-25 ° C., measured in 1% by weight ethanolic solution
- water-dispersible means polymers which form a fluid in contact with the water within 24 hours and which, without optical aids, does not reveal any solid particles to the eye.
- 100 mg of the polymer in the form of a 100 ⁇ m thick film are placed in 100 ml of water (20 ° C.) and shaken for 24 hours on a commercially available shaking table. If after shaking no more solid particles can be seen, but the fluid is cloudy, the polymer is water-dispersible; without cloudiness it is said to be water soluble.
- polymers such as, for example, homopolymers and copolymers of ethylenically unsaturated monomers, and also polyamides, polyurethanes or polyesters, may also be present in the polymerization of the monomers.
- the polyamides, polyurethanes, polyesters are preferably ionically modified, e.g. with carboxylate or sulfonate groups.
- the polymers are prepared in a customary manner using initiators, such as peroxo or azo compounds, for example dibenzoyl oxide, t-butyl perpivalate, t-butyl per-2-ethylhexanoate, di-t-butyl peroxide, t-butyl hydroperoxide, 2,5- Dimethyl-2, 5-di (t) butylperoxy (hexane), alkali metal or ammonium persulfates, azo-bis-isobutyronitrile, 2, 2 '-azo-bis- (2-methylbutyronitrile), 2, 2' -azo-bis- (2, 4-dimethylvaleronitrile), 1, 1 '-azo-bis- (1-cyclohexanecarbonitrile), 2, 2' -azo-bis- (2-amidino-propane) salts, 4,4'-azo-bis- (4-cyanovaleric acid) or 2- (carbamoylazo) isobutyronitrile etc
- the emulsion polymerization is usually carried out with the exclusion of oxygen at temperatures in the range from 20 to 200.degree.
- the polymerization can be carried out batchwise or continuously.
- the monomers, initiators and alkanethiols are metered uniformly into the reaction vessel during the polymerization.
- the monomers, the alkanethiol and the initiator can, however, also be placed in the reactor and polymerized, with cooling possibly being necessary.
- post-polymerization with the addition of suitable initiators can be carried out in a known manner in order to reduce the residual monomer content.
- physical deodorization can also be carried out in the usual way, for example by introducing water vapor.
- the K value desired in each case can be divided in a manner known per se by choosing the polymerization conditions, for example the polymerization temperature and the initiator concentration. If necessary, especially when using emulsion and suspension polymerization, the use of regulators, in particular sulfur compounds such as mercaptoethanol, 2-ethylhexylthioglycolate, thioglycolic acid or dodecyl mercaptan, can be appropriate to reduce the K value.
- the K values are measured according to Fikentscher, Cellulosechemie, vol. 13, pp. 58 to 64 (1932) at 25 ° C in 1% by weight ethanolic solution and represent a measure of the molecular weight.
- the dispersion obtained can either be incorporated directly into an aqueous, aqueous-alcoholic or alcoholic cosmetic preparation, for example a hair-setting preparation, or drying, e.g. Spray drying, the dispersion, so that the polymer can be used and processed as a powder.
- the invention further relates to polymers obtainable by the process according to claims 1 to 13.
- the polymers obtainable in this way are notable for their low odor, low allergenic potential and, at the same time, good hair cosmetic properties.
- Another object of the invention relates to the use of the polymers according to the invention in particular in powder form in cosmetic preparations, in particular in hair cosmetic preparations.
- hair cosmetic preparations are hair treatments, hair lotions, hair rinses, hair emulsions, tip fluids, leveling agents for perms, hot oil treatment preparations, conditioners, curl relaxers, styling wrap lotions, setting lotions, shampoos, hair waxes, pomades, hair foams, hair colorants or hair sprays. It is particularly preferred to use the acrylate polymers in hairstyle fixers, which are in the form of spray preparations and / or hair foams.
- the polymers according to the invention are notable for their high compatibility with the nonpolar blowing agents in spray preparations, in particular with hydrocarbons such as n-propane, isopropane, n-butane, isobutane, n-pentane and mixtures thereof. They have a good hair-setting effect and are characterized by the fact that they practically do not stick the hair together.
- the polymers In addition to being odorless, the polymers have excellent results in terms of the application properties in hair cosmetic preparations. They are clearly soluble in alcohols such as ethanol or isopropanol and in mixtures of these alcohols with water. The clarity of the solutions is also retained when the solutions are used in standard spray formulations together with blowing agents such as dimethyl ether.
- the hair fixatives according to the invention can be washed out of the hair without any problems. Hair treated with them has increased suppleness and a pleasant natural feel. At the same time, the setting effect is high, so that in principle it is possible to reduce the amount of film former required in the hairspray formulation. Due to the odorlessness of the polymers, there is no need to add odor-covering perfume oils if necessary. For the reasons mentioned, the polymers are particularly suitable as film formers in hair cosmetic preparations.
- wt .-% preferably 20 to 60 wt .-%, in particular 25 to 50 wt .-% of a common organic solvent such as especially ethanol, isopropanol and dirthhoxymethane and also acetone, n-propanol, n-butanol , 2-methoxypropan-l-ol, n-pentane, n-hexane, cyclohexane, n-heptane, n-octane or dichloromethane or mixtures thereof 0 to 90% by weight, preferably 30 to 80% by weight, in particular 45 to 60% by weight, of a conventional blowing agent such as n-propane, iso-propane, n-butane, isobutane, 2,2-dimethylbutane, n -Pentane, isopentane, dimethyl ether, difluoroethane, fluorotrichloromethane
- blowing agents of the compounds mentioned are, above all, the hydrocarbons, in particular propane, n-butane,
- the hair cosmetic preparations according to the invention are also particularly suitable for pump spray preparations without the addition of blowing agents or also for aerosol sprays with conventional compressed gases such as nitrogen, compressed air or carbon dioxide as blowing agents.
- a water-containing standard spray formulation has, for example, the following composition:
- the polymers according to the invention can be present in final preparations as aqueous or aqueous-alcoholic solutions, 0 / W and 35 W / 0 emulsions in the form of shampoos, creams, foams, lotion, mousse, sprays (pump spray or aerosol), gels or gel sprays and, accordingly, with usual additional auxiliaries can be formulated.
- auxiliaries are: surfactants, oil bodies, emulsifiers, co-emulsifiers, superfatting agents, pearlescent waxes, consistency agents, thickeners, fats, waxes, silicone compounds, hydrotropes, preservatives, perfume oils, dyes, stabilizers, pH value regulators, cosmetic care and
- active ingredients such as AHA acids, fruit acids, ceramides, phytantriol, bisabolol, panthenol, collagen, provitamins and vitamins, e.g. vitamins A, E and C, proteins and protein hydrolyzates (e.g. Wheat, almond or pea proteins), solubilizers, complexing agents, repellents, bleaches, colorants, tinting agents, browning agents (for example dihydroxyacetone), micropigments such as titanium dioxide or zinc oxide and the like. Polymers can also be included.
- active ingredients such as AHA acids, fruit acids, ceramides, phytantriol, bisabolol, panthenol, collagen, provitamins and vitamins, e.g. vitamins A, E and C, proteins and protein hydrolyzates (e.g. Wheat, almond or pea proteins), solubilizers, complexing agents, repellents, bleaches, colorants, tinting agents, browning agents (for example dihydroxyacetone), micropigments such as titanium dioxide or zinc oxide and
- Suitable anionic surfactants are, for example, alkyl sulfates, alkyl ether sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl succinates, alkyl sulfosuccinates, N-alkoyl sarcosinates, acyl taurates, acyl isethionates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylates, alpha-olefin alkali metal salts, in particular the alkali metal alkali metal sulfates, in particular the alkali metal alkali metal sulfates, in particular the alkali metal alkali metal sulfonates, in particular the alkali metal alkali metal sulfonates, in particular the alkali metal alkali metal sulfonates, in particular the alkali metal alkali metal sulfonates
- sodium lauryl sulfate, ammonium lauryl sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium lauryl sarcosinate, sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium dodecylbenzenesulfonate, triethanolamine decylbenzene sulfonate are suitable.
- Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines, alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates or propionates, alkylamphodiacetates or dipropionates.
- cocodi ethyl sulfopropyl betaine lauryl betaine, cocamidopropyl betaine or natrium cocamphopropionate can be used.
- Suitable nonionic surfactants are, for example, the reaction products of aliphatic alcohols or alkylphenols with 6 to 20 carbon atoms in the alkyl chain, which can be linear or branched, with ethylene oxide and / or propylene oxide.
- the amount of alkylene oxide is about 6 to 60 moles per mole of alcohol.
- Alkylamine oxides, mono- or dialkylalkanolamides, fatty acid esters of polyethylene glycols, ethoxylated fatty acid amides, alkylpolyglycosides or sorbitan ether esters are also suitable.
- the agents can contain customary cationic surfactants, such as quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
- customary cationic surfactants such as quaternary ammonium compounds, for example cetyltrimethylammonium chloride.
- the agents according to the invention in particular in the form of shampoo formulations, usually contain anionic surfactants as the base side and amphoteric and nonionic surfactants as the side side.
- compositions usually contain 2 to 50% by weight of surfactants, preferably 5 to 40% by weight, particularly preferably 8 to 30% by weight.
- Animal and vegetable oils such as e.g. Sunflower oil, coconut oil, avocado oil, olive oil or lanolin.
- Suitable emulsifiers are nonionic surfactants from at least one of the following groups:
- alkyl mono- and oligoglycosides with 8 to 22 carbon atoms in the alkyl radical and their ethoxylated analogs
- polystyrene resin such as polystyrene resin
- polyglycerol esters such as.
- 12-hydroxystearic acid and glycerin polyglycerin, pentaerythritol, dipentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g. methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose);
- sugar alcohols e.g. sorbitol
- alkyl glucosides e.g. methyl glucoside, butyl glucoside, lauryl glucoside
- polyglucosides e.g. cellulose
- adducts of ethylene oxide and / or of propylene oxide with fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters and sorbitan mono- and diesters of fatty acids or with castor oil are known, commercially available products. These are mixtures of homologs, the middle of which
- Ci 2 / i 8 fatty acid monoesters and diesters of adducts of ethylene oxide with glycerol are known from DE-PS 2024051 as refatting agents for cosmetic preparations.
- Cs / is alkyl mono- and oligoglycosides, their preparation and their use are known from the prior art. They are produced in particular by reacting glucose or oligosaccharides with primary alcohols with 8 to 18 carbon atoms.
- both monoglycosides in which a cyclic sugar residue is glycosidically bonded to the fatty alcohol and oligomeric glycosides with a degree of oligomerization of up to preferably about 8 are suitable.
- the degree of oligomerization is a statistical mean value which is based on a homolog distribution customary for such technical products.
- Zwitterionic surfactants can also be used as emulsifiers.
- Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
- Particularly suitable zwitterionic surfactants are the so-called betaines such as the N-alkyl-N, N-dimethylammonium glycinate, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinate, for example coconut acylaminopropyl dimethylammonium glycinate, and 2-alkyl-3 carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group and the cocoacylaminoethylhydroxyethyl carboxymethylglycinate.
- the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred.
- Suitable emulsifiers are also ampholytic
- Ampholytic surfactants are surface-active compounds which, in addition to a Cs / is alkyl or acyl group, contain at least one free amino group and at least one -C00H or -S0 3 H group in the molecule and are capable of forming internal salts.
- ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkyl sarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid each with about 8 to 18 carbon atoms in the alkyl group.
- Particularly preferred ampholytic surfactants are N-cocoalkylamino propionate, cocoacylaminoethylaminopropionate and Cat 2 / i 8 acyl sarcosine.
- quaternary emulsifiers are also suitable, those of the esterquat type, preferably methylquaternized difatty acid triethanolamine ester salts, being particularly preferred.
- Substances such as, for example, lanolin and lecithin and polyethoxylated or acylated lanolin and lecithin derivatives, polyol fatty acid esters, monoglycerides and fatty acid alkanolamides can be used as superfatting agents, the latter simultaneously serving as foam stabilizers.
- Pearlescent waxes for example, are: alkylene glycol esters, special ethylene glycol masterate; Fatty acid alkanolamides, especially coconut fatty acid diethanoamide; Partial glycerides, especially stearic acid monoglyceride; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms, especially long-chain esters of tartaric acid; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which have a total of at least 24 carbon atoms, especially lauron and distearyl ether; Fatty acids such as stearic acid, hydroxystearic acid or behenic acid, ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms and / or polyols with 2 to 15 carbon atoms and
- the main consistency factors are fatty alcohols or
- Hydroxy fatty alcohols with 12 to 22 and preferably 16 to
- Suitable thickeners are, for example, polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, cellulose derivatives, e.g. Carboxymethyl cellulose and hydroxyethyl cellulose, as well as higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates (e.g.
- surfactants such as ethoxylated fatty acid glycerides, esters of fatty acids with polyols such as, for example, pentaethylene Trimethylolpropane, fatty alcohol ethoxylates with a narrow homolog distribution or alkyl oligoglucosides as well as electrolytes such as table salt and ammonium chloride.
- Typical examples of fats are glycerides; beeswax, carnauba wax, candelilla wax, montan wax, paraffin wax or microwaxes are suitable waxes, if appropriate in combination with hydrophilic waxes, for example cetylstearyl alcohol or partial glycerides.
- Metal salts of Fatty acids such as magnesium, aluminum and / or zinc stearate or ricinoleate can be used.
- Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds, which can be both liquid and resinous at room temperature.
- Typical examples of fats are glycerides, waxes include Beeswax, carnauba wax, candelilla wax, montan wax, paraffin wax or micro waxes, optionally in combination with hydrophilic waxes, e.g. Cetylstearyl alcohol or partial glycerides in question.
- Metal salts of fatty acids such as e.g. Magnesium, aluminum and / or zinc stearate can be used.
- Suitable solvents are in particular water and lower monoalcohols or polyols with 1 to 6 carbon atoms and mixtures thereof; preferred monoalcohols or polyols are ethanol, i-propanol, propylene glycol, glycerin and sorbitol.
- Hydrotropes such as ethanol, isopropyl alcohol or polyols can also be used to improve the flow behavior.
- Polyols that come into consideration here preferably have 2 to 15 carbon atoms and at least two hydroxyl groups. Typical examples are
- Alkylene glycols such as, for example, ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexylene glycol and polyethylene glycols with an average molecular weight of 100 to 1000 daltons; technical oligoglycerol mixtures with a degree of self-condensation of 1.5 to 10 such as technical diglycerol mixtures with a diglycerol content of 40 to 50% by weight;
- Methyl compounds such as in particular trimethylolethane, trimethylolpropane, trimethylolbutane, pentaerythritol and dipentaerythritol;
- Lower alkyl glucosides especially those with 1 to 8 carbons in the alkyl radical, such as methyl and butyl glucoside;
- Sugar alcohols having 5 to 12 carbon atoms such as, for example, sorbitol or mannitol;
- Sugars with 5 to 12 carbon atoms such as glucose or sucrose
- Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid and the other classes of substances listed in Appendix 6, Parts A and B, of the Cosmetics Ordinance.
- Triclosan 2, 4, 4'-trichloro-2 'hydroxydiphenyl ether
- chlorhexidine 1,1' -hexamethylene bis [5- (4-chlorophenyl) biguanide
- TTC 3,4,4 'trichlorocarbanilide
- Quaternary ammonium compounds are also suitable in principle, but are preferably used for disinfectant soaps and washing lotions.
- Numerous fragrances also have antimicrobial properties.
- Special combinations with particular effectiveness against gram-positive bacteria are used for the composition of so-called deodorants.
- a large number of essential oils and their characteristic ingredients such as Clove oil (eugenol), mint oil (menthol) or thyme oil (thymol) have a pronounced antimicrobial effect.
- the preservatives are usually used in concentrations of approximately 0.1 to 0.3% by weight.
- Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, cumin, juniper), fruit peel (bergamot, lemon, Oranges), roots (mace, angelica, celery, cardamom, costus, iris, calmus), wood (pine, sandal, guaiac,
- Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
- Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexylpropylyl allyl pentyl propionate.
- the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyelamenaldehyde, hydroxycitronellal, lilial and bourgeonate, the ketones, for example, the jonones, cc-isomethyl ions and methyl cedryl ketone Alcohols Anethof, Citronellol, Eugenol, Isoeugenol, Geraniol, Linalool, Phenylethylalkohol and Terioneol, the hydrocarbons mainly include the terpenes and balms.
- fragrance oils of lower volatility which are mostly used as aroma components, are also suitable as perfume oils, for example sage oil, kale oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden flower oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavolanum oil and lavolanum oil.
- the dyes which can be used are the substances which are suitable and approved for cosmetic purposes, as compiled, for example, in the publication "Cosmetic Dyes” by the Dye Commission of the German Research Foundation, Verlag Chemie, Weinheim, 1984, pp. 81-106. These dyes are usually used in concentrations of 0.001 to 0.1% by weight, based on the mixture as a whole.
- the polymers according to the invention may be advantageous to use as a mixture with other hair-fixing polymers.
- anionic, cationic, amphoteric and neutral polymers are suitable as other polymers.
- anionic polymers are homopolymers and copolymers of acrylic acid and methacrylic acid or their salts, homopolymers and copolymers of acrylic acid and acrylamide and their salts, sodium salts of polyhydroxycarboxylic acids, water-soluble or water-dispersible polyesters, polyurethanes (for example Luviset® PUR) and polyureas.
- Particularly suitable polymers are copolymers of tert. -Butyl acrylate, ethyl acrylate, methacrylic acid (e.g. Luvimer® 100 P), copolymers of ethyl acrylate and methacrylic acid (e.g.
- Luviflex® Soft copolymers of N-tert-butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold Strong®), copolymers of vinyl acetate , Crotonic acid and possibly other vinyl esters (eg Luviset CA66®), maleic anhydride copolymers, optionally reacted with alcohols, anionic polysiloxanes, for example carboxy-functional copolymers of vinylpyrrolidone, tert. -Butyl acrylate, methacrylic acid (e.g. Luviskol® VBM), terpolymers made from tert-butyl acrylate, methacrylic acid and dimethicone copolyol (e.g. Luviflex Silk).
- methacrylic acid e.g. Luviskol® VBM
- terpolymers made from tert-butyl acrylate, methacrylic acid and dimethicone copolyol e.g. Luviflex
- Copolymers of acrylic acid and methacrylic acid with hydrophobic monomers including C 4 -C 3 O-alkyl esters of (meth) acrylic acid, C 4 -C 3 O-alkyl vinylester, C 4 -C 3 O-alkyl vinyl ether and hyaluronic acid and further under the Tradenames known polymers Amerhold DR-25, Ul- trahold, Luviset® PUR, Acronal®, Acudyne®, Lovocryl®, Versatyl®, Amphomer® (28-4910, LV-71), Placise® L53, Gantrez® ES 425, Advantage Plus®, Omnirez® 2000, Resyn® 28-1310, Resyn® 28-2930, Balance® (0/55), Acudyne® 255, Aristoflex®A or Eastman AQ®.
- Polysilicone-7 and Polysilicone-8 are the polymers available under the INCI designation Polysilicone-7 and Polysilicone-8 (Plus TM SA70, Plus TM VS70).
- Designation polyquaternium e.g. Copolymers from vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care), copolymers from N-vinylpyrrolidone / diethylaminoethyl methacrylate, quaternized with diethyl sulfate (Luviquat® PQ N-), copolymers Vinylcaprolactam / N-vinylpyrrolidone / N-vinylimidazolium salts (Luviquat® Hold), cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-), Styleeze TM CC-10, Aquaflex® SF-40 and chitosan derivatives.
- Copolymers from vinylpyrrolidone / N-vinylimidazolium salts (L
- Neutral polymers are also suitable as further polymers, such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and / or vinyl propionate, polysiloxanes, polyvinylcapro-lacta and copolymers with N-vinylpyrrolidone, polyethyleneimines and their salts, polyvinylamines and their salts, cellulose derivatives, polyaspartic derivatives and derivatives.
- These include the polymer Luviskol® (K, VA, Plus), PVP K, PVP / VA, Advantage® HC and H 2 0LD EP-1 known under the following trade names.
- biopolymers ie polymers which are obtained from naturally renewable raw materials and which are built up from natural monomer building blocks, for example cellulose derivatives, chitin, chitosan, DNA, hyaluronic acid and RNA derivatives.
- Other polymers include betaine polymers such as Yukaformer (R205, SM) and Diaformer.
- the total proportion of auxiliaries and additives can be 1 to 50, preferably 5 to 40,% by weight, based on the composition.
- the auxiliaries can be present during the polymerization and / or can be added after the polymerization.
- the polymers are particularly suitable for use in cosmetic products.
- they can be used in cosmetic products for cleaning the skin.
- Such cosmetic cleaning agents are selected from bar soaps, such as toilet soaps, core soaps, transparent soaps, luxury soaps, deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, liquid soaps such as pasty soaps, soft soaps and washing pastes, and liquid washing, showering, and bath preparations, such as washing lotions, shower baths and gels, foam baths, oil baths and scrub preparations, shaving foams, lotions, creams.
- the preparations according to the invention can also be used in cosmetic preparations for skin care.
- the skin care products are in particular available as W / O or O / W skin creams, day and night creams, eye creams, face creams, anti-wrinkle creams, moisturizing creams, bleaching creams, vitamin creams, skin lotions, care lotions and moisturizing lotions. They are also suitable for skin cosmetic preparations such as facial tonic, face masks, deodorants and other cosmetic lotions.
- polymers according to the invention can be used as strips for pore cleaning or skin tightening, in anti-acne agents, repellents, shaving agents, hair removal agents, intimate hygiene products, foot care products and in baby care.
- polymers in preparations of decorative cosmetics in particular the polymers in powder form, is very particularly preferred.
- a polymer which is obtainable by free-radical polymerization of a monomer mixture according to claim 1 and / or 2 from is particularly suitable for cosmetic preparations
- R 1 -CH 3
- R 4 -H; -C0CH 3 , alkyl with C ⁇ ⁇ C 4
- n 1 to 6, in particular 2 to 4, preferably 3
- x and y are integers such that the molecular weight of the polysiloxane block is between 1000 and 10,000, a, b can be integers between 0 and 50, with the proviso that the sum of a and b is greater than 0.
- Preparations for decorative cosmetics include, for example, concealers, theater paint, mascara and eyeshadow, lipsticks, kohl pencils, eyeliner, makeup, foundations, blushes and powders and eyebrow pencils, and in particular nail polishes.
- the polymers are usually present in the cosmetic preparations in an amount in the range from about 0.001 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the preparations.
- Feed 1 789 g tert-butyl acrylate 261 g methacrylic acid 540 g water 63 g Disponil FES77 4.53 g n-tetradecylthiol.
- Example 2 The preparation according to Example 2 is carried out according to Example 1, instead of n-tetradecylthiol, n-eicosylthiol was used.
- a solution was prepared from 1290 g of water, 6.9 g of Disponol FES77 and 126 g of dimethicone copolyol (Belsil DMC6031) and 113 g of feed 1 and this was heated to 80.degree. Then 24 g of a 7% aqueous sodium persulfate solution were added. Feed 1 was metered in over 2 hours. After another 2 hours and Cooling to 65 ° C., 5.4 g of hydrogen peroxide (30% aqueous solution) were added. After steam distillation, the mixture was cooled to 60 ° C. and 108 g of potassium hydrogen carbonate solution (10% strength) were metered in.
- Example 4 was prepared according to Example 3, n-eicosylthiol was used instead of the n-tetradecylthiol.
- Example 5 was prepared according to Example 3, instead of n-tetradecylthiol, n-decylthiol was used.
- Example 6 was prepared according to Example 3, instead of n-tetradecylthiol, n-dodecylthiol was used.
- Example 8 was prepared according to Example 7, instead of n-tetradecylthiol, n-eicosylthiol was used. Comparative example
- the comparative example was prepared as in Example 7, but ethyl hexylthioglycolate was used instead of n-tetradecylthiol.
- the dispersions prepared according to Examples 1 to 8 and Comparative Example were converted into powder form by means of spray drying.
- the polymers prepared according to the examples were dried, dissolved in 30% ethanolic solution and then formulated as a 3% aqueous solution and 100% neutralized with 2-amino-2-methylpropanol.
- they were dissolved in 30% ethanolic solution and then formulated and neutralized as a 3% aqueous solution.
- the evaluation of the olfactory properties is based on the following classification: w l "no smell” 2 "weak, unpleasant smell” 3 "strong, unpleasant smell.
- Powders and dispersions were evaluated in terms of odor as follows, grade 1: V3, V4, V6 (each dispersion and powder) grade 2: VI, V2, V5, V7 and V8 (each dispersion and powder) grade 3: comparative example (dispersion and powder) ,
- Phase B 0.50% powder according to V1-V8
- Vitamin E acetate tocopheryl acetate 0.87 d, 1-alpha-tocopherol tocopherol 0.58
Abstract
Description
Claims
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DE10163523A DE10163523A1 (de) | 2001-12-21 | 2001-12-21 | Verfahren zur Herstellung von Polymerisaten |
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PCT/EP2002/014397 WO2003054088A1 (de) | 2001-12-21 | 2002-12-17 | Verfahren zur herstellung von polymerisaten |
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EP1603960A2 (de) * | 2003-03-07 | 2005-12-14 | Basf Aktiengesellschaft | Polymere produkte |
FR2915388B1 (fr) * | 2007-04-27 | 2010-12-24 | Oreal | Film hydrosoluble cosmetique |
AU2010333833B2 (en) * | 2009-12-23 | 2014-08-21 | Trinseo Europe Gmbh | Method for the preparation of low odour copolymer latexes |
FR3075631B1 (fr) | 2017-12-21 | 2020-04-03 | Lvmh Recherche | Composition de mascara contenant un ester de tetrahydroxypropylethylene diamine |
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DE4414465C1 (de) * | 1994-04-26 | 1995-05-11 | Goldschmidt Ag Th | Polymethacrylsäureester-Polysiloxan-Blockmischpolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung als Modifizierungsmittel und als Lackadditive |
DE59814329D1 (de) * | 1997-07-23 | 2009-02-05 | Basf Se | Verwendung von polysiloxanhaltigen polymeren für kosmetische formulierungen |
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